Patent Description:
Hydrosilylation reaction which is addition reaction of a Si-H functional compound to a compound having a carbon-carbon double bond or triple bond is a useful means for the synthesis of organosilicon compounds and an industrially important synthesis reaction.

As the catalyst for hydrosilylation reaction, Pt, Pd and Rh compounds are known. Among others, Pt compounds as typified by Speier catalyst and Karstedt catalyst are most commonly used.

While several problems arise with reaction in the presence of Pt compounds as the catalyst, one problem is that upon addition of a Si-H functional compound to terminal olefin, a side reaction due to internal rearrangement of olefin takes place. Since this system does not exert addition reactivity to the internal olefin, unreacted olefin is left in the addition product. To drive the reaction to completion, it is necessary to use an excess amount of olefin in advance by taking into account the fraction left as a result of side reaction.

Another problem is that the selectivity of α- and β-adducts is low depending on the type of olefin.

The most serious problem is that all the center metals Pt, Pd and Rh are quite expensive noble metal elements. As metal compound catalysts which can be used at lower cost are desired, a number of research works have been made thereon.

With regard to hydrosilylation reaction in the presence of iron complex catalysts, for example, reaction in the presence of iron-carbonyl complexes (Fe(CO)<NUM>, Fe<NUM>(CO)<NUM>) is known from Non-Patent Document <NUM>, although this reaction requires reaction conditions including as high a temperature as <NUM> or light irradiation (Non-Patent Document <NUM>).

For these iron-carbonyl complexes, it is reported in Non-Patent Document <NUM> and Patent Document <NUM> that dehydrogenation silylated products are obtained rather than the addition reaction.

Also Non-Patent Document <NUM> and Patent Document <NUM> report a reaction of methylvinyldisiloxane and methylhydrogendisiloxane in the presence of an iron-carbonyl complex coordinated with a cyclopentadienyl group. Since dehydrogenation silylation reaction takes place along with the relevant reaction, the selectivity of addition reaction is low.

With respect to reaction in the presence of an iron catalyst having a terpyridine ligand (Non-Patent Document <NUM>), a large excess of a reducing agent (NaBHEt<NUM>) is necessary as a reaction co-agent. Although PhSiH<NUM> and Ph<NUM>SiH<NUM> add to olefins, more useful trialkylsilanes, alkoxysilanes and siloxanes have poor addition reactivity to olefins.

Non-Patent Document <NUM> reports that from reaction in the presence of an iron catalyst having a terpyridine ligand and a bistrimethylsilylmethyl group, an addition reaction product is obtained in high yields. This method needs some steps until the catalyst is synthesized, including first synthesizing a terpyridine-iron complex as a catalyst precursor and introducing a bistrimethylsilylmethyl group therein at a low temperature, which steps are not easy industrially.

Also, Non-Patent Documents <NUM> and <NUM> report iron complexes having a bisiminopyridine ligand. It is disclosed that they exhibit high reactivity to alkoxysilanes and siloxanes under mild conditions.

The reaction using the complex, however, suffers from several problems including low reactivity with internal olefin, the use of sodium amalgam consisting of water-prohibitive sodium and highly toxic mercury and requiring careful handling (or use of water-prohibitive NaBEtsH) for complex synthesis, low stability of the complex compound itself, a need for a special equipment like a glove box for handling, and a need for storage in an inert gas atmosphere such as nitrogen at low temperature.

Non-Patent Documents <NUM> to <NUM> report examples of reaction in the presence of cobalt-carbonyl complexes (e.g., Co<NUM>(CO)<NUM>), but they are unsatisfactory in reaction yield and reaction molar ratio. No reference is made to addition reactivity to siloxanes.

Also an example of reaction of olefin with trialkylsilane in the presence of a cobalt-carbonyl complex substituted with a trialkylsilyl group is reported in Non-Patent Document <NUM>, but the yield is low and the selectivity is low.

Non-Patent Document <NUM> reports reaction of olefin with trialkylsilane in the presence of a cobalt-phosphite complex coordinated with a cyclopentadienyl group, and Non-Patent Document <NUM> reports reaction of olefin with trihydrophenylsilane in the presence of a cobalt complex coordinated with N-heterocyclocarbene. Because of low stability, these complex compounds require a special equipment like a glove box for handling and an inert gas atmosphere and a low temperature for storage.

Also Patent Documents <NUM> to <NUM> report iron, cobalt and nickel catalysts having terpyridine, bisiminopyridine and bisiminoquinoline ligands. Like the above-cited Non-Patent Documents <NUM> to <NUM>, there are problems including industrial difficulty of synthesis of a catalyst precursor or synthesis of the complex catalyst from the precursor, low stability of the complex compound itself, and a need for a special equipment for handling.

Patent Document <NUM> discloses a method of conducting reaction in the presence of a complex catalyst having a bisiminoquinoline ligand, using Mg(butadiene) ·2THF or NaEtsBH as the catalyst activator. There are the same problems as above and the yield of the desired product is less than satisfactory.

Many examples of the nickel complex catalyst are reported. For example, a catalyst having a phosphine ligand (Non-Patent Document <NUM>) lacks in selectivity and requires careful handling and storage.

With a vinylsiloxane-coordinated catalyst (Non-Patent Document <NUM>), a dehydrogenation silylated product becomes predominant, indicating low selectivity of addition reaction.

With an allylphosphine-coordinated catalyst (Non-Patent Document <NUM>), the yield is low, and trihydrophenylsilane is not a substrate of industrial worth.

A bisamide-bearing catalyst (Non-Patent Document <NUM>) needs careful handling and storage, and dihydrodiphenylsilane is not a substrate of industrial worth.

A catalyst having N-heterocyclocarbene ligand (Non-Patent Document <NUM>) has low selectivity of reaction, and trihydrophenylsilane is not of industrial worth.

Many rhodium complex catalysts are reported. For example, catalysts having a carbonyl or cyclooctadienyl (COD) group and a N-heterocarbene ligand (Non-Patent Documents <NUM>, <NUM>) are low in stability of complex compound.

Non-Patent Document <NUM> discloses to conduct reaction in the presence of an ionic liquid in order to enhance reactivity. The step of separating the ionic liquid from the reaction product is necessary. Since the catalyst used therein has a COD group and a N-heterocarbene group as the ligand, the same problems as described above are left.

Also Non-Patent Document <NUM> reports an exemplary catalyst which allows for preferential progress of dehydrogenation silylation reaction.

Furthermore, Non-Patent Document <NUM> reports an example in which a carbene compound is added to a complex catalyst to form a catalyst, which is used in hydrosilylation reaction without isolation. A study on reactivity with three types of silanes shows that the order of reactivity is from dimethylphenylsilane, which gives the highest yield (yield <NUM>%), next triethylsilane (yield <NUM>%), to triethoxysilane (yield <NUM>%). The reactivity with triethoxysilane which is of the most industrial worth among the three types of silanes is not so high, while the reactivity with siloxanes is reported nowhere.

In addition, the precursor catalyst having a COD group as the ligand requires careful handling and storage.

On the other hand, Non-Patent Document <NUM> reports that a rhodium catalyst having an acetylacetonato or acetate group enables addition reaction of triethoxysilane in high yields.

Although this method has the advantage of easy storage and handling of the catalyst, no study is made on reactivity with siloxanes which are more useful from the industrial standpoint.

In addition, rhodium is likewise an expensive noble metal element. Its catalytic function must be further increased to a higher activity before it can be used in practice as a platinum replacement.

The catalysts with their application to organopolysiloxanes being borne in mind include a catalyst having a phosphine ligand (Patent Document <NUM>), a catalyst having an aryl-alkyl-triazenide group (Patent Document <NUM>), a colloidal catalyst (Patent Document <NUM>), a catalyst coordinated with a sulfide group (Patent Document <NUM>), and a catalyst coordinated with an amino, phosphino or sulfide group and an organosiloxane group (Patent Document <NUM>).

However, reactivity is empirically demonstrated with respect to only platinum, palladium, rhodium and iridium which are expensive metal elements. Thus the method is not regarded cost effective.

In Examples of Patent Documents <NUM> and <NUM>, only well-known platinum catalysts are demonstrated to exert a catalytic effect while the structure which is combined with another metal to exert catalytic activity is indicated nowhere.

