bluuebunny/crossref_metadata_2025_split huggingface dataset:
Hybrid Diborolyl/Dicarbaboranyl Triple‐Deckers: [(μ5‐Cyclopentadienyl)cobalt][μ,η5‐1,3‐diborolyl)cobalt[dicarba‐heptacarboranyl and ‐nonacarboranyl Complexes
Authors: Weinmann Wolfgang , Metzner Frank , Pritzkow Hans , Siebert Walter , Sneddon Larry 
Published: July 2007

AbstractThe three‐component reactions of the sandwich anion [(η5‐C5H5)Co(η5‐Et4MeC3B2)]− (4‐H)− and various dicarbaborane anions with metal halides are described. Thus, (4‐H)−, nido‐4,5‐C2B6H9− (5), and CoCl2 form the 30VE triple‐decker [η5‐C5H5)Co(μ,η5‐Et4MeC3B2)Co(η5‐2,3‐C2B5H7)] (6). An analogous three‐component reaction of (4‐H)−, arachno‐4,5‐C2B7H−2 (7), and CoCl2 yields [(η5‐C5H5)Co(μ,η5‐Et4‐MeC3B2)Co(η5‐6,9‐C2B7H9)] (8), which rearranges on heating (57°C) to give the 1,6‐isomer [(η5‐C5H5)Co(μ,η5‐Et4‐MeC3B2)Co(η5‐1,6‐C2B7H9)] (9) with an activation energy of 127 · 10 kJ/mol. The thermodynamically most stable 1,10‐isomer [(η5‐C5H5)Co(μ,η5‐Et4MeC3B2)Co(η5‐1,10‐C2B7H9)] (10) is formed by heating of 9 at 180°C. An alternative route to 9 is provided by the reaction of arachno‐6,8‐C2B7H12− (11) with (4‐H)− and CoCl2. The analogous reaction with RhCl3 leads to [(η5‐C5H5)Co(μ,η5‐Et4MeC3B2)Rh(1,6‐C2B7H9)] (15) and unexpectedly to closo‐2‐(η5‐C5H5)Co(1,6‐C2B7H9) (12). The constitutions of the described compounds are derived from their 1H‐, 11B‐, 13C‐NMR data as well as mass spectral data. The X‐ray structure analyses of 10 and 12 show the expected metal complexes with a CoC2B7H9 framework. In 10 the carbon atoms occupy the capping positions of a bicapped square antiprism. The short Co‐Co distance of 3.20 Å is in agreement with the 30VE configuration of 10. In both 10 and 12, the distance from the cobalt to the four‐coordinate C4 is the shortest Co‐to‐cage atom distance.
Tripod‐Cobalt‐Formiat‐Komplexe in den Oxidationsstufen +II und +I
Authors: Sernau Volker , Huttner Gottfried , Scherer Johannes , Walter Olaf 
Published: July 2007

Tripod‐Cobalt Formate Complexes of Oxidation States +II and +IThe syntheses of the (tripod)cobalt formate complexes [(tri‐pod)Co(O2CH)]n+ (1/1+; n = 0, 1; tripod = CH3C(CH2PPh2)3) are presented. The structures are established by X‐ray analyses as well as the usual analytical techniques.
Thermally Stable Self‐assembling Open‐Frameworks: Isostructural Cs+ and (CH3)4N+ Iron Germanium Sulfides
Authors: Bowes Carol L. , Lough Alan J. , Malek Andrzej , Ozin Geoffrey A. , Petrov Srebri , Young David 
Published: July 2007

AbstractHere we report on investigations that have revealed for the first time that the Cs+ ion templates the same metal germanium sulfide open‐framework as (CH3)4N+ (TMA+), and that metal complexing agents enhance crystal size by at least two orders of magnitude. The synthesis, structures and thermal properties of Cs2FeGe4S10 ·× H2O and TMA2FeGe4S10 are also described. Both have 3D zinc blende‐type open‐framework structures. These materials have the same connectivity as TMA2MnGe4S10. The tetrahedral sites in the lattice are alternately substituted by pseudo‐tetrahedral Fe2+ and adamantanoid Ge4S104‐ building blocks, covalently linked together by Fe(μ‐S)Ge bridge bonds, to give a tetragonal unit cell. The charge‐balance of the anionic framework [Fe‐Ge4S10]2‐ is maintained by either Cs+ or TMA+ ions in the cavity spaces. Synthesis of these materials demonstrates an interesting example of a self‐assembly process in which a 3D framework is built from molecular precursors. Water adsorption‐desorption cycling from room temperature to 200 °C reveals framework flexibility between larger and smaller tetragonal unit cell 14 isotypes. The compound TMA2FeGe4S10 is stable in nitrogen at 350 °C and under vacuum at 450 °C. The corresponding temperatures for Cs2FeGe4S10 are 530 °C and 630°C; it is stable on cooling to room temperature under vacuum, and after subsequent exposure to air. Six hundred thirty degrees celsius is the highest recorded temperature at which the integrity of a non‐oxide framework has been maintained. The framework stability and flexibility of “all‐inorganic” Cs2FeGe4S10 provides an encouraging example for researchers interested in developing sulfide‐based framework materials with practical applications.
Cäsium‐Fluor‐Vierringe als Strukturmotiv in Cäsium‐Triorganofluorometallaten der Gruppe 13
Authors: Werner Bert , Neumüller Bernhard 
Published: July 2007

Cesium‐Fluorine Four‐Membered Rings as Structural Motive in Cesium Triorganofluoro Metalates of Group 13The reactions of AlMe3, GaMe3, and InMe3 with CsF in acetonitrile furnish the corresponding trimethylfluoro metalates Cs[Me3MF] (1: M = Al, 2: M = Ga, 3: M = In). The salt‐like compounds 1 – 3 were characterized by NMR, IR, and MS techniques as well as by X‐ray structure analysis. Cs2F2 four‐membered rings are the structure‐dominating units in all three compounds. Compound 1 consists of puckered layers of weakly associated Cs2F2 rings parallel to (100), while the four‐membered rings in 2 form infinite ladder‐type chains. The Cs–F rings in 3 build up a heterocubane with a Cs4F4 core by ring stacking.
The Chemistry of ArsenicCarbon Multiple Bonds: Arsaalkenes and Arsaalkynes
Authors: Weber Lothar 
Published: July 2007

AbstractThe present article gives an account of the synthesis and structure as well as the spectroscopic and chemical properties of arsaalkenes R1AsCR2R3 and arsaalkynes RCAs. Arsaalkenes are significantly less stable and more reactive than the corresponding phosphaalkenes. Only one kinetically stabilized arsaalkyne has been described so far.
(tert‐Butoxy)aluminium and ‐gallium Hydrides
Authors: Veith Michael , Faber Stefan , Wolfanger Holger , Huch Volker 
Published: July 2007

AbstractThe crystal structures obtained by X‐ray methods of (tert‐ butoxy)alane and ‐gallane (tBuOMH2) are isotypic and are composed of discrete centrosymmetric dimers. The dimers arise from almost symmetrical AlOAl [1.810(3), 1.815(3) Å] and GaOGa [1.902(9), 1.908(9) Å] bridges forming a central rhombohedral four membered M2O2 cycle [OAlO 81.0(2)°, OGaO 78.6(5)°] with the metallic atoms in a distorted tetrahedral environment. When one of the hydride ligands on the metals is further substituted by tert‐butoxy, the formation of (tBuO)2AlH and (tBuO)2 GaH is observed. These two compounds crystallize in different lattices and space groups, but they are nevertheless very similar in their structure: the centrosymmetric M2O2 cycle is maintained [AlO 1.817(3), 1.817(3) Å; GaO 1.904(4), 1.907(4) Å] As expected, the terminal Al–O [1.675(3) Å] and GaO [1.783(4) Å] distances are considerably shorter than the bridging ones.
Interpretation of 31P‐NMR Coordination Shifts for Phosphane Ligands. Ab Initio ECP/DFT Study of Chemical Shift Tensors in M(CO)5L [M = Cr, Mo, W; L = PH3, P(CH3)3, PF3, PCl3]
Authors: Kaupp Martin 
Published: July 2007

AbstractThe 31P chemical shift tensors of the transition‐metal phosphane complexes M(CO)5PX3 (M = Cr, Mo, W; X = H, CH3, F, Cl) were studied using a combination of density functional theory and ab initio effective‐core potentials. The calculated isotropic shifts agree well with experimental results both for the free ligands and for the complexes, with the largest deviations occuring for the tungsten complexes. A breakdown of the computed phosphorus shielding tensors into contributions from localized molecular orbitals (LMOs) indicates that the positive coordination shift of PH3 and P(CH3)3 is due to increased paramagnetic contributions from the phosphorus lone pair (P‐M s̀ bonding) LMO to δ⊥. A similar increase of this contribution is found for PF3 and PCl3. However, for PCl3 complexes these terms are overcompensated by a reduction in the paramagnetic contributions from the P‐Cl bonds and by shielding contributions from metal‐centered orbitals. This results in a negative overall coordiantion shift. A partial cancellation is found with P(CH3)3 and with PF3. The changes in the 31P‐shift tensors of the same phosphane ligands upon protonation are qualitatively and quantitatively very different from the coordination shifts and do not provide good models for the latter.
Metal‐Catalyzed Oxidations, 4. The Reaction of Molybdenumperoxo Complexes with Brønsted and Lewis Acids
Authors: Thiel Werner R. 
Published: July 2007

AbstractNMR studies of the reaction of complexes of the type (L‐L)MoO(O2)2 (L – L= bidentate ligand) with strong Brønsted and Lewis acids prove that protons are transferred preferentially to an η2‐peroxo and not to the oxo ligand. This behavior in proton transfer reactions is one critical point of the catalytic activity of such complexes in olefin epoxidation. EH calculations on the model complex (NH3)2MoO(O2)2 support the spectroscopic investigations.
Conformation of tripod Metal Templates in CH3C(CH2PPh2)3MLn (n = 2, 3): Neural Networks in Conformational Analysis
Authors: Beyreuther Stefan , Hunger Johannes , Huttner Gottfried , Mann Susanne , Zsolnai Laszlo 
Published: July 2007

AbstractThe conformational space spanned by tripod metal templates CH3C(CH2Ph2)3M is analysed on the basis of the solid‐state structures of 82 tripodCo templates in compounds tripodCoL2 and tripodCoL3. Systematic analysis, including the techniques of conformational space group scatter graphs, principal‐component analysis, and partial least squares, reveals a series of basic regularities: The torsion of the phenyl groups is strongly linked to the torsional skew of the bicyclooctane‐type framework of the chelate cage. For one sense of this skew there are two classes of low‐energy conformation that differ by the helicity of the phenyl arrangement and by the degree of torsional skew in the chelate backbone. From the scatter graphs it is evident that a change in helicity may occur by one‐ or by two‐ring flip mechanisms. The basic regularities found by the above methods are also evident from the analysis of the same data by a neural network approach. The fact that these regularities are found for tripodCoL2 and tripodCoL3, irrespective of the widely different coligands L and crystal environments, means that the conformation of the tripod metal templates is governed by the forces acting within them and not so much by the forces imposed on them by their individual chemical or crystal environment. It is shown that the classifications, although derived from a data basis only containing Co compounds, are characteristic for tripod metal templates irrespective of the specific metal involved.
The First SiH Complex, Dihydridotetrakis(3‐picoline)silicon Dichloride–Tetrakis(chloroform), [H2Si(3pic)4]Cl2 · 4 CHCl3: Formation, Chemical Equilibria, and Structural Investigation by NMR Spectroscopy and Single‐Crystal X‐ray Diffraction
Authors: Fleischer Holger , Hensen Karl , Stumpf Thorsten 
Published: July 2007

AbstractBis(dichlorosilyl)amine reacts in chloroform solution with 2‐picoline to give H3SiCl, H2SiCl2, and HSiCl3, whereas with 3‐picoline the two hypervalent silicon compounds H2SiCl2‐(3pic)2 and [H2Si(3pic)4]Cl2 · 4 CHCl3 containing hexacoordinated Si atoms are formed. These complexes are in a chemical equilibrium with each other in chloroform solution, from which crystals of [H2Si(3pic)4]Cl2 · 4 CHCl3 could be isolated. The crystal structure of the latter was determined by single‐crystal X‐ray diffraction. The complex can be regarded as an “contact ion trio” of [H2Si(3pic)4]2+ and two Cl– ions. The N–Si bond lengths, r(Si–N) = 196.9(3) and 197.5(3) pm, are similar to those found in neutral hexacoordinated Si complexes. The data obtained from a 1H1H ROESY experiment suggest that dissolution has no significant impact on the molecular structure of [H2Si(3pic)4]Cl2 · 4 CHCl3.
New Bis(lithiomethyl)silanes: Building Blocks for Organosilanes
Authors: Strohmann Carsten , Lüdtke Silke , Wack Eric 
Published: July 2007

AbstractThe first high yield preparation of non π‐stabilized bis(lithio‐methyl)silanes was performed by the reductive cleavage of C–S bonds with electron transfer reagents. Bis[(phenylthio)‐methyl]silanes synthesized by the reaction of dichlorosilanes with [(phenylthio)methyl]lithium were transformed to the corresponding bis(lithiomethyl)silanes 7 by reaction with lithium naphthalenide (LiC10H8) or lithium p,p′‐di‐tert‐butyl‐biphenylide (LiDBB) as an electron transfer reagent and were characterized by their reaction with Bu3SnCl. The C–S bonds of bis[(phenylthio)methyl]silanes can be cleaved selectively making possible the introduction of two different groups. – The silicon atom plays a central role in the reactivity of the presented structural types. The bis(lithiomethyl)silanes are used as new building blocks for the preparation of organosilanes, Si–H‐functionalized organosilanