bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthesis of Mono‐, Di‐, and Tri‐arylgold(III) Complexes Using Organomercury Compounds – Synthesis of the First Aurated Schiff Bases
Authors: Vicente Jose , Berm údez María‐Dolores , Carri ón Francisco‐José , Jones Peter G. 
Published: July 2007

AbstractThe formylarylmercury(II) complex [Hg{C6H(CHO)‐6‐(OMe)3‐2,3,4}2] reacts with 4‐butylaniline (1:2) to give [Hg{C6H(CH=NC6H4C4H9‐4′)‐6‐(OMe) 3‐2,3,4}2] (1) by a condensation reaction. This complex reacts with Me4‐N[AuCl4] (1:1) to give [Hg{C6H(CH=NC6H4C4H9‐4′)‐6‐(OMe) 3‐2,3,4}Cl] (2) and the monoarylgold(III) compound cis‐C6H4‐nBu‐4′)‐6‐(OMe)3‐2,3,4}Cl2] (3). This complex reacts with PPh3 (1:1) to give the adduct cis‐[Au{C6H(CH=NC6H4‐n, Bu‐4′)‐6‐(OMe)3‐2,3,4}Cl2(PPh3)] (4) and with AgClO4 (1:1) in acetone to give the ketonyl complex cis‐[C6H4‐nBu‐4′)‐6‐ (OMe)3‐2,3,4}‐{CH2C(O)Me}Cl] (5). cis‐Me4N[Au(C6H4NO2‐2)2Cl 2] react with [Hg{C6H3(N=NC6H4OMe‐4′)‐2‐(OMe)‐5}Cl] and Me4NCl (1:1:1) to give cis‐[C6H4OMe‐4′)‐2‐ (OMe)‐5}(C6H4NO2‐2)2] (6): Similarly, cis‐Me4N‐[Au(C6H4CF3‐2)2 Cl2] (7), obtained by treating [Hg(C6H4CF3‐2)2] with Me4N[AuCl4] and Me4NCl (1:1:1), reacts with [Hg(C6H4CH2NMe2‐2)Cl] and Me4NCl (1:1:1) to give the triarylgold(III) complex cis‐[Me2‐2)(C6H4CF3‐2)2] (8). This complex can also be obtained by treating cis‐[Me2‐2)Cl2] with [Hg(C6H4CF3‐2)2] and Me4NCl (1:1:1). The crystal structure of 3 reveals the presence of two independent molecules, in one of which the butylphenyl group is disordered. The geometry at the gold atom is square planar; distortions may be attributed to the narrow bite angle and steric repulsion between a chloride ligand and the ortho‐methoxy group. The greater trans influence of the aryl ligand causes a great difference in Au–Cl bond lengths.
Molecular Gymnastics of Alkynes Orchestrated by Ruthenium Complexes
Authors: Trost Barry M. 
Published: July 2007

AbstractRuthenium complexes catalyze a variety of addition or isomerization reactions that are highly atom economical. Terminal alkynes react with allyl alcohols to form β,γ‐unsaturated ketones that can be readily isomerized to α,β‐unsaturated ketones via transient vinylidene complexes. A cyclization via a transient allenylidene complex concomitant with this addition represents a novel way to build heterocycles. Ancillary studies with these catalysts revealed an internal oxidation reduction whereby allyl alcohols are isomerized to saturated ketones and propargyl alcohols are isomerized to α,β‐unsaturated carbonyl compounds. Consideration of the reaction mechanism led to a general Alder ene type reaction wherein alkynes serve as the enophile and alkenes serve as the ene component. These discoveries have led to a number of efficient total syntheses of biologically interesting targets. Mechanistic investigations into the activation of a ruthenium complex led to the discovery of a novel bis‐homo‐Diels‐Alder reaction of 1,4‐cyclooctadiene.
Direct Synthesis of Organometallics, IV. The Mechanism of the Activation of Aromatic Hydrocarbons with Lithium Atoms: Spectroscopic Results and Their Ab initio Interpretation
Authors: Tacke Matthias 
Published: July 2007

AbstractIn the presence of THF, lithium atoms are known to be able to activate benzene derivatives under cryogenic reaction conditions. This synthesis affords solid lithium hydride and ring‐metalated products selectively. For the determination of the reaction mechanism, the cocondensation reaction was repeated on a reduced scale in a 77‐K cryostate, which allowed the measurement of UV/Vis and IR spectra. The spectroscopic results exclude any generation of free electrons; their interpretation suggests that small solvated lithium clusters activate the hydrocarbon bonds. A model reaction was developed by using the spectroscopic results and ab initio calculations. Thus, benzene was added to a Li2 cluster, which reduces the carbon‐hydrogen bond to the phenyl anion and hydride on the surface without the formation of free radicals. In the last step the intermediate mixed organolithium species dismutate to solid lithium hydride and phenyllithium.magnified imageThe reduction process on the cluster surface is facilitated by coordinating THF to the lithium, which results in a higher redox potential. The complete mechanism is discussed in the terms of geometries of the intermediates and reaction enthalpies in connection with the experimental values. Thus, a distinct new reaction pathway for a substitution on the benzene ring is established.
(Allyl)zirconium(IV) Complexes with the N,N′ ‐bis(trimethylsilyl)benzamidinato (“siam”) Ligand — Molecular Structures and η1–η3 Interconversions of the Allyl Groups
Authors: Walther Dirk , Fischer Reinald , Friedrich Manfred , Gebhardt Peter , Görls Helmar 
Published: July 2007

AbstractComplexes of the type (siam)2Zr(allyl)2 (1a) and (siam)Zr(allyl)nClm are described (2a: n = 1, m = 2; 2b: n = 2, m = 1; 2c: n = 3, m = 0; siam: N,N′ ‐bis(trimethylsilyl)benzamidinato group). The molecular structure of 1a shows that both allyl groups are differently bonded. One allyl ligand is η3‐, the other η1‐coordinated. The X‐ray crystal structure of the tris‐(allyl) complex 2c shows a chiral molecule with two η3‐allyl ligands. The third allyl ligand is coordinated in a mode intermediate between η3 and η1, thus serving as a model for an intermediate in the η3‐η1 intramolecular rearrangement of the allyl ligands observed in solution. Temperature‐dependent 1H‐ and 13C‐NMR spectra of 1a, 2b and 2c indicate a rapid η1‐η3 rearrangement of the allyl groups at 60°C. At −50°C two different coordination modes of the allyl groups can be observed in the case of 2b and 2c.
Reactions of Tetrakis[bis(trimethylsilyl)methyl]digallane(4) with Carboxylic Acids — Substituent Exchange and Bridging of the GaGa bond by two Carboxylato Groups
Authors: Uhl Werner , Hahn Ingo , Reuter Hans 
Published: July 2007

AbstractYellow tetrakis[bis(trimethylsilyl)methyl]digallane(4) 1 reacts with two equivalents of the carboxylic acids RCOOH (R = −C6H5, −p−BrC6H4, −3,5‐Me2C6H3, −CMe3) to yield almost quantitatively colorless products in which two bis(trimethylsilyl)methyl groups are replaced by two carboxylato ligands. As shown by a crystal structure determination with the 4‐bromo‐phenyl derivative (3), the GaGa bond is bridged by both carboxylato groups in a chelating manner. The GaGa distance is shortened to 238.5(2) pm (1: 254.1(1) pm) and the coordination number of the Ga atoms increased to four.
The Coordination and Transformations of a Dicarboxylate Substituted Allene on a Dimanganese Carbonyl Grouping
Authors: Adams Richard D. , Huang Mingsheng 
Published: July 2007

AbstractTwo products, Mn2(CO)7(PMe2Ph)[μ‐η2‐η2‐MeO2C(H)CCC‐(H)CO2Me] (1) in 9% yield and Mn2(CO)6(PMe2Ph)[μ‐η3‐η1‐MeO2CC(H)CC(H)CO2Me] (2) in 34% yield, were obtained from the reaction of Mn2(CO)8(PMe2Ph)(MeCN) with MeO2C(H)C=C=C(H)CO2Me. Compound 1 contains a bridging η2‐η2‐MeO2C(H)CCC(H)CO2Me allene ligand and compound 2 contains a bridging η3‐η1‐MeO2C(H)CCC(H)‐CO2Me allene ligand in which the oxygen atom of one of the carbonyl groups is also coordinated. Compound 1 slowly converts to 2, which establishes that it is a precursor to 2. Compound 2 reacts with NEtH2 to give the mononuclear manganese complex fac‐Mn(CO)3(PMe2Ph)[MeO2CCH2‐C=C(H)CO2Me] (3) in 96% yield. Compound 3 contains a chelating 1,3‐di(methoxycarbonyl)propenyl grouping formed by addition of a hydrogen atom to the allene and the loss of a manganese grouping. Compounds 1–3 were characterized by single crystal x‐ray diffraction methods.
Mass Spectrometric Study of [Fe,C3,H6,O]+ Isomers Relevant in the Gas‐phase Oxidation of Hydrocarbons by “Bare” FeO+
Authors: Schwarz Joseph , Wesendrup Ralf , Schröder Detlef , Schwarz Helmut 
Published: July 2007

AbstractThe structures and energetics of [Fe,C3,H6,O]+ isomers are probed by mass spectrometric means. The complexes Fe‐(CH3COCH3)+, Fe(CH3CH2CHO)+, Fe(CH3OCH=CH2)+, Fe(CH2O)(C2H4)+, c‐(FeOCH2CH2CH2)+, Fe(CH2=CH‐CH2OH)+, and Fe(OH)(C3H5)+ can be distinguished by comparing their reactivity toward benzene and their collision‐induced dissociation mass spectra, respectively. These findings are used to interpret the formation of [Fe,C3,H6,O]+ in oxidation reactions of hydrocarbons by the highly reactive FeO+ cation. For example, in the reactions of FeO+ with norbornane and pentanol Fe(OH)(C3H5)+ is produced, while the reaction of FeO+ with norbornane to yield [Fe,C3,H6,O]+ is one of the rare cases of initial CC bond activation by a “bare” transition‐metal oxide. The reaction of FeO+ with propene involves formation of metalla oxetanes as primary products. In general, “bare” FeO+ is not selective and allylic CH bond activation of propene competes efficiently, thus pointing to a potentially rich chemistry.
1,3‐Heterobinuclear Cyclobutenylidene Complexes with an Exocyclic CC bond — Synthesis, Structure, and Spectroscopic Properties
Authors: Fischer Helmut , Leroux Frédéric , Stumpf Rüdiger , Roth Gerhard 
Published: July 2007

AbstractPentacarbonyl(allenylidene)chromium and ‐tungsten, [(CO)5MCCCR2] (M=Cr, R=C6H4CH3‐p(1a), C6H4OCH3 (1b); M=W, R=C6H4CH3‐p (1c), react with the alkynyl complexes [Cp(CO)2FeCCR′] (R′ = nBu (2), Ph (4)), [Cp*(CO)2FeCCnBu] (6), [Cp(CO){P(OMe)3}‐FeCCnBu] (8) and [Cp(PPh3)NiCCnBu] (10) by cycloaddition of the CC bond of the alkynyl complexes to the Cα=Cβ bond of the allenylidene ligand to give 3a–c), (5), (7), and respectively. The cycloaddition is highly selective. The spectroscopic data of these 1,3‐heterobinuclear complexes indicate a delocalized π‐system (M=Cr, W; Y=[Fe(CO)2Cp], [Fe(CO)(P{OMe}3)Cp], [Fe(CO)2Cp*], [Ni(PPh3)‐Cp]). X‐ray structural analyses of the compounds 3a, 9a, and 11c reveal a “butterfly” conformation of the four‐membered ring. Its puckering angle is 142° (3a), 152° (9a), and 151° (11c). All Complexes exhibit a moderate to strong negative solvatochromic behavior. The extent of the solvatochromic effect depends on [(CO)5M] and Y and considerably decreases when C=CR2 is replaced by e.g. CMe2.
Preparation and Crystal Structure of the New Quaternary Europium‐polysulfide KCuEu2s6
Authors: Bensch Wolfgang , Dürichen Peter 
Published: July 2007

AbstractThe new quaternary europium polysulfide KCuEu2S6 was obtained using the reactive flux method at an intermediate temperature of 380°C by reacting K2S3 with elemental Cu, EuS and an excess of sulfur. The Eu3+ ions exhibit a bicapped trigonal prismatic coordination and the Cu+ ions are in a tetrahedral environment. The crystal structure is characterized by anionic layers of interconnected Eu and Cu polyhedra with K+ ions residing between the anionic sheets [Cu‐Eu2S6]nn—. The Cu+ ions occupy one half of the tetrahedral sites in an ordered fashion.
Mixed Bent Sandwich Titanium Complexes with the [2‐(Diisopropylamino)ethyl]cyclopentadienyl Ligand — Catalysts for the Polymerization of Ethylene and the Dehydrocoupling of Phenylsilane
Authors: Jutzi Peter , Redeker Thomas , Neumann Beate , Stammler Hans‐Georg 
Published: July 2007

AbstractMixed bent sandwich titanium (IV) complexes containing the donor‐substituted [2‐(diisopropylamino)ethyl]cyclopentadienyl (C5H4CH2CH2NiPr2  CpN) ligand are described. The highly moisture‐sensitive metallocene dichloride (C5H4CH2CH2NNiPr2)(C5H4SiMe3)TiCl2 (1) was synthesized by reaction of CpNLi with CpSTiCl3 (CpS  C5H4SiMe3). Complex 1 reacts with one equivalent of HCl with protonation of the amino group to give the air‐ and water‐stable metallocene dichloride‐hydrochloride [(C5H4CH2CH2‐N(H)iPr2)(C5H4SiMe3)TiCl2]+Cl− (2). The structure of 2 was determined by a single‐crystal X‐ray diffraction study. Compounds 1 and 2 are precursors for ethylene polymerization catalysts. The reaction of 2 with one equivalent of Na+B[3,5‐(CF3)2C6H3]4− afforded the borate [(C5H4CH2CH2N(H)iPr2)‐(C5H4SiMe3)TiCl2]+B[3,5‐(CF3)2C6H3]4− (3). The dimethyl compounds (C5H4CH2CH2NiPr2)(C5H4SiMe3)Time2 (4) was obtained by reaction of 1 with two equivalents of methyllithium. The diphenoxy complex (C5H4CH2CH2‐NiPr2)(C5H4SiMe3)Ti(OPh)2 (5) was prepared analogously with a stoichiometric amount of lithium phenoxide. Compounds 4 and 5 show remarkable activity in the catalytic dehydrocoupling of phenylsilane.
Derivate des Imidazols, XIX. Koordination oder Reduktion? Zur Reaktion von 1,3‐Diisopropyl‐4,5‐dimethylimidazol‐2‐yliden mit Schwefelhalogeniden und Schwefeloxidhalogeniden
Authors: Kuhn Norbert , Bohnen Hans , Fahl Joanna , Bläser Dieter , Boese Roland 
Published: July 2007

Imidazole Derivatives, XIXPart XVIII: Ref.[1]

.
— Coordination or reduction? On the Reaction of 1,3‐Diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene with Sulfur Halides and Sulfur Oxygen Halides

Herrn Professor Max Herberhold zum 60. Geburtstag gewidmet.
The reaction of 1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene (4, Im) with sulfur halides and sulfur oxygen halides may be described as a coordination (1) or reduction (2) process in respect to the sulfur centre. With SCl2 and SOCl2 the hypervalent sulfur compounds Im · SCl2 (5) and Im · S(O)Cl2 (13) are obtained. The SF2 adduct Im · SF2 (11) is formed on treatment of 5 with AgF. 13 is alkylated by methyl iodide to give the Im · S(Me)OCl2 cation (15). Surprisingly, reduction of the sulfur centre (2) occurs on treatment of 4 with SF4 to form the ImF+SF3− salt 18 containing the new SF3 anion. As expected, the same type of reaction occurs with the sulfuryl halides SO2ClF and SO2F2 to give the fluorosulfites ImCl+‐SO2F− (21) and ImF+SO2F− (23). The X‐ray structures of 5, 13 and 23 are reported.
Tripodliganden mit Neopentangrundgerüst und zwei verschiedenen Donorfunktionen CH3C(CH2PPh2)2(CH2SR): Synthese, Struktur, Redoxchemie und Spektroskopie von Komplexen des Typs tripodM{ortho‐(X)(Y)C6H4}
Authors: Körner Volkmar , Huttner Gottfried , Zsolnai Laszlo , Büchner Michael , Jacobi Albrecht , Günauer Diethelm 
Published: July 2007

Tripod Ligands with Neopentane Frame and two Different Donor Groups CH3C(CH2PPh2)2(CH2SR): Synthesis, Structure, Redox Chemistry, and Spectroscopy of the Complexes tripodM{ortho‐(X)(Y)C6H4}Prof. Dr. Jörn Müller zum 60. Geburtstag gewidmet.
Neopentane‐based tripod ligands CH3C(CH2PPh2)2(CH2Z) (Z = SBn, SH, S−) form pentacoordinate compounds [tripodM{ortho(X)(Y)C6H4}]m 1–4 with ortho‐phenylene‐bridged coligands (X)(Y)C6H4 (X, Y = O−, S−, NH−) and Co(II), Co(III), Fe(II), or Fe(III) as the metal centers. The structures of these complexes are very similar to those observed for CH3C(CH2PPh2)3 as the tripod ligand. The redox potentials, however, for the corresponding one‐electron oxidation and reduction processes are highly affected by the change in the tripod donor groups. Both potentials are shifted by a maximum of 700 mV upon replacement of a PPh2 donor group by a sulfur‐centered donor with the difference between the potential of the oxidation step and the potential of the reduction step staying almost constant for the whole series of compounds. This difference of around 1.7 eV nicely corresponds to the energy of the HOMO‐LUMO chargetransfer bands observed around 2 eV for all of the compounds. It may be inferred therefore that both observations (electron spectroscopy and cyclic voltammetry) refer in a similar way to the HOMO‐LUMO gap of the compounds. It is shown that the formation of [tripodCo(III){ortho‐(NH)2C6H4}]+(BF) from ortho‐phenylenediamine as the source of the coligand involves precoordination of the amine ligand followed by deprotonation of the coordinated ligand. The capability of the tripodCo(II) template to form five‐coordinate compounds with diamines is further corroborated by the characterization of [tripodCo(en)]2+ (52+). In addition to the standard analytical data, EPR, UV/Vis, cyclovoltammetric data and X‐ray structure analyses are presented where appropriate.
Photochemical reactions of transition metal organyl complexes with olefins, 17. Light‐Induced [6+2] Cycloadditions of Dienes to Tricarbonyl(η6‐1,3,5,7‐cyclooctatetraene)chromium(0)
Authors: Kreiter Cornelius G. , Eckert Ralf 
Published: July 2007

AbstractTricarbonyl(η6‐1,3,5,7‐cyclooctatetraene)chromium (1) yields upon UV irradiation in ether at 233 K with 2,3‐dimethyl‐1,3‐butadiene (2) or 2‐methyl‐1,3‐butadiene (3) by [6+2] cycloadditions the correspondingly substituted tricarbonyl(η6‐bicyclo[4.2.2]deca‐2,4,7‐triene)chromium complexes 4, 5a and 5b. With ammonium cerium(IV) nitrate the organic ligand of complex 4, 9‐isopropenyl‐9‐methyl‐bicyclo[4.2.2]‐deca‐2,4,7‐triene (6) is liberated. The complexes 4, 5a and 5b were characterised by IR and NMR spectroscopy, the ligand 6 by NMR spectroscopy.
Synthesis of the Hexakis[(triphenylphosphane)gold(I)]methanium(2+) Cation from Trimethylsilyldiazomethane; Crystal Structure Determination of the Tetrafluoroborate Salt
Authors: Gabbaï FraņOis P. , Schier Annette , Riede Jürgen , Schmidbaur Hubert 
Published: July 2007

AbstractA new synthetic route to the bis(tetrafluoroborate) salt of the hexakis[(triphenylphosphane)gold(I)]methanium dication has been opened up through the reaction of trimethylsilyldiazomethane and tris[(triphenylphosphane)gold(I)]oxonium tetrafluoroborate in dichloromethane. Yields are close to 65% if the reaction is carried out in the presence of triethylamine as a base. The process is a sequence of desilylation, deprotonation and deazotation reactions at the carbon function of the diazomethane, as shown by the detection of intermediates. The crystal structure of the title compound (with three equivalents of crystal dichloromethane) has been determined in a single‐crystal X‐ray study. The dication has no crystallographically imposed symmetry, but the core is a distorted, carbon‐centered octahedron of gold atoms. This result confirms the data from previous structural studies of salts with other anions and interstitial solvents.
The Gas‐Phase Structure of Trifluoromethyl Vinyl Sulfide, CF3SC(H)CH2
Authors: Lieb Max , Oberhammer Heinz 
Published: July 2007

AbstractThe geometric structure of trifluoromethyl vinyl sulfide, CF3SC(H)CH2, was determined by gas electron diffraction and ab initio calculations (HF/3‐21G* and MP2/6‐31G*). A single conformer with a dihedral angle ϕ(CC–S–C) = 129(4)° is present. The conformational properties are compared to those of the parent compound, CH3SC(H)CH2, and of the perfluorinated species CF3SC(F)CF2.
Synthesis and Electrochemistry of Diels‐Alder Adducts of [60] Fullerene with a Phthalocyanine and a Hemiporphyrazine
Authors: Dürr Kai , Fiedler Stefan , Linßen Torsten , Hirsch Andreas , Hanack Michael 
Published: July 2007

AbstractThe synthesis of a new Diels‐Alder adduct 7 of [60]fullerene and a phthalocyaninenickel compound containing a longer spacer than the originally reported Diels‐Alder adduct 1 is described. The bisenophilic hemiporphyrazinenickel compound 11 reacts with [60]fullerene to form a Diels‐Alder adduct 12 containing two fullerene units. Spectroelectrochemical investigations of 7 and 12 reveal multiple reductions, which are attributed to the corresponding subunits of the molecules. In contrast to 1, the election acceptor properties of the [60]fullerene unit in both molecules have no influence on the electronic properties of the phthalocyanine and hemiporphyrazine, respectively.
Tetramethylguanidine and Benzophenoneimine as Ligands in Gold Chemistry
Authors: Schneider Wolfgang , Bauer Andreas , Schier Annette , Schmidbaur Hubert 
Published: July 2007

Abstract(Tetramethylguanidine)gold(I) chloride (1) and bromide (2) are readily prepared in high yield from (Me2N)2CNH and [AuCl(Me2S)] or [AuBr(tht) (tht = tetrahydrothiophene), repectively. NMR spectra of chloroform solutions of the two products indicate equilibria of the type 2 LAuX = L2Au+AuX2−. The cationic complex [Au(NHC(NMe2)2)(PPh3)]+ is obtained as the triflate salt 3 from tetramethylguanidine and [Au(PPh3)]+O3SCF3−. In solution at low temperature (−60°C), this compound adopts a rigid structure whereby the NMe2 groups are rendered non‐equivalent, but at ambient temperature there is coalescence of the NMe2 signals in the 1H‐ and 13C‐NMR spectra. The related benzophenoneimine complex [Au{NHCPh2}(PPh3)]+BF4− (4), which was synthesized as a reference3 compound, exhibits similar behaviour. In solution at low temperature (‐60°C) the two phenyl rings of the ligand are diastereotopic. In contrast, the triisopropylphosphane derivative [Au[NHCPh2](PiPr3)]+BF4− (5) is rigid on the NMR time scale, even at 25°C. Thbe solid‐state structures of 2, 3, 4, and 5 have been determined by single‐crystal X‐ray diffraction. Compound 2 crystallizes in the ionic form with discrete Au … Au bonded ion pairs [Au[NHC(NMe2)2]2]+ [AuBr2]− [Au … Au 3.1413(8) Å]. The cations of 3, 4, and 5 show the [Au(PPh3)]+ units N‐coordinated to the imino groups, with the nitrogen atoms in a trigonal‐planar configuration.
Reactivity of the Heavier Group‐13 Monochlorides [{CH(SiMe3)2}2AlCl], InCl, TlCl, and of the Elements Ga and Hg Towards the Unsupported Ni‐Ni Bond of [{(η5‐Cp)Ni(PEt3)}2] — A Straightforward Synthetic Approach to the Synthesis of Mixed Main‐Group/Transition‐Metal Clusters Containing Unsupported Metal‐Metal Bonds
Authors: Schneider Jörg J. , Denninger Uwe , Hagen Jörg , Krüger Carl , Bläser Dieter , Boese Roland 
Published: July 2007

AbstractThe dinuclear compound [{(η5—Cp)Ni(PEt3)}2] (1) containing an unbridged Ni‐Ni bond reacts with the heavier group 13 monochlorides [{CH(SiMe3)2)2}AlIIICl], InCl, and TlCl by scission of the metal‐metal bond. In the case of InCl and TlCl the chloro‐bridged dimmers [{(η5‐Cp)Ni(PEt3)2ECl2Ecl}2] (E = In 2, Tl 5) were formed. The Tl compound 5 is unstable and decomposes via disproportionation a and formation of the halogen‐free Tl [III] compound [{(η5‐Cp)Ni(PEt3)}3Tl] (6). 2 can be dehalogenated with activated magnesium to yield the halogen‐free In [III] compund [{(η5‐Cp}Ni(PEt3)}3In] (4). The Ga analogue of 4 and 6 [{(η5‐Cp)Ni(PEt3)}3Ga] (7) is accessible by a conproportionation of 1 with Ga metal in refluxing THF. In contrast to InCl and TlCl the aluminium (III) monochloride [{CH(SiMe3)2}2AlCl] reacts with 1 by a ligand redistribution reaction and formation of the salt [{(η5‐Cp)Ni(PEt3)2]+‐[{CH(SiMe3)2]2AlCl]2−. (8). Elemental Hg or Mg amalgam show the same activity as elemental Ga towards 1 and insert into the NiNi bond by forming the linear Hg‐bridged complex [(n3‐Cp)Ni(PEt3)]2Hg] (9). The molecular structures of 2, 4, 8, and 9 were determined by X‐ray crystallography. The In atom in 4 has a distorted trigonal‐planar configuration with the central In atom being surrounded by three [(n5‐Cp)Ni(PEt3)] fragments. 4 represents the first Ni‐In cluster containing exclusively unsupported In—Ni bonds, as well as the first carbonyl‐free Ni—In cluster. On the basis of spectroscopic data the same structure is assigned to the Ga and Tl analogues of 4. The NiHgNi arrangement in 9 is exactly linear, as determined by X‐ray crystallography.
Hydrocarbon‐Bridged Metal Complexes, XLI. Addition of Aniline Tricarbonyl Chromium Complexes to the Cyclohexadienyl Ligand of (μ5‐C6H7)M(CO)3+ (M = Fe, Ru)
Authors: Bentele Hans‐Jörg , Sünkel Karheinz , Beck Wolfgang 
Published: July 2007

AbstractThe addition of aniline tricarbonyl chromium complexes (η6‐C6H4(R)NHR1)Cr(CO)3 (RH, CH3; R1H, CH3) to [(n5‐C6H7)M(CO)3]+ (MFe, Ru) gives the heterobimetallic ligand‐bridged complexes (OC)3Cr(n6‐C6H4(R)N(R1)C6H7‐n4)M(CO)3. The structure of (OC)3Cr(n6‐C6H4(CH3)N(H)‐C6H7‐n4)Ru(CO)3 has been determined by X‐ray diffraction.