Patent Documents <NUM> to <NUM> disclose catalysts coordinated with carbene. Patent Document <NUM> does not discuss whether or not the catalyst is effective to hydrosilylation reaction.

Patent Documents <NUM> and <NUM> disclose catalysts coordinated with carbene and vinylsiloxane, but describe only platinum catalysts in Examples.

In addition, the metal catalysts coordinated with carbene require careful handling because the complex compounds have low storage stability.

Likewise, as an example of the catalyst coordinated with carbene, Patent Documents <NUM> and <NUM> disclose only platinum catalysts.

Also Patent Document <NUM> discloses a metal-carbene complex catalyst obtained from reaction of a Ni-carbene complex with a metal precursor. However, the Ni-carbene complex must be separately synthesized. The metal precursor to be reacted is a metal compound having a ligand such as phosphine or COD. The metal precursor having such a ligand is low in storage stability.

Patent Documents <NUM> and <NUM> disclose complex catalysts obtained by reacting Pd, Pt and Ni complexes having olefinic ligands with carbene. However, the metal complexes having olefinic ligands except well-known Pt catalysts having vinylsiloxane ligands are low in storage stability.

Patent Document <NUM> discloses a Co-carbene complex, which is active to hydrosilylation reaction on ketones.

Patent Documents <NUM> and <NUM> disclose the application of a metal-carbene complex to curing reaction of organopolysiloxane. Only Pt is referred to as the metal. The synthesis method is reaction of a well-known Pt complex having vinylsiloxane ligand with carbene.

Patent Documents <NUM> and <NUM> disclose ruthenium catalysts coordinated with η<NUM>-arene or η<NUM>-triene. These catalysts have inferior reactivity to platinum catalysts and require careful handling because the complex compounds have low storage stability.

Patent Documents <NUM> to <NUM> disclose a method of mixing a metal salt with a compound which coordinates to the metal and using the product as a catalyst rather than the use of metal complexes as the catalyst. Although these Patent Documents describe the progress of hydrosilylation with several exemplary combinations, the yield and other data are described nowhere, and the extent to which the reaction takes place is not evident.

For example, Patent Documents <NUM> and <NUM> describe Examples in which compounds corresponding to carbene are added to halides or trimethylsilylamide salts of Co or Fe. These catalysts are regarded as having reactivity to only phenyltrihydrosilane, but not having reactivity to heptamethyltrisiloxane.

Likewise, Patent Document <NUM> discloses exemplary Ni compounds and carbene compounds. Only one example is regarded as having activity to addition reaction of heptamethyltrisiloxane, whereas some other examples have activity to only phenyltrihydrosilane, and many other examples have activity to neither phenyltrihydrosilane nor heptamethyltrisiloxane.

Patent Documents <NUM> and <NUM> disclose exemplary Ir or Ru compounds and carbene compounds. Of these, only metal compounds having a COD or η<NUM>-aryl group as an olefinic ligand exhibit reactivity.

In all examples described in Patent Documents <NUM> to <NUM>, ionic salts or hydride reducing agents are used as the activator. Nevertheless, almost all examples exhibit no catalytic activity.

An object of the invention, which has been made under the above-mentioned circumstances, is to provide a hydrosilylation iron catalyst which uses iron, i.e., the most inexpensive element among transition metals, is easy to synthesize, and helps hydrosilylation reaction take place under mild conditions; and a method for preparing an addition compound by hydrosilylation reaction using the same.

Making extensive investigations to attain the above objects, the inventors have found that a catalyst which is obtained using a specific iron complex as the catalyst precursor and a two-electron ligand exerts a high activity to hydrosilylation reaction and helps addition reaction take place under mild conditions. The invention is predicated on this finding.

The invention provides a catalyst and a method as defined in the claims.

The iron complex compound from which the hydrosilylation iron catalyst of the invention is prepared is readily available since it may be synthesized by a well-known method.

The iron complex compound has no catalytic activity for hydrosilylation when used alone, but exhibits catalytic activity when combined with a two-electron ligand.

In order to use an inert iron complex to generate a reactive species, a reducing agent is often necessary. According to the invention, the desired addition reaction by hydrosilylation takes place without a need to separately add a reducing agent because the reactant, hydrosilane itself is utilized as the reducing agent.

The catalyst prepared from the iron complex as precursor and the two-electron ligand may be used after isolation from a catalyst preparation or it may be prepared in situ in a hydrosilylation reaction system and used without isolation.

If hydrosilylation reaction between a compound containing an aliphatic unsaturated group and a silane having a Si-H group or polysiloxane is carried out in the presence of the catalyst prepared from the iron complex as precursor and the two-electron ligand, addition reaction is possible under such conditions as room temperature to <NUM>. In particular, addition reaction with industrially useful polysiloxanes, trialkoxysilanes and dialkoxysilanes takes place effectively.

Although the cited documents describe that in the relevant reaction using an iron complex, addition reaction to an unsaturated group and reaction to produce an unsaturated group-containing compound by dehydrogenation silylation reaction often take place at the same time, and dehydrogenation silylation reaction takes place preferentially, the use of the inventive catalyst ensures selective progress of addition reaction to an unsaturated group. The invention is thus quite useful in the silicone industry.

Below the invention is described in more detail.

The invention provides a hydrosilylation iron catalyst which is a mono-, bi- or tri-nuclear complex of iron having the formula (<NUM>) as a catalyst precursor combined with a two-electron ligand (L) :.

wherein Fe has bonds solely with carbon atoms in X, and the total number of Fe-carbon bonds is <NUM> to <NUM>.

In formula (<NUM>), X is each independently a C<NUM>-C<NUM> ligand, exclusive of cyclopentadienyl groups, selected from aryl groups, aralkyl groups, cyclic or acyclic olefins, cyclic or acyclic olefinyl groups, which may be substituted with a halogen atom, alkoxy group or haloalkyl.

The subscript "a" is an integer of <NUM> to <NUM> per Fe atom, preferably <NUM>.

The alkyl groups may be straight, branched or cyclic, preferably C<NUM>-C<NUM>, more preferably C<NUM>-C<NUM> alkyl groups. Examples include straight or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-eicosanyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, norbornyl, and adamantyl.

The aryl groups are preferably C<NUM>-C<NUM>, more preferably C<NUM>-C<NUM> aryl groups. Examples include phenyl, <NUM>-naphthyl, <NUM>-naphthyl, anthryl, phenanthryl, o-biphenylyl, m-biphenylyl, and p-biphenylyl.

The aralkyl groups are preferably C<NUM>-C<NUM>, more preferably C<NUM>-C<NUM> aralkyl groups. Examples include benzyl, phenylethyl, phenylpropyl, naphthylmethyl, naphthylethyl, and naphthylpropyl.

Exemplary cyclic olefins include cyclic monoolefins such as cyclobutane, cyclopentene, methylcyclopentene, dimethylcyclopentene, cyclohexene, methylcyclohexene, dimethylcyclohexene, trimethylcyclohexene, tetramethylcyclohexene, cyclooctene, methylcyclooctene, dimethylcyclooctene, tetramethylcyclooctene, cyclodecene, cyclododecene and norbornene; and cyclic polyenes having at least two unsaturated groups in the molecule such as cyclobutadiene, cyclohexadiene, cyclooctadiene, cyclooctatriene, cyclooctatetraene, cyclodecadiene, cyclodecatriene, cyclodecatetraene, and norbornadiene.

Exemplary acyclic olefins include acyclic (chainlike) monoolefins such as ethylene, propylene, butene, isobutene, pentene, hexene, octene, decene and undecene; and acyclic (chainlike) polyenes having at least two unsaturated groups in the molecule such as butadiene, <NUM>-methylbutadiene, pentadiene, methylpentadiene, dimethylpentadiene, hexadiene, hexatriene, octadiene, octatriene, octatetraene, decadiene, decatriene, and decatetraene.

Exemplary cyclic olefinyl groups include monoolefinyl groups such as cyclobutenyl, cyclopentenyl, methylcyclopentenyl, dimethylcyclopentenyl, cyclohexenyl, methylcyclohexenyl, dimethylcyclohexenyl, trimethylcyclohexenyl, tetramethylcyclohexenyl, cyclooctenyl, methylcyclooctenyl, dimethylcyclooctenyl, tetramethylcyclooctenyl, cyclodecenyl, and norbornyl; and cyclic polyenyl groups having at least two unsaturated groups in the molecule such as cyclobutadienyl, cyclohexadienyl, cyclooctadienyl, cyclooctatrienyl, cyclooctatetraenyl, cyclodecadienyl, cyclodecatrienyl, cyclodecatetraenyl, and norbornadienyl, exclusive of cyclopentadienyl.

Exemplary acyclic olefinyl groups include acyclic (chainlike) monoolefinyl groups such as vinyl, allyl, methallyl, butenyl, isobutenyl, pentenyl, hexenyl, octenyl, and decenyl; and acyclic (chainlike) polyenyl groups having at least two unsaturated groups in the molecule such as butadienyl, methylbutadienyl, dimethylbutadienyl, pentadienyl, methylpentadienyl, dimethylpentadienyl, hexadienyl, hexatrienyl, octadienyl, octatrienyl, octatetraenyl, decadienyl, decatrienyl, and decatetraenyl.

Each of the foregoing ligands may be partially substituted with a halogen atom selected from fluorine, chlorine, bromine and iodine; alkoxy group such as methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, octyloxy, or decyloxy; or haloalkyl group such as trifluoromethyl, pentafluoroethyl, trifluoropropyl, nonafluorobutyl, trichloromethyl or trichloropropyl.

The bonds between Fe and carbon atoms in ligands X may be solely covalent bonds, solely coordinate bonds, or both.

Inter alia, the preferred iron complex is a binuclear complex in which ligand X is an aryl group and the total number of bonds of Fe with carbon atoms in ligands X is <NUM>.

Also preferred are mononuclear complexes in which the total number of bonds of Fe with carbon atoms in ligands X is <NUM> to <NUM>, more preferably <NUM>.

Herein, ligand X is preferably selected from among cyclic olefin, acyclic olefin, cyclic olefinyl and acyclic olefinyl groups having <NUM> to <NUM> unsaturated bonds in the molecule, more preferably from among cyclic polyene, acyclic polyene, cyclic polyenyl and acyclic polyenyl groups having at least <NUM> unsaturated bonds in the molecule. Notably, at least <NUM> unsaturated bonds in the molecule may be either continuous or discontinuous.

On the other hand, the two-electron ligand (L) is a ligand containing two electrons coordinating with Fe.

The two-electron ligand is selected from carbene compounds containing a non-covalent electron pair (odd electron) such as nitrogen, phosphorus, oxygen or sulfur and isocyanide compounds containing both odd electron and π electron.

Preferred alkoxy groups are C<NUM>-C<NUM> groups although the carbon count is not critical. Examples include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, n-hexoxy, n-heptyloxy, n-octyloxy, n-nonyloxy, and n-decyloxy.

Preferred isocyanide compounds are those of the formula (<NUM>): Y-NC, but not limited thereto.

Herein Y is an optionally substituted C<NUM>-C<NUM> monovalent organic group which may be separated by at least one atom selected from oxygen, nitrogen, sulfur and phosphorus.

The C<NUM>-C<NUM> monovalent organic groups are preferably C<NUM>-C<NUM> monovalent hydrocarbon groups, but not limited thereto.

Suitable monovalent hydrocarbon groups include alkyl, alkenyl, alkynyl, aryl and aralkyl groups. Examples of the alkyl, aryl and aralkyl groups are as exemplified above.

The alkenyl groups are preferably C<NUM>-C<NUM> alkenyl groups. Examples include ethenyl, n-<NUM>-propenyl, n-<NUM>-propenyl, <NUM>-methylethenyl, n-<NUM>-butenyl, n-<NUM>-butenyl, n-<NUM>-butenyl, <NUM>-methyl-<NUM>-propenyl, <NUM>-methyl-<NUM>-propenyl, <NUM>-ethylethenyl, <NUM>-methyl-<NUM>-propenyl, <NUM>-methyl-<NUM>-propenyl, n-<NUM>-pentenyl, n-<NUM>-decenyl, and n-<NUM>-eicosenyl.

The alkynyl groups are preferably C<NUM>-C<NUM> alkynyl groups. Examples include ethynyl, n-<NUM>-propynyl, n-<NUM>-propynyl, n-<NUM>-butynyl, n-<NUM>-butynyl, n-<NUM>-butynyl, <NUM>-methyl-<NUM>-propynyl, n-<NUM>-pentynyl, n-<NUM>-pentynyl, n-<NUM>-pentynyl, n-<NUM>-pentynyl, <NUM>-methyl-n-butynyl, <NUM>-methyl-n-butynyl, <NUM>-methyl-n-butynyl, <NUM>,<NUM>-dimethyl-n-propynyl, n-<NUM>-hexynyl, n-<NUM>-decynyl, n-<NUM>-pentadecynyl, and n-<NUM>-eicosynyl.

The C<NUM>-C<NUM> monovalent organic group may have a substituent or a plurality of identical or different substituents at arbitrary positions.

Examples of the substituent include halogen atoms such as fluorine and chlorine, alkoxy groups such as methoxy, ethoxy and propoxy, and amino groups such as dialkylamino.

Examples of the isocyanide compound which may be preferably used herein as the ligand include, but are not limited to, alkyl isocyanides such as methyl isocyanide, ethyl isocyanide, n-propyl isocyanide, cyclopropyl isocyanide, n-butyl isocyanide, isobutyl isocyanide, sec-butyl isocyanide, t-butyl isocyanide, n-pentyl isocyanide, isopentyl isocyanide, neopentyl isocyanide, n-hexyl isocyanide, cyclohexyl isocyanide, cycloheptyl isocyanide, <NUM>,<NUM>-dimethylhexyl isocyanide, <NUM>-adamantyl isocyanide, and <NUM>-adamantyl isocyanide; aryl isocyanides such as phenyl isocyanide, <NUM>-methylphenyl isocyanide, <NUM>-methylphenyl isocyanide, <NUM>,<NUM>-dimethylphenyl isocyanide, <NUM>,<NUM>-dimethylphenyl isocyanide, <NUM>,<NUM>-dimethylphenyl isocyanide, <NUM>,<NUM>,<NUM>-trimethylphenyl isocyanide, <NUM>,<NUM>,<NUM>-tri-t-butylphenyl isocyanide, <NUM>,<NUM>-diisopropylphenyl isocyanide, <NUM>-naphthyl isocyanide, <NUM>-naphthyl isocyanide, and <NUM>-methyl-<NUM>-naphthyl isocyanide; and aralkyl isocyanides such as benzyl isocyanide and phenylethyl isocyanide.

The carbene compounds are preferably those of the formula (<NUM>), but not limited thereto.

In formula (<NUM>), Z is a carbon, nitrogen or oxygen atom, b is <NUM> when Z is a carbon atom, b is <NUM> when Z is a nitrogen atom, b is <NUM> when Z is an oxygen atom.

R<NUM> and R<NUM> are each independently a C<NUM>-C<NUM> alkyl, aryl or aralkyl group which may be substituted with a halogen atom or alkoxy group. Any one of R<NUM> and any one of R<NUM> may bond together to form a divalent organic group so that the compound has a cyclic structure. In this case, the cyclic structure may contain a nitrogen atom and/or unsaturated bond therein.

Examples of the halogen atom, C<NUM>-C<NUM> alkyl, aryl and aralkyl groups, and alkoxy groups are as exemplified above.

Preferred are cyclic carbene compounds of the formula (<NUM>).

In formula (<NUM>), A is a C<NUM>-C<NUM> divalent organic group which may contain a nitrogen atom and/or unsaturated bond. Exemplary groups include methylene, ethylene, propylene, trimethylene, n-butylene, isobutylene, s-butylene, vinylene, and prop-<NUM>-ene-<NUM>,<NUM>-diyl (propenylene).

Examples of the cyclic carbene compound are given below, but not limited thereto. <CHM>
<CHM>
<CHM>
<CHM>.

Besides, hydrosilylation reaction may be performed while an imidazolium salt as a precursor is reacted with a base such as KOtBu to generate a carbene compound in the system.

Examples of the imidazolium salt as a precursor include the following compounds, but are not limited thereto. <CHM>
<CHM>
<CHM>
<CHM>.

In preparing the inventive hydrosilylation iron catalyst, the amounts of the iron complex as precursor and the two-electron ligand used are not particularly limited. Preferably the two-electron ligand is used in an amount of about <NUM> to <NUM> equivalents, more preferably <NUM> to <NUM> equivalents, and even more preferably <NUM> to <NUM> equivalents per equivalent of the iron complex.

When hydrosilylation reaction is carried out in the presence of the inventive hydrosilylation iron catalyst, the amount of the catalyst used is not particularly limited. In order that the reaction take place under mild conditions of the order of room temperature to <NUM> to form the desired product in high yields, the catalyst is preferably used in an amount of at least <NUM> mol%, more preferably at least <NUM> mol% of metal compound per mole of the substrate, aliphatic unsaturated bond-containing compound.

Although no upper limit is imposed on the amount of metal compound used, the upper limit is preferably about <NUM> mol%, more preferably <NUM> mol% per mole of the substrate, as viewed from the economic standpoint.

The inventive hydrosilylation iron catalyst may be used after isolation from an iron complex catalyst prepared from the iron complex as precursor and the two-electron ligand. In an alternative embodiment, the catalyst may be prepared from the iron complex as precursor and the two-electron ligand in situ in a system where hydrosilylation reaction of a compound having an aliphatic unsaturated bond with a hydrosilane compound having a Si-H group or organohydropolysiloxane compound is carried out. The latter embodiment wherein the catalyst is prepared in situ and used without isolation is preferable from the standpoint of convenience of operation.

In this embodiment, once the catalyst is prepared from the iron complex as precursor and the two-electron ligand, the compound having an aliphatic unsaturated bond and the hydrosilane compound having a Si-H group or organohydropolysiloxane compound may be added thereto, or separate sets of some components may be fed, or all components may be fed at a time.

Although the reaction conditions for the iron complex as precursor and the two-electron ligand are not particularly limited, generally the reaction temperature is about <NUM> to about <NUM>, preferably <NUM> to <NUM> and the reaction time is about <NUM> to about <NUM> hours.

Although an organic solvent may be used during catalyst preparation and hydrosilylation reaction, the invention favors a solventless or neat system.

The organic solvent, if used, may be of any type as long as the reaction is not affected. Examples include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and cyclohexane, ethers such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran and <NUM>,<NUM>-dioxane; and aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene.

In conducting hydrosilylation reaction using the inventive hydrosilylation iron catalyst, as long as a compound having an aliphatic unsaturated bond such as an olefin, silane or organopolysiloxane compound having an aliphatic unsaturated bond and a silane or organopolysiloxane compound having a Si-H bond are used in combination, no limit is imposed on the structure of the respective compounds.

The hydrosilylation reaction using the inventive hydrosilylation iron catalyst is applicable to all applications which are industrially implemented using prior art platinum catalysts, including silane coupling agents obtained from an olefin compound having an aliphatic unsaturated bond and a silane compound having a Si-H bond, and modified silicone oils obtained from an olefin compound having an aliphatic unsaturated bond and an organopolysiloxane having a Si-H bond, as well as silicone cured products obtained from an organopolysiloxane compound having an aliphatic unsaturated bond and an organopolysiloxane having a Si-H bond.

Synthesis Examples, Examples and Comparative Examples are given below by way of illustration.

For the synthesis of metal complexes, all operations were carried out in nitrogen or argon atmosphere using the Schlenk tube technique or glove box. All solvents were deoxygenated and dehydrated by well-known methods before they were used in the preparation of metal compounds.

Hydrosilylation reaction and solvent purification of alkenes were always carried out in an inert gas atmosphere. The solvents and other ingredients were purified, dried and deoxygenated by well-known methods before they were used in various reactions.

Analyses of <NUM>H and <NUM>C-NMR spectroscopy were performed by JNM-ECA <NUM> and JNM-LA <NUM> of JEOL Ltd. , IR spectroscopy by FT/IR-<NUM> of JASCO Corp. , elemental analysis by 2400II/CHN of Perkin Elmer, x-ray crystallography analysis by VariMax (MoK α-ray <NUM> angstrom) of Rigaku Corp.

It is understood that hydrogen atoms are omitted from the chemical structural formula, shown below, according to the conventional expression. NHC stands for N-heterocyclic carbene.

With reference to<NPL>, the compound was synthesized by the following procedure.

A <NUM> two-neck recovery flask was charged with <NUM> (<NUM> mmol) of magnesium ribbon and <NUM> of THF, after which <NUM> (<NUM> mmol) of bromomesitylene was slowly added dropwise. It was confirmed that exotherm ceased at the end of dropwise addition, after which the reaction solution was stirred at <NUM> for <NUM> hours. The solution was filtered through a glass filter, obtaining a THF solution of mesitylmagnesium bromide Grignard reagent.

A <NUM> Schlenk flask was charged with <NUM> (<NUM> mmol) of FeCl<NUM>, <NUM> of THF, and <NUM> of <NUM>,<NUM>-dioxane and cooled down to -<NUM>. The THF solution of mesitylmagnesium bromide Grignard reagent was slowly added to the flask, followed by stirring at <NUM> for <NUM> hours. On this occasion, the reaction solution turned from a brown suspension to a red suspension. Thereafter, the precipitated solid was separated by centrifugation and dried in vacuum. The resulting red solid was dissolved in diethyl ether, after which the solid was separated again by centrifugation and recrystallized at -<NUM>, obtaining a crystal (<NUM>, yield <NUM>%). The crystal was identified by <NUM>H-NMR analysis in C<NUM>D<NUM>. <NUM>H-NMR (<NUM>, C<NUM>D<NUM>) δ:.

With reference to Non-Patent Document (<NPL>), iron biscyclooctatetraene was synthesized by the following procedure.

A <NUM> Schlenk flask was charged with <NUM> (<NUM> mmol) of iron triacetylacetonate, <NUM> of diethyl ether, and <NUM> (<NUM> mmol) of cyclooctatetraene. The mixture was cooled down to -<NUM>, to which <NUM> (<NUM>) of hexane solution of triethylaluminum was slowly added dropwise. After the addition of the entire amount, the solution was stirred at -<NUM> for <NUM> hours. The solution was stirred at room temperature for <NUM> minutes, cooled down to -<NUM> again, and held for <NUM> hours, allowing a crystal to precipitate out. With the supernatant removed, the resulting crystal was dissolved in diethyl ether again and recrystallized at -<NUM>, obtaining iron biscyclooctatetraene (abbreviated as Fe(COT)<NUM>, hereinafter) in black crystal form (<NUM>, yield <NUM>%). The crystal was identified by <NUM>H-NMR analysis in C<NUM>D<NUM>. <NUM>H-NMR (<NUM>, C<NUM>D<NUM>) δ:
<NUM> (s, <NUM>).

With reference to Non-Patent Document (<NPL>, iron bis(<NUM>-methylpentadienyl) was synthesized by the following procedure.

A <NUM> two-neck recovery flask was charged with <NUM> (<NUM> mmol) of potassium t-butoxide, <NUM> of hexane, and <NUM> (<NUM> mmol) of a hexane solution of <NUM> n-butyl lithium, followed by stirring. To the flask, <NUM> (<NUM> mmol) of <NUM>-methylpentadiene was added, followed by stirring at room temperature for <NUM> hour. The reaction solution turned from white to red while a precipitate formed. With the supernatant removed, the residue was washed with hexane and dried in vacuum. This was dissolved in <NUM> of THF, obtaining a THF solution of <NUM>-methylpentadienylpotassium.

A <NUM> Schlenk flask was charged with <NUM> (<NUM> mmol) of FeCl<NUM> and <NUM> of THF, and cooled down to -<NUM>. To the flask, the THF solution of <NUM>-methylpentadienylpotassium was slowly added dropwise. At the end of dropwise addition, the solution was stirred at room temperature for <NUM> hours. The reaction product was vacuum dried, dissolved in pentane, filtered through Celite, and recrystallized at -<NUM>. The resulting red solid was purified by sublimation at <NUM> in vacuum, obtaining iron bis(<NUM>-methylpentadienyl) (abbreviated as (MPDE)<NUM>Fe, hereinafter) in red solid form (<NUM>, yield <NUM>%). The solid was identified by <NUM>H-NMR analysis in C<NUM>D<NUM>. <NUM>H-NMR (<NUM>, C<NUM>D<NUM>) δ:.

With reference to Non-Patent Document (<NPL>, iron bis(<NUM>,<NUM>-dimethylpentadienyl) was synthesized by the following procedure.

A <NUM> two-neck recovery flask was charged with <NUM> (<NUM> mmol) of potassium t-butoxide, <NUM> of hexane, and <NUM> (<NUM> mmol) of a hexane solution of <NUM> n-butyl lithium, followed by stirring. To the flask, <NUM> (<NUM> mmol) of <NUM>,<NUM>-dimethylpentadiene was added, followed by stirring at room temperature for <NUM> hour. The reaction solution turned from white to red while a precipitate formed. With the supernatant removed, the residue was washed with hexane and dried in vacuum. This was dissolved in <NUM> of THF, obtaining a THF solution of <NUM>,<NUM>-dimethylpentadienylpotassium.

A <NUM> Schlenk flask was charged with <NUM> (<NUM> mmol) of FeCl<NUM> and <NUM> of THF, and cooled down to -<NUM>. To the flask, the THF solution of <NUM>,<NUM>-dimethylpentadienylpotassium was slowly added dropwise. At the end of dropwise addition, the solution was stirred at room temperature for <NUM> hours. The reaction product was vacuum dried, dissolved in pentane, filtered through Celite, and recrystallized at -<NUM>. The resulting red solid was purified by sublimation at <NUM> in vacuum, obtaining iron bis(<NUM>,<NUM>-dimethylpentadienyl) (abbreviated as (DMPDE)<NUM>Fe, hereinafter) in red solid form (<NUM>, yield <NUM>%). The solid was identified by <NUM>H-NMR analysis in C<NUM>D<NUM>. <NUM>H-NMR (<NUM>, C<NUM>D<NUM>) δ:.

A <NUM> Schlenk flask was charged with <NUM> (<NUM> mmol) of Fe(COT)<NUM>, <NUM> of pentane, and <NUM> (<NUM> mmol) of t-butyl isocyanide (abbreviated as tBuNC, hereinafter), followed by stirring at room temperature for <NUM> hours. Thereafter, the solution was filtered and the residue was recrystallized at -<NUM>, obtaining a black crystal (<NUM>, yield <NUM>). The crystal was identified by x-ray crystallography analysis, elemental analysis and NMR spectroscopy. <FIG> shows the structure of the resulting Iron complex A, <FIG> shows the data of <NUM>H-NMR spectroscopy, and <FIG> shows the data of <NUM>C-NMR spectroscopy.

A <NUM> Schlenk flask was charged with <NUM> (<NUM> mmol) of Fe(COT)<NUM>, <NUM> of toluene, and <NUM> (<NUM> mmol) of <NUM>-isocyanoadamantane (abbreviated as AdNC, hereinafter), followed by stirring at room temperature for <NUM> hour. Thereafter, the solution was filtered. Pentane was added to the residue, which was recrystallized at -<NUM>, obtaining a black crystal (<NUM>, yield <NUM>). The crystal was identified by x-ray crystallography analysis, elemental analysis and NMR spectroscopy. <FIG> shows the structure of the resulting Iron complex B, <FIG> shows the data of <NUM>H-NMR spectroscopy, and <FIG> shows the data of <NUM>C-NMR spectroscopy.

A <NUM> Schlenk flask was charged with <NUM> (<NUM> mmol) of Fe(COT)<NUM>, <NUM> of pentane, and <NUM> (<NUM> mmol) of tBuNC, followed by stirring at room temperature for <NUM> hours. Thereafter, the solution was filtered and the residue was recrystallized at - <NUM>, obtaining a red crystal (<NUM>, yield <NUM>%). The crystal was identified by x-ray crystallography analysis, elemental analysis and NMR spectroscopy. <FIG> shows the structure of the resulting Iron complex C, <FIG> shows the data of <NUM>H-NMR spectroscopy, and <FIG> shows the data of <NUM>C-NMR spectroscopy.

A <NUM> Schlenk flask was charged with <NUM> (<NUM> mmol) of Fe(COT)<NUM>, <NUM> of toluene, and <NUM> (<NUM> mmol) of AdNC, followed by stirring at room temperature for <NUM> hour. Thereafter, the solution was filtered, and the residue was combined with pentane and recrystallized at -<NUM>, obtaining a red crystal (<NUM>, yield <NUM>). The crystal was identified by x-ray crystallography analysis, elemental analysis and NMR spectroscopy. <FIG> shows the structure of the resulting Iron complex D, <FIG> shows the data of <NUM>H-NMR spectroscopy, and <FIG> shows the data of <NUM>C-NMR spectroscopy.

A screw-top vial was charged with <NUM> (<NUM> mmol) of [Fe(mesityl)(µ-mesityl)]<NUM> in Synthesis Example <NUM>, <NUM>µL (<NUM> mmol) of tBuNC, <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane, and <NUM>µL (<NUM> mmol) of <NUM>-octene. The vial was closed, after which the contents were stirred at <NUM> for <NUM> hours.

After cooling, <NUM> mmol of anisole as an internal standard was added to the reaction solution and stirred. A minute amount of the solution was dissolved in deuterochloroform, passed through an alumina column to remove the catalyst, and analyzed by <NUM>H-NMR spectroscopy to determine the structure and yield of the product. It is noted that in the following Examples, a test sample was prepared according to the same procedure and analyzed by <NUM>H-NMR spectroscopy. As a result, it was confirmed that the signal assigned to the ethylene site of <NUM>-octene as the reactant disappeared completely. Instead, a multiplet near <NUM> ppm indicative of the signal assigned to proton on silicon-adjoining carbon in the desired product, <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyl-<NUM>-octyldisiloxane was observed, from which a yield was determined. The results are shown in Table <NUM>. <NUM>H-NMR (<NUM>, CDCl<NUM>) δ:.

A screw-top vial was charged with <NUM> (<NUM> mmol) of [Fe(mesityl)(µ-mesityl)]<NUM> in Synthesis Example <NUM>, <NUM> (<NUM> mmol) of <NUM>,<NUM>-dimesitylimidazol-<NUM>-ylidene, <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane, and <NUM>µL (<NUM> mmol) of <NUM>-octene. The vial was closed, after which the contents were stirred at <NUM> for <NUM> hours.

After cooling, analysis was made by <NUM>H-NMR spectroscopy to determine the structure and yield of the product. As a result, it was confirmed that the signal assigned to the reactant disappeared completely. Instead, a multiplet near <NUM> ppm indicative of the signal assigned to the desired product was observed, from which a yield was determined. The results are shown in Table <NUM>.

A screw-top vial was charged with <NUM> (<NUM> mmol) of Fe(COT)<NUM> in Synthesis Example <NUM>, <NUM> mmol of an isocyanide listed in Table <NUM>, <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane and <NUM>µL (<NUM> mmol) of styrene. The vial was closed, after which the contents were stirred at <NUM> for <NUM> hours. After cooling, analysis was made by <NUM>H-NMR spectroscopy to determine the structure and yield of the product. As a result, it was confirmed that the signal assigned to the reactant disappeared completely. Instead, a multiplet near <NUM> ppm indicative of the signal assigned to proton on silicon-adjoining carbon in the desired product, <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyl-<NUM>-phenethyldisiloxane was observed, from which a yield was determined. The results are shown in Table <NUM>. <NUM>H-NMR (<NUM>, CDCl<NUM>) δ:.

A screw-top vial was charged with <NUM> (<NUM> mmol) of Fe(COT)<NUM> in Synthesis Example <NUM>, <NUM>µL (<NUM> mmol) of tBuNC, <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane and <NUM>µL (<NUM> mmol) of styrene. The vial was closed, after which the contents were stirred at <NUM> for <NUM> hours. After cooling, analysis was made by <NUM>H-NMR spectroscopy to determine the structure and yield of the product. As a result, it was confirmed that the signal assigned to the reactant disappeared completely. Instead, a multiplet near <NUM> ppm indicative of the signal assigned to the desired product was observed, from which a yield was determined. The results are shown in Table <NUM>.

Reaction was carried out according to the same procedure as in Example <NUM> aside from using <NUM>µL (<NUM> mmol) of <NUM>-methoxystyrene instead of styrene. As a result, it was confirmed that the signal assigned to the ethylene site of <NUM>-methoxystyrene as the reactant disappeared completely. Instead, a multiplet at <NUM> ppm indicative of the signal assigned to proton on silicon-adjoining carbon in the desired product, <NUM>-(<NUM>-methoxyphenylethyl)-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane was observed, from which a yield was determined. The results are shown in Table <NUM>. <NUM>H-NMR (<NUM>, CDCl<NUM>) δ:.

Reaction was carried out according to the same procedure as in Example <NUM> aside from using <NUM>µL (<NUM> mmol) of <NUM>-t-butylstyrene instead of styrene. As a result, it was confirmed that the signal assigned to the ethylene site of <NUM>-t-butylstyrene as the reactant disappeared completely. Instead, a multiplet near <NUM> ppm indicative of the signal assigned to proton on silicon-adjoining carbon in the desired product was observed, from which a yield was determined. The results are shown in Table <NUM>.

Thereafter, the reaction solution was purified by silica gel column chromatography (developing solvent, hexane/ethyl acetate = <NUM>/<NUM> by volume), obtaining <NUM>-(<NUM>-(t-butyl)phenylethyl)-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane (<NUM>, isolation yield <NUM>%).

Reaction was carried out according to the same procedure as in Example <NUM> aside from using <NUM>µL (<NUM> mmol) of <NUM>-chlorostyrene instead of styrene. As a result, it was confirmed that the signal assigned to the ethylene site of <NUM>-chlorostyrene as the reactant disappeared completely. Instead, a multiplet at <NUM> ppm indicative of the signal assigned to proton on silicon-adjoining carbon in the desired product was observed, from which a yield was determined. The results are shown in Table <NUM>.

Thereafter, the reaction solution was purified by silica gel column chromatography (developing solvent, hexane), obtaining <NUM>-(<NUM>-chlorophenylethyl)-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane (<NUM>, isolation yield <NUM>%).

Reaction was carried out according to the same procedure as in Example <NUM> aside from using <NUM>µL (<NUM> mmol) of <NUM>-fluorostyrene instead of styrene. As a result, it was confirmed that the signal assigned to the ethylene site of <NUM>-fluorostyrene as the reactant disappeared completely. Instead, a multiplet at <NUM> ppm indicative of the signal assigned to proton on silicon-adjoining carbon in the desired product was observed, from which a yield was determined. The results are shown in Table <NUM>.

Thereafter, the reaction solution was purified by silica gel column chromatography (developing solvent, hexane/ethyl acetate = <NUM>/<NUM> by volume), obtaining <NUM>-(<NUM>-fluorophenylethyl)-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane (<NUM>, isolation yield <NUM>%).

Reaction was carried out according to the same procedure as in Example <NUM> aside from using <NUM> (<NUM> mmol) of ethyl <NUM>-vinylbenzoate instead of styrene. As a result, it was confirmed that the signal assigned to the ethylene site of ethyl <NUM>-vinylbenzoate as the reactant disappeared completely. Instead, a multiplet at <NUM> ppm indicative of the signal assigned to proton on silicon-adjoining carbon in the desired product was observed, from which a yield was determined. The results are shown in Table <NUM>.

Thereafter, the reaction solution was purified by silica gel column chromatography (developing solvent, hexane/ethyl acetate = <NUM>/<NUM> by volume), obtaining ethyl <NUM>-(<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxanyl)ethyl-<NUM>-benzoate (<NUM>, isolation yield <NUM>%).

Reaction was carried out according to the same procedure as in Example <NUM> aside from using <NUM> (<NUM> mmol) of <NUM>-vinylnaphthalene instead of styrene. As a result, it was confirmed that the signal assigned to the ethylene site of <NUM>-vinylnaphthalene as the reactant disappeared completely. Instead, a multiplet at <NUM> ppm indicative of the signal assigned to proton on silicon-adjoining carbon in the desired product was observed, from which a yield was determined. The results are shown in Table <NUM>.

Thereafter, the reaction solution was purified by silica gel column chromatography (developing solvent, hexane), obtaining <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyl-<NUM>-(<NUM>-(<NUM>-naphthalenyl)ethyl)disiloxane (<NUM>, isolation yield <NUM>%).

Reaction was carried out according to the same procedure as in Example <NUM> aside from using <NUM>µL (<NUM> mmol) of <NUM>-octene instead of styrene. As a result, it was confirmed that the signal assigned to the ethylene site of <NUM>-octene as the reactant disappeared completely. Instead, a multiplet at <NUM> ppm indicative of the signal assigned to proton on silicon-adjoining carbon in the desired product was observed, from which a yield was determined. The results are shown in Table <NUM>.

Reaction was carried out according to the same procedure as in Example <NUM> aside from using <NUM>µL (<NUM> mmol) of <NUM>-octene instead of styrene. As a result, it was confirmed that the signal assigned to the ethylene site of <NUM>-octene as the reactant diminished. Instead, a multiplet at <NUM> ppm indicative of the signal assigned to proton on silicon-adjoining carbon in the desired product was observed, from which a yield was determined. The results are shown in Table <NUM>. <NUM>H-NMR (<NUM>, CDCl<NUM>) δ:.

Reaction was carried out according to the same procedure as in Example <NUM> aside from using <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyl-<NUM>-vinyldisiloxane instead of styrene. As a result, it was confirmed that the signal assigned to the ethylene site of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyl-<NUM>-vinyldisiloxane as the reactant disappeared completely. Instead, a singlet at <NUM> ppm indicative of the signal assigned to proton on silicon-adjoining carbon in the desired product was observed, from which a yield was determined. The results are shown in Table <NUM>. <NUM>H-NMR (<NUM>, CDCl<NUM>) δ:
<NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>).

Reaction was carried out according to the same procedure as in Example <NUM> aside from using <NUM>µL (<NUM> mmol) of allylbenzene instead of styrene. As a result, it was confirmed that the signal assigned to the ethylene site of allylbenzene as the reactant diminished. Instead, a multiplet at <NUM> ppm indicative of the signal assigned to proton on silicon-adjoining carbon in the desired product was observed, from which a yield was determined. The results are shown in Table <NUM>. <NUM>H-NMR (<NUM>, CDCl<NUM>) δ:.

Reaction was carried out according to the same procedure as in Example <NUM> aside from using <NUM>µL (<NUM> mmol) of α-methylstyrene instead of styrene. As a result, it was confirmed that the signal assigned to the ethylene site of α-methylstyrene as the reactant diminished. Instead, a multiplet at <NUM> ppm indicative of the signal assigned to proton on silicon-adjoining carbon in the desired product was observed, from which a yield was determined. The results are shown in Table <NUM>. <NUM>H-NMR (<NUM>, CDCl<NUM>) δ:.

In a nitrogen-blanketed glove box, <NUM> (<NUM> mmol) of Fe(COT)<NUM> in Synthesis Example <NUM>, <NUM>µL (<NUM> mmol) of t-BuNC, <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane, and <NUM>µL (<NUM> mmol) of cyclopentene were added to a screw-top vial with a stirrer. The vial was closed, after which the contents were stirred at <NUM> for <NUM> hours. After cooling, analysis was made by <NUM>H-NMR spectroscopy to determine the structure and yield of the product. As a result, it was confirmed that the signal assigned to the ethylene site of cyclopentene as the reactant diminished. Instead, a multiplet near <NUM> ppm indicative of the signal assigned to proton on silicon-adjoining carbon in the desired product was observed, from which a yield was computed. The results are shown in Table <NUM>. <NUM>H-NMR (<NUM>, CDCl<NUM>) δ:.

In a nitrogen-blanketed glove box, <NUM> (<NUM> mmol) of Fe(COT)<NUM> in Synthesis Example <NUM>, <NUM>µL (<NUM> mmol) of tBuNC, <NUM> (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane, and <NUM> (<NUM> mmol) of styrene were added to a screw-top vial with a stirrer. The vial was closed, after which the contents were stirred at <NUM> for <NUM> hours. After cooling, analysis was made by <NUM>H-NMR spectroscopy to determine the structure and yield of the product. As a result, it was confirmed that the signal assigned to the reactant disappeared completely. Instead, a multiplet near <NUM> ppm indicative of the signal assigned to the desired product was observed, from which a yield was computed. The results are shown in Table <NUM>.

Thereafter, the reaction solution was passed through an alumina column to remove the catalyst and purified by distillation at a vacuum of <NUM> Pa and <NUM>, obtaining a clear solution (<NUM> (<NUM> mmol), isolation yield <NUM>%).

Reaction was carried out according to the same procedure as in Example <NUM> aside from using <NUM>µL (<NUM> mmol) of dimethylphenylsilane instead of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane. As a result, it was confirmed that the signal assigned to the ethylene site of styrene as the reactant disappeared completely. Instead, a multiplet at <NUM> ppm indicative of the signal assigned to proton on silicon-adjoining carbon in the desired product, dimethyl(phenethyl)phenylsilane was observed, from which a yield was computed. The results are shown in Table <NUM>. <NUM>H-NMR (<NUM>, CDCl<NUM>) δ:.

In a nitrogen-blanketed glove box, <NUM> (<NUM> mmol) of Fe(COT)<NUM> in Synthesis Example <NUM>, <NUM>µL (<NUM> mmol) of tBuNC, <NUM> (<NUM> mmol) of dual end dimethylhydrosilyl-blocked polydimethylsiloxane (n=<NUM>), and <NUM>µL (<NUM> mmol) of styrene were added to a screw-top vial with a stirrer. The vial was closed, after which the contents were stirred at <NUM> for <NUM> hours. After cooling, analysis was made by <NUM>H-NMR spectroscopy to determine the structure and yield of the product. As a result, it was confirmed that the signal assigned to the ethylene site of styrene as the reactant disappeared completely. Instead, a multiplet at <NUM> ppm indicative of the signal assigned to proton on silicon-adjoining carbon in the desired product was observed, from which a yield was computed. The results are shown in Table <NUM>. <NUM>H-NMR (<NUM>, CDCl<NUM>) δ:.

In a nitrogen-blanketed glove box, <NUM> (<NUM> mmol) of Fe(COT)<NUM> in Synthesis Example <NUM>, <NUM> (<NUM> mmol) of AdNC, <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane, and <NUM>µL (<NUM> mmol) of styrene were added to a screw-top vial with a stirrer. The vial was closed, after which the contents were stirred at room temperature (RT) for <NUM> hours. After cooling, analysis was made by <NUM>H-NMR spectroscopy to determine the structure and yield of the product. As a result, it was confirmed that the signal assigned to the reactant disappeared completely. Instead, a multiplet near <NUM> ppm indicative of the signal assigned to the desired product was observed, from which a yield was computed. The results are shown in Table <NUM>.

Reaction was carried out according to the same procedure as in Example <NUM> aside from using <NUM> mmol of the alkenes listed in Table <NUM> instead of styrene and in Examples <NUM> and <NUM>, changing to the temperature shown in Table <NUM>. The results are shown in Table <NUM>.

Reaction was carried out according to the same procedure as in Example <NUM> aside from using <NUM> (<NUM> mmol) of AdNC instead of tBuNC. As a result, it was confirmed that the signal assigned to the reactant disappeared completely. Instead, a multiplet at <NUM> ppm indicative of the signal assigned to proton on the desired product was observed, from which a yield was computed. The results are shown in Table <NUM>.

Reaction was carried out according to the same procedure as in Example <NUM> aside from using <NUM> (<NUM> mmol) of AdNC instead of tBuNC. As a result, it was confirmed that the signal assigned to the reactant disappeared completely. Instead, a multiplet at <NUM> ppm indicative of the signal assigned to the desired product was observed, from which a yield was computed. The results are shown in Table <NUM>.

A screw-top vial was charged with <NUM> (<NUM> mmol) of Fe(COT)<NUM> in Synthesis Example <NUM>, <NUM> mmol of the ligand listed in Table <NUM>, <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane, and <NUM>µL (<NUM> mmol) of styrene. The vial was closed, after which reaction was conducted under the conditions shown in Table <NUM>. After cooling, analysis was made by <NUM>H-NMR spectroscopy to determine the structure and yield of the product. As a result, it was confirmed that the signal assigned to the reactant diminished. Instead, a multiplet near <NUM> ppm indicative of the signal assigned to the desired product was observed. A conversion and yield were determined from the <NUM>H-NMR data. The results are shown in Table <NUM>.

Reaction was carried out according to the same procedure as in Reference Example <NUM> aside from using <NUM>µL (<NUM> mmol) of <NUM>-octene instead of styrene. As a result, it was confirmed that the signal assigned to the reactant diminished. Instead, a multiplet at <NUM> ppm indicative of the signal assigned to the desired product was observed. A conversion and yield were determined from the <NUM>H-NMR data. The results are shown in Table <NUM>.

A screw-top vial was charged with <NUM> (<NUM> mmol) of (MPDE)<NUM>Fe in Synthesis Example <NUM>, <NUM>µL (<NUM> mmol) of tBuNC, <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane, and <NUM>µL (<NUM> mmol) of styrene. The vial was closed, after which the contents were stirred at <NUM> for <NUM> hours. After cooling, analysis was made by <NUM>H-NMR spectroscopy to determine the structure and yield of the product. As a result, it was confirmed that the signal assigned to the reactant disappeared completely. Instead, a multiplet near <NUM> ppm indicative of the signal assigned to proton in the desired product was observed, from which a yield was determined. The results are shown in Table <NUM>.

Reaction was carried out according to the same procedure as in Example <NUM> aside from using <NUM> (<NUM> mmol) of (DMPDE)<NUM>Fe in Synthesis Example <NUM> instead of (MPDE)<NUM>Fe. As a result, it was confirmed that the signal assigned to the ethylene site of styrene as the reactant disappeared completely. Instead, a multiplet near <NUM> ppm indicative of the signal assigned to proton on silicon-adjoining carbon in the desired product, <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyl-<NUM>-phenethyldisiloxane was observed, from which a yield was determined. The results are shown in Table <NUM>.

A screw-top vial was charged with like amounts of like reactants as in Example <NUM>. The vial was closed, after which the contents were stirred at <NUM> for <NUM> hours. After cooling, analysis was made by <NUM>H-NMR spectroscopy to determine the structure and yield of the product. As a result, it was confirmed that the signal assigned to the ethylene site of styrene as the reactant disappeared completely. Instead, a multiplet near <NUM> ppm indicative of the signal assigned to the desired product was observed, from which a yield was determined. The results are shown in Table <NUM>.

A screw-top vial was charged with <NUM> (<NUM> mmol) of (MPDE)<NUM>Fe in Synthesis Example <NUM>, <NUM> (<NUM> mmol) of <NUM>,<NUM>-dimesitylimidazol-<NUM>-ylidene, <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane, and <NUM>µL (<NUM> mmol) of <NUM>-octene. The vial was closed, after which the contents were stirred at <NUM> for <NUM> hours. After cooling, analysis was made by <NUM>H-NMR spectroscopy to determine the structure and yield of the product. As a result, it was confirmed that the signal assigned to the reactant disappeared completely. Instead, a multiplet near <NUM> ppm indicative of the signal assigned to the desired product was observed, from which a yield was determined. The results are shown in Table <NUM>.

In a nitrogen-blanketed glove box, <NUM> mmol of the iron catalyst listed in Table <NUM>, <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane, and <NUM>µL (<NUM> mmol) of styrene were added to a screw-top vial with a stirrer. The vial was closed, after which reaction was run under the conditions shown in Table <NUM>. After cooling, analysis was made by <NUM>H-NMR spectroscopy to determine the structure and yield of the product. As a result, it was confirmed that the signal assigned to the reactant disappeared completely. Instead, a multiplet near <NUM> ppm indicative of the signal assigned to the desired product was observed. A yield was computed from the <NUM>H-NMR data. The results are shown in Table <NUM>.

Reaction was conducted as in Example <NUM> by using <NUM> (<NUM> mmol) of iron biscyclooctatetraene in Synthesis Example <NUM>, <NUM>µL (<NUM> mmol) of tBuNC, <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane, and <NUM>µL (<NUM> mmol) of styrene and stirring the contents at <NUM> for <NUM> hours. The yield of the desired product was <NUM>% when determined as in Example <NUM>.

Reaction was conducted as in Example <NUM> by using <NUM> (<NUM> mmol) of iron biscyclooctatetraene in Synthesis Example <NUM>, <NUM> (<NUM> mmol) of AdNC, <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane, and <NUM>µL (<NUM> mmol) of styrene and stirring the contents at <NUM> for <NUM> hour. The yield of the desired product was <NUM>% when determined as in Example <NUM>.

Reaction was conducted as in Example <NUM> by using <NUM> (<NUM> mmol) of iron bis(<NUM>-methylpentadienyl) in Synthesis Example <NUM>, <NUM>µL (<NUM> mmol) of tBuNC, <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane, and <NUM>µL (<NUM> mmol) of styrene and stirring the contents at <NUM> for <NUM> hours. The yield of the desired product was <NUM>% when determined as in Example <NUM>.

Reaction was conducted as in Example <NUM> by using <NUM> (<NUM> mmol) of iron bis(<NUM>-methylpentadienyl) in Synthesis Example <NUM>, <NUM> (<NUM> mmol) of AdNC, <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane, and <NUM>µL (<NUM> mmol) of styrene and stirring the contents at <NUM> for <NUM> hours. The yield of the desired product was <NUM>% when determined as in Example <NUM>.

Reaction was conducted as in Example <NUM> by using <NUM> (<NUM> mmol) of iron bis(<NUM>-methylpentadienyl) in Synthesis Example <NUM>, <NUM> (<NUM> mmol) of AdNC, <NUM> (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane, and <NUM> (<NUM> mmol) of styrene and stirring the contents at <NUM> for <NUM> hours. The yield of the desired product was <NUM>% when determined as in Example <NUM>.

Reaction was conducted as in Example <NUM> by using <NUM> (<NUM> mmol) of iron bis(<NUM>-methylpentadienyl) in Synthesis Example <NUM>, <NUM> (<NUM> mmol) of MePDI, <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane, and <NUM>µL (<NUM> mmol) of styrene and stirring the contents at <NUM> for <NUM> hours. The yield of the desired product was <NUM>% when determined as in Example <NUM>.

Reaction was conducted as in Example <NUM> by using <NUM> (<NUM> mmol) of iron bis(<NUM>-methylpentadienyl) in Synthesis Example <NUM>, <NUM> (<NUM> mmol) of EtPDI, <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane, and <NUM>µL (<NUM> mmol) of styrene and stirring the contents at <NUM> for <NUM> hours. The yield of the desired product was <NUM>% when determined as in Example <NUM>.

Reaction was conducted as in Example <NUM> by using <NUM> (<NUM> mmol) of iron bis(<NUM>-methylpentadienyl) in Synthesis Example <NUM>, <NUM> (<NUM> mmol) of <NUM>,<NUM>-bis[<NUM>-(<NUM>,<NUM>-diisopropyl-phenylimino)ethyl]pyridine (iPrPDI), <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane, and <NUM>µL (<NUM> mmol) of styrene and stirring the contents at <NUM> for <NUM> hours. The conversion was <NUM>% and the yield of the desired product was <NUM>% when determined as in Example <NUM>.

Reaction was conducted as in Example <NUM> by using <NUM> (<NUM> mmol) of iron bis(<NUM>-methylpentadienyl) in Synthesis Example <NUM>, <NUM> (<NUM> mmol) of <NUM>,<NUM>':<NUM>',<NUM>"-terpyridine, <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane, and <NUM>µL (<NUM> mmol) of styrene and stirring the contents at <NUM> for <NUM> hours. The conversion was <NUM>% and the yield of the desired product was <NUM>% when determined as in Example <NUM>.

Reaction was conducted as in Example <NUM> by using <NUM> (<NUM> mmol) of iron bis(<NUM>-methylpentadienyl) in Synthesis Example <NUM>, <NUM> (<NUM> mmol) of MePDI, <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane, and <NUM>µL (<NUM> mmol) of <NUM>-octene and stirring the contents at <NUM> for <NUM> hours. The conversion was at least <NUM>% and the yield of the desired product was <NUM>% when determined as in Example <NUM>.

Reaction was conducted as in Example <NUM> by using <NUM> (<NUM> mmol) of iron bis(<NUM>-methylpentadienyl) in Synthesis Example <NUM>, <NUM> (<NUM> mmol) of EtPDI, <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane, and <NUM>µL (<NUM> mmol) of <NUM>-octene and stirring the contents at <NUM> for <NUM> hours. The conversion was at least <NUM>% and the yield of the desired product was <NUM>% when determined as in Example <NUM>.

Reaction was conducted as in Example <NUM> by using <NUM> (<NUM> mmol) of iron bis(<NUM>-methylpentadienyl) in Synthesis Example <NUM>, <NUM> (<NUM> mmol) of iPrPDI, <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane, and <NUM>µL (<NUM> mmol) of <NUM>-octene and stirring the contents at <NUM> for <NUM> hours. The conversion was at least <NUM>% and the yield of the desired product was <NUM>% when determined as in Example <NUM>.

Reaction was conducted as in Example <NUM> by using <NUM> (<NUM> mmol) of iron bis(<NUM>-methylpentadienyl) in Synthesis Example <NUM>, <NUM> (<NUM> mmol) of <NUM>,<NUM>':<NUM>',<NUM>"-terpyridine, <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane, and <NUM>µL (<NUM> mmol) of <NUM>-octene and stirring the contents at <NUM> for <NUM> hours. The conversion was <NUM>% and the yield of the desired product was <NUM>% when determined as in Example <NUM>.

Reaction was conducted as in Example <NUM> by using <NUM> (<NUM> mmol) of iron bis(<NUM>-methylpentadienyl) in Synthesis Example <NUM>, <NUM>µL (<NUM> mmol) of tBuNC, <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane, and <NUM>µL (<NUM> mmol) of <NUM>-chlorostyrene and stirring the contents at <NUM> for <NUM> hours. The yield of the desired product was <NUM>% when determined as in Example <NUM>.

Reaction was conducted as in Example <NUM> by using <NUM> (<NUM> mmol) of iron bis(<NUM>-methylpentadienyl) in Synthesis Example <NUM>, <NUM> (<NUM> mmol) of AdNC, <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane, and <NUM>µL (<NUM> mmol) of <NUM>-chlorostyrene and stirring the contents at <NUM> for <NUM> hours. The yield of the desired product was <NUM>% when determined as in Example <NUM>.

Reaction was conducted as in Example <NUM> by using <NUM> (<NUM> mmol) of iron bis(<NUM>-methylpentadienyl) in Synthesis Example <NUM>, <NUM>µL (<NUM> mmol) of tBuNC, <NUM>µL (<NUM> mmol) of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyldisiloxane, and <NUM>µL (<NUM> mmol) of <NUM>-methoxystyrene and stirring the contents at <NUM> for <NUM> hours. The yield of the desired product was <NUM>% when determined as in Example <NUM>.

Claim 1:
A hydrosilylation iron catalyst which is
a mono-, bi- or tri-nuclear complex of iron having the formula (<NUM>) as a catalyst precursor combined with a two-electron ligand (L):

        Fe(X)a     (<NUM>)

wherein each X is a C<NUM>-C<NUM> ligand, exclusive of cyclopentadienyl groups, selected from aryl groups, aralkyl groups, cyclic or acyclic olefins, cyclic or acyclic olefinyl groups, which may be substituted with a halogen atom, alkoxy group or haloalkyl, and a is an integer of <NUM> to <NUM> per Fe atom, the Fe having bonds solely with carbon atoms in ligands X, and the total number of Fe-carbon bonds with carbon atoms in ligands X being <NUM> to <NUM>,
wherein L is at least one two-electron ligand (L) selected from isocyanide and carbene.