bluuebunny/crossref_metadata_2025_split huggingface dataset:
Oligophosphane Ligands, XLI. Oxidative Additions of Transition Metal–Hydrogen Bonds: Reactions of CpM(CO)3H (M = Mo, W) with [tBuP(CH2CH2CH2PPh2)2]M′Cl(M′ = Rh, Ir)
Authors: Dahlenburg Lutz , Halsch Eva , Moll Matthias , Höck Niels 
Published: July 2007

AbstractTreatment of (PP2)IrCl[PP2 = tBuP(CH2CH2CH2PPh2)2] with an equimolar quantity of CpM(CO)3H (M = Mo, W) or with HCl in THF resulted in smooth protonation of the d8 substrate producing [(PP2)Ir(H)Cl]X {X– = [CpMo(CO)3]– (1), [CpW(CO)3]– (2), Cl– (3)}. Combination of (PP2)IrCl and CpM(CO)3H in a 2:1 stoichiometry gave (PP2)Ir(H)Cl2 (7) together with [(PP2)IrCO]‐[Mo(CO)3Cp] (8) or [(PP2)IrCO][W(CO)3Cp] (9). The rhodium analogues (PP2)Rh(H)Cl2 (4), [(PP2)RhCO][Mo(CO)3Cp] (5), and [(PP2)RhCO][W(CO)3Cp] (6) were obtained similarly from (PP2)RhCl and CpM(CO)3H. Structural assignments for [(PP2)Ir(H)Cl]+ and (PP2)M′(H)Cl2 (M′ = Rh, Ir) as diastereomers in which the hydrido ligand and the tBu substituent on the central phosphorus atom are located on the same side or on opposite sides of the PP2 reference plane of the meridionally bound tBuP(CH2CH2CH2PPh2)2 ligand are made on the basis of (i) correlations with known structures and reactivities of similar [(RP(CH2CH2CH2PR′2)2M′(H)Cl]+ cations and (ii) an X‐ray structure determination of 4. The crystal structure analysis of a [(PP2)RhCO]+ salt, closely related to 5/6 and 8/9, [(PP2)Rh(CO)][OCO2H] (10), demonstrates that in the solid state the four‐coordinate [(PP2)RhCO]+ cation and its counterion exist as essentially charge‐neutralized Rh ⃛O‐contacted ion pairs, two of which are linked by OH ⃛O bridges to centrosymmetric dimers. Ion pairing was also observed by IR spectroscopy for THF solutions of metalates 5/6 and 8/9.
New β‐Amino Alcohols as Chiral Ligands for the Catalytic Enantioselective Reduction of Prochiral Ketones and the Nucleophilic Addition of Diethylzinc to Benzaldehyde
Authors: Peper Viola , Martens Jürgen 
Published: July 2007

AbstractNew optically active β‐amino alcohols, derived from various acyclic and cyclic amino acids with alkyl groups on the carbinol carbon atom, were used in the enantioselective reduction of prochiral ketones. The attachment of alkyl groups to the nitrogen atom of the catalyst (R)‐1b was shown to influence favorably the enantioselectivity of the addition of diethylzinc to benzaldehyde. In both cases the resulting secondary alcohols were obtained in moderate to high optical yields.
Synthese und Kristallstrukturen der Amido‐Komplexe [Na(12‐Krone‐4)2][M{N(SiMe3)2}3] mit M = Mn, Fe und Co
Authors: Putzer Markus A. , Neumüller Bernhard , Dehnicke Kurt , Magull Jörg 
Published: July 2007

Syntheses and Crystal Structures of the Amido Complexes [Na(12‐Crown‐4)2][M{N(SiMe3)2}3] with M = Mn, Fe, and CoThe ionic amido complexes [Na(12‐crown‐4)2][M[N‐(SiMe3)2}3] with M = Mn (1), Fe (2) and Co (3) were prepared by the reaction of M[N(SiMe3)2]2 (M = Mn, Co) and Fe[N‐(SiMe3)2]3, respectively, with sodium bis(trimethylsilyl)amide in toluene solution in the presence of 12‐crown‐4. 1–3 were characterized by IR spectroscopy and by crystal structure determinations. The complexes consist of cations [Na(12‐crown‐4)2]+ with a sandwich‐like structure and anions [M{N(SiMe3)2}3]– in which the metal atoms are planarly coordinate by the three nitrogen atoms of the bis(trimethylsilyl)amido groups.
Silyl Triflates – Valuable Synthetic Materials in Organosilicon Chemistry
Authors: Uhlig Wolfram 
Published: July 2007

AbstractThe highly reactive silyl triflates R4–nSi(OSO2CF3)n are valuable materials in organosilicon chemistry. Numerous new triflate derivatives of mono‐, oligo‐, and polysilanes were prepared by stepwise substitution of trifluoromethylsulfonyl groups for phenyl groups or other leaving groups. Conversions of silyl triflates with nucleophiles proceed regioselectively and, in most cases, quantitatively at low temperatures with short reaction times. Therefore, silyl triflates are suitable reagents for the synthesis and functionalization of linear and cyclic oligosilanes. Novel polycarbosilanes, polysilylalkynes, and polysilylphenylenes, which show a regular alternating arrangement of silylene groups and organic units, were prepared from α,ω‐bis[(trifluoromethylsulfonyloxy)silyl]‐substituted compounds and dinucleophiles. Branched polysilanes and polysilynes were obtained by reductive coupling of polymeric silyl triflates with potassium‐graphite.
Structural and Electrochemical Comparison of NiII in an N2S2 Plane with Two, One and No Axial Ligands: Isolation and Characterization of a Five‐Coordinate Nickel(II) Complex
Authors: Buonomo Rizalia M. , Reibenspies Joseph H. , Darensbourg Marcetta Y. 
Published: July 2007

AbstractAddition of two equivalents of benzyl bromide to [N,N′‐bis(2‐mercaptoethyl)‐1,5‐diazacyclooctane]nickel(II) (Ni‐1) produced the green dibenzyl dithioether complex [Ni‐1‐Bzl2Br2] structurally characterized by X‐ray crystallography as a six‐coordinate octahedral complex in a monoclinic crystal system and the P21/c space group. Benzylation of the methyl thioether/thiolate [(Ni‐1‐Me)+I– yielded the mixed benzyl/methyl dithioether [(Ni‐1‐BzlMe)Br]I, structurally characterized by X‐ray crystallography as a five‐coordinate square pyramidal nickel(II) complex with a Ni–Br distance of 2.451 Å. The complex crystallizes in the orthorhombic Cmca space group. The latter is the first nickel(II) pentacoordinate complex isolated for the N,N′‐bis(2‐mercaptoethyl)‐1,5‐diazacyclooctane (daco) ligand. Structural comparison of these two complexes with the square‐planar dimethyl compound [Ni‐1‐Me2]I2 found an expansion of the N2S2 plane upon addition of axial ligands. The five‐coordinate nickel complex showed a displacement of the Ni ion from the N2S2 plane by 0.43 Å toward the axial bromide ligand, a common observation of pentacoordinate complexes of this ligand with metals such as Zn and Fe. Electrochemical studies as well as the X‐ray crystal structures for complex [Ni‐1‐Bzl2Br2] and [(Ni‐1‐BzlMe)Br]I are presented and discussed in detail.
Cyclobutadiene Complexes, XII. Alkynyl‐Substituted Tricarbonyl(cyclobutadiene)iron Complexes: Stille Coupling of Iodocyclobutadiene Complexes with Stannylalkynes
Authors: Bunz Uwe H. F. , Wiegelmann‐Kreiter Jutta E. C. 
Published: July 2007

AbstractThe synthesis of mono‐, di‐, tri‐ and tetraalkynylated tricarbonyl(cyclobutadiene)iron complexes is accomplished by a repetitive metalation/iodination/coupling sequence. Application of this sequence leads to the synthesis of oligomeric cyclobutadiene complexes with various topologies, inter alia to the synthesis of a perethynylated dimer 24. Alternatively a one‐step coupling procedure (Stille‐Farina) has been used to synthesize tetraalkynylated tricarbonyl(cyclobutadiene)‐irons 26.
Silver(I) Sandwich Complexes of Oxa‐Crowned Derivatives of Dithiomaleonitrile
Authors: Drexler Hans‐Joachim , Reinke Helmut , Holdt Hans‐Jürgen 
Published: July 2007

AbstractThe coordination chemistry of the four oxa‐crowned derivatives of dithiomaleonitrile mn‐12S2O2, mn‐15S2O3, mn‐18S2O4, and mn‐21S2O5 as well as of the acyclic bis(methylthio)maleonitrile mn‐S2 with AgI was investigated by X ray structural and spectroscopic methods. The 2:1 complexes (ligand/AgI) [Ag(mn‐12S2O2)2]PF6, [1]PF6, [Ag(mn‐15S2O3)2]PF6, [2]PF6, and [Ag(mn‐S2)2]PF6, [6]PF6, and the 1:1 complexes [Ag(mn‐15S2O3)]ClO4, [3]ClO4, [Ag(mn‐18S2O4)]PF6, [4]PF6, and [Ag(mn‐21S2O5)]PF6 [5]PF6, were obtained with AgPF6 or AgClO4 in MeOH. The stoichiometry of the macrocyclic AgI complexes and the coordination mode of mn‐S2On+1 coronands (n = 1–4) is determined by the length of the macrocyclic oligoethylene chain. – The mn‐crown dithioethers mn‐12S2O2 and mn‐15S2O3 form with AgPF6 the new sandwich complexes [Ag(mn‐12S2O2)2]PF6, [1]PF6, and [Ag(mn‐15S2O3)2]PF6, [2]PF6. [1]PF6 crystallises in the triclinic space group P1. In the centrosymmetric cation [1]+ each mn‐12S2O2 ligand is coordinated to the AgI centre in an endo manner via both S atoms and one O atom. The distance of the second O atom of mn‐12S2O2 to AgI is somewhat longer than a normal Ag–Oether bond. The overall environment around AgI in [1]+ is that of a distorted cubic S4O4 set of donors. [2]PF6 crystallises in the monoclinic space group C2/c. In the centrosymmetric cation [2]+ silver(I) is planar‐coordinated by the four S atoms of both mn‐15S2O3 molecules. The six O atoms of both mn‐15S2O3 ligands show only long‐range interactions to the AgI ion. They surround AgI almost vertically to the planar S4 set of donors in a crown‐like manner. – The crystal structures of the 1:1 complexes [Ag(mn‐18S2O4)]PF6, [4]PF6, and [Ag(mn‐21S2O5)]PF6, [5]PF6, consist of linear chain polymers. [5]PF6 forms an N‐bridged chain polymer of endocyclic [Ag(mn‐21S2O5)]+ units with S1O4NNitrile coordination at the AgI centre. In the 2:1 complex [Ag(mn‐S2)2]PF6, [6]PF6, each mn‐S2 acts as a monodentate NNitrile donor. – 13C‐NMR studies in nitromethane solution confirm that the AgI ions in the complexes of the mn‐crown dithioethers remain coordinated. However, the AgI ion in complex of mn‐S2 is decoordinated.
(Di‐tertbutylmethylsilyl)amide – a Building Block for Azasilacyclobutane Synthesis
Authors: Ruwisch Lutz , Klingebiel Uwe , Rudolph Stefanie , Herbst‐Irmer Regine , Noltemeyer Mathias 
Published: July 2007

AbstractDi‐tert‐butylmethylsilylamide reacts with n‐BuLi to give the tetrameric lithium di‐tert‐butylmethylsilylamide 1. Reactions of lithium (di‐tert‐butylmethylsilyl)amide 1 with SiF4 give the mono‐ (2), bis‐ (3), tris‐ (4), and tetrakis‐ (5) ‐[(di‐tert‐butylmethylsilyl)amino]silanes. Lithiated 3 reacts with Me3SiCl to form (di‐tert‐butylmethylsilyl‐trimethylsilyl)amino‐(di‐tert‐butylmethylsilyl)amino‐difluorosilane (6); the 1,3‐diaza‐2,4‐disilacyclobutane 7 is obtained by LiF elimination. The lithium derivative of 6 (compound 8) crystallizes with formation of a (SiFNLi) four‐membered ring system. The 19F‐NMR spectrum proves that the Li–F bond fluctuates in solution. Reactions of 1 with (Me3Si)2C(SiF3)2 afford different products (9, 10) by controlling the reaction sequence. An excess of 1 reacts to give a four‐membered CSi2N ring system, the 1‐(di‐tert‐butylmethylsilyl)‐2,4‐bis‐[(di‐tert‐butylmethylsilyl)‐amino]‐2,4‐difluoro‐3‐bis(trimethylsilyl)‐1‐aza‐2,4‐disila‐cyclobutane (9), disubstitution with formation of bis[(di‐tert‐butylmethylsilyl)aminodifluorosilyl]bis(trimethylsilyl)methane (10) occurs in a molar ratio of 2:1. The cyclodisilazane 11 is obtained from dilithiated 10 in an intramolecular interconversion reaction. The crystal structures of 1, 8, 9, and 11 are reported.
Metall‐π‐Komplexe von Benzolderivaten, 50. Arylborane als Sandwichliganden: Darstellung von [(iPrO)2B(η6‐Ph)]2M und [Mes2B(η6‐Ph)]2M (M = V, Cr). Redoxeigenschaften und EPR Untersuchung M(d5)‐konfigurierter Neutralkomplexe sowie Bor‐zentrierter Radikalanionen
Authors: Elschenbroich Christoph , Kühlkamp Peter , Koch Jürgen , Behrendt Andreas 
Published: July 2007

Metal π Complexes of Benzene Derivatives, 50. – Arylboranes as Sandwich Ligands: Preparation of [(iPrO)2B(η6‐Ph)]2M and [Mes2B(η6‐Ph)]2M (M = V, Cr). Redox Properties and EPR Study of M(d5) Neutral Complexes and Boron‐Centered Radical AnionsBis(η6‐arene)metal complexes bearing peripheral boryl substituents have been prepared by means of metal‐atom ligand‐vapor cocondensation leading to [(iPrO)2B‐η6‐C6H5]2Cr (7) and [(iPrO)2B‐η6‐C6H5]2V (8) as well as by lithiation and subsequent reaction with Mes2BF with formation of [Mes2B‐η6‐C6H5]2Cr (11) and [Mes2B‐η6‐C6H5]2V (12). According to the NMR spectra, rotation about the η‐C–BR2 bonds in 7 and 11 is free at 25°C, restrictions setting in at –85°C. The neutral radicals 8• and 12• have been studied by EPR spectroscopy: despite of the profound difference in the electron‐accepting properties of the groups (iPrO)2B‐ and Mes2B, the hyperfine coupling constants a(51V) differ by 5% only; the extent of perturbation of the electronic structure manifests itself more clearly in the g tensor, which is tetragonal for 8 but orthorhombic for 12, the degeneracy of the LUMO's e1g being raised in the latter. Cyclovoltammetry on 11 exhibits reversible oxidation as well as reduction processes. Reduction which, according to EPR, is ligand‐centered, occurs in two steps which are separated by the redox splitting ΔE1/2 = 570 mV. This value, which is a measure of electronic communication between the two Mes2B groups, lies between those of 1,4‐bis(dimesitylboryl)benzene (δE1/2 = 690 mV) and 4,4′‐bis(dimesitylboryl)biphenyl (ΔE1/2 = 270 mV). The EPR spectrum of the radical anion 11−• reveals hyperfine coupling to one boron nucleus of a magnitude very similar to that of the free ligand radical anion Mes2BC6H. Therefore, reduction of 11 is ligand‐centered, and an intramolecular electron exchange between the boron centers is slow on the EPR time scale. As inferred from the observation of the hyperfine interactions a(53Cr) and a(1H), oxidation of 11 is metal‐centered; relative to parent bis(η6‐benzene)chromium (9), the two Mes2B groups cause an anodic shift of 290 mV for the couple 11+/0. The radical cations 11+• are prone to protodeborylation, in this aspect resembling the respective silyl derivatives.
Stepwise Insertion of Alkylisocyanides into the Metal‐Alkyne Bond of Half‐Sandwich Type Rhodium Complexes: Synthesis and Structural Characterization of Metallacyclobutenes and Metallacyclopentenes
Authors: Werner Helmut , Heinemann Anja , Windmüller Bettina , Steinert Paul 
Published: July 2007

AbstractThe cyclopentadienyl complexes [C5H5Rh(RCCR′)(SbiPr3)] (5–8), which were prepared from trans‐[RhCl‐(RCCR′)(SbiPr3)2] (1–4) and NaC5H5 and which contain a labile Rh–SbiPr3 bond, reacted with CO and CNR″ (R″ = Me, tBu) to give the carbonyl and isocyanide derivatives [C5H5Rh(RCCR′)(CO)] (9–11) and [C5H5Rh(RCCR′)‐(CNR″)] (12–16), respectively. On treatment of 12 (R = R′ = Ph; R″ = Me) with SbiPr3, the metallacyclobutene complex [C5H5Rh{κ2(C,C}‐C( = NMe)CPh=CPh}(SbiPr3)] (17) was formed; it reacts with excess CNMe or CNtBu to yield the metallacyclopentenes [C5H5Rh{κ2(C,C)‐C(NMe)CPhCPhC‐(NR)}(CNR)] (18, 19). Similar compounds 20–23 containing a five‐membered RhC4 metallacycle were prepared either from [C5H5Rh(RCCR′)(SbiPr3)] (7, 8) or [C5H5Rh‐(PhCCPh)(CNtBu)] (14) and excess isocyanide. The crystal and molecular structures of 17 and 18 (R = Me) have been determined.
Semiconductor‐Catalysed Photoaddition: γ,δ‐Unsaturated Amines from Cyclopentene and Schiff Bases
Authors: Schindler Wolfram , Knoch Falk , Kisch Horst 
Published: July 2007

AbstractIrradiation of methanolic cadmium sulfide suspensions in the presence of Schiff bases and cyclopentene opens an easy access to new γ,δ‐unsaturated amines. Their formation can be described as a kind of paired photoelectrolysis induced by the photogenerated electron‐hole pair trapped at reactive surface sites of CdS. At the reductive site the imine is converted to an α‐aminobenzyl radical by a proton‐coupled electron transfer, while at the oxidative site cyclopentene is transformed to the cyclopentenyl radical through deprotonation of the intermediate radical cation. C–C coupling of these radicals affords the addition products. Competitive dimerisation of the radicals produces hydrodimers of the imines and dehydrodimers of the olefin, as demonstrated in the case of 1‐phenylcyclohexene. Using optical active imines, we found no significant diastereoselectivity. In the absence of an olefin the alcoholic solvent was added to the imine. The molecular structure of one hydrodimer was resolved by X‐ray analysis. When CdS/Pt was used as photocatalyst, hydrolysis products of the imine were formed, suggesting involvement of an intermediate OH radical.
Synthesis, Spectroscopic Characterization, and Crystal Structure Determination of Cationic [(Cyclopentadienyl)dicarbonyliron](alkynyl)‐aminocarbene Complexes
Authors: Rück‐Braun Karola , Kühn Jörg , Schollmeyer Dieter 
Published: July 2007

Abstract(Alkynoyl)iron complexes 1, Cp(CO)2Fe(OCCCR) (R = CH3, Ph, SiMe3), were synthesized by applying a mixed anhydride procedure and transformed into the cationic methoxycarbene complexes 2, [Cp(CO)2 Fe(C(OMe)CCR)+]‐[PF6–]. Primary amines H2NR′ react with the methoxycarbene complexes to furnish exclusively cationic aminocarbene complexes 3, [Cp(CO)2 Fe(C(NHR′)CCR)+][PF6–], or (2‐methoxyvinyl)aminocarbene complexes 5. The spectroscopic properties of the new complexes are discussed. The (alkynyl)‐aminocarbene complexes 3e and 3f were characterized by X‐ray crystal structure analysis.
Preparation, Properties, and Reactions of Metal‐Containing Heterocycles, XCV. Transition‐Metal‐Mediated Cyclocotrimerization of Selenophosphinites with Activated Alkynes
Authors: Lindner Ekkehard , Bosch Elke , Fawzi Riad , Steimann Manfred , Mayer Hermann A. , Gierling Karlheinz 
Published: July 2007

AbstractSelenophosphinito complexes (OC)4Mn(η2‐Se\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}PR21) (2a, b) [R1 = cyc‐Hex (a), tBu (b)] are formed by the reaction of BrMn(CO)5 with the phosphane selenides R21HPSe (1a, b) in the presence of the auxiliary base Et(iPr)2N. According to an X‐ray structural analysis, 2a crystallizes in the space group \documentclass{article}\pagestyle{empty}\begin{document}$ P\bar 1 $\end{document} with Z = 2. The dimeric complex [(OC)4Mn(μ‐Se\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}PMe2)]2 (4c) is not obtained in a straightforward way. Compound 4c is only obtained via the intermediate Br(OC)4Mn–Se\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}P(H)Me2 (3c) by HBr elimination with nBuLi. Complex 3c is formed by replacement of carbon monoxide in BrMn(CO)5 by Me2HPSe (1c). A dissociative equilibrium between [(OC)4 Mn(μ‐Se\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}PMe2)]2 (4c) and the monomeric species (OC)4Mn(\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}2‐Se\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}PMe2) was not observed. The cyclocotrimerization of the >P\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}Se function with the activated alkynes ZCCZ [Z = CO2R2; R2 = Me (d), Et (e), iPr (f), cyc‐Hex (g)] was successful only in the case of the cyclohexyl derivative 2a to give the selenaphosphamanganabicycloheptadienes 5d – g. An X‐ray structural analysis proved that 5d crystallizes in the space group \documentclass{article}\pagestyle{empty}\begin{document}$ P\bar 1 $\end{document} with Z = 2. Under CO pressure 5d was degraded to the selenophene 6.
A YBa2 Cluster Based on Simple Ligands (OtBu)
Authors: Borup Björn , Streib William E. , Caulton Kenneth G. 
Published: July 2007

AbstractReaction of a 1:2 mixture of Y[N(SiMe3)2]3 and Ba[N(SiMe3)2]2 with tBuOH (8 mol equivalents) in Et2O at 25°C yields YBa2(OtBu)7(tBuOH), which has a triangular structure with two μ3‐OtBu and three μ2‐OtBu ligands, one terminal OtBu on Y and on one Ba, and one terminal tBuOH on the second Ba. All metals are thus five‐coordinate. The crystal structure is comprised of chains of triangles of triangles held together by hydrogen bonds from tBuOH of one YBa2 unit to the terminal OtBu on Ba of the next YBa2 unit. This serves as support for the idea that, in certain cases, the heterometallic alkoxide product from alcoholysis of a mixture of two metal complexes can faithfully duplicate the global solution metal stoichiometry.
Self‐Assembly of Substituted 6‐Hydroxy‐trans‐3‐hexenoic Acids – Formation of Extended Ribbon‐Like Structures by Hydrogen Bonds
Authors: Strauch Hans Christian , Erker Gerhard , Fröuhlich Roland 
Published: July 2007

AbstractThe substituted 6‐hydroxy‐trans‐3‐hexenoic acids 2a and 2b are prepared by an organometallic template reaction involving a sequence of CC coupling reactions between a CO2 equivalent, butadiene, and 3‐cyclopenten‐1‐one or 3,4‐diphenyl‐3‐cyclopenten‐1‐one, respectively. In the crystal 2a assembles to form an infinite ribbon‐type structure, exhibiting an alternating array of 12 and 18 atom‐containing loops. The former are each constructed by an alternating CO2H/OH/CO2H/OH sequence, originating from four different monomeric units, that are linked together by means of hydrogen bonds. Two complementary ribbons of 2a are connected by van der Waals interactions to form staples that constitute the microscopic building blocks of the true (2a)n structure in the crystal. Stacks of cyclopentene π bonds are oriented inside the columnar structure of 2a. Acid 2b also forms a related ribbon‐like assembly in the solid state. Here the bulky 3,4‐diphenylcyclopentadienylidene moieties are oriented laterally at the ribbons, and van‐der‐Waals interactions with adjacent ribbons construct a three‐dimensional hydroxyhexenoic acid network.
Syntheses, Structures, and Reactivity of 1‐Phosphanylnaphth‐2‐ols
Authors: Heinicke Joachim , Kadyrov Renat , Kindermann Markus K. , Kloss Matthias , Fischer Axel , Jones Peter G. 
Published: July 2007

AbstractP‐tertiary or amino‐substituted 1‐phosphanylnaphth‐2‐yl silyl ethers 3 are synthesized by stepwise reaction of lithium 1‐lithio‐2‐naphtholate 1 with chlorophosphanes and ClSiMe3. The free phosphanylnaphthols 4 are prepared by alcoholysis. As established by characteristic coupling constants and X‐ray structural analyses (of 3c, 4c), 3 exhibit in solution and in the solid state a cis‐bisecting conformation, whereas 4 prefers the opposite trans‐bisecting arrangement, allowing easy protonation and formation of chelate complexes. Substitution reactions of phosphanylnaphtholates 2 with Ph2PCl and formation of chelate complexes LNi‐η5‐Cp and L2Pd are described. Attempts to prepare secondary and primary phosphanylnaphthols failed because of facile cleavage of the P–C(naphthyl) bond in PH‐substituted 1‐phosphanylnaphth‐2‐ols.
Control of the SO2 Coordination Mode at the (Monochelate)rhodium Complex ClRh(P∼O) with the Hemilabile Ligand Cy2PCH2CH2OCH3
Authors: Lindner Ekkehard , Keppeler Berthold , Fawzi Riad , Steimann Manfred 
Published: July 2007

AbstractThe SO2 coordination mode at the rhodium complex [ClRh(P∼O)()] (1) [  η2(O,P)‐chelated Cy2PCH2CH2OCH3 ligand; P∼O  1(P)‐coordinated] is controlled by the hemilabile ligand Cy2PCH2CH2OCH3 and shows a dependence on the polarity of the solvent. In polar organic solvents (e.g. acetone) the addition of sulfur dioxide results in the formation of a trigonal‐pyramidal oriented SO2 group in [ClRh(η1‐SO2)(P∼O)()] (2a). However, in nonpolar media (e.g. n‐hexane) a trigonal‐coplanar geometry of the SO2 unit in [ClRh(η1‐SO2)(P∼O)2] (2b) is favored.
Übergangsmetall‐Stannyl Komplexe, 10[1]. Molybdocen‐ und Wolframocen‐Derivate mit zwei unterschiedlichen Liganden der 4. Hauptgruppe
Authors: Seebald Steffen , Möller Frank , Schubert Ulrich , Kickelbick Guido 
Published: July 2007

Transition‐Metal Stannyl Complexes, 10 – Molybdocen and Wolframocen Derivatives with Two Different Main‐Group‐4 LigandsReactions of Li[Cp2MSnPh3] (M  Mo, W) with CH3I, BuBr, PhCH2Br, PhC(O)Cl or Br(CH2)nBr (n  4,5) yield Cp2M(R)SnPh3 [R  CH3, Bu, CH2Ph, C(O)Ph, (CH2)nBr], while tBuBr or CH3C(O)Cl give the hydrido complexes Cp2M(H)SnPh3. A silyl stannyl complex is only obtained from Li[Cp2WSnPh3] and Me3SiOSO2CF3, but not with Me3SiCl or from the anionic Mo complex. In contrast, the reactions of chlorostannanes provide the bis(stannyl) complexes Cp2M(SnR′3)SnPh3 or Cp2M(SnR′2Cl)SnPh3. R/Cl exchange at the tin atom is observed when an excess of the chlorostannane is used. Upon reaction of Li[Cp2MSnPh3] with Ph3PbCl only Cp2M(PbPh3)SnPh3 is formed, while a mixture of Cp2M(PbMe3)SnPh3 and Cp2M(PbMe2Cl)SnPh3 is obtained with Me3PbCl due to redistribution reactions. The structures of Cp2W(SnPh3)C(O)Ph, Cp2W(SnPh3)SntBu2Cl and Cp2W(SnPh3)PbMe2Cl were determined by X‐ray structure analyses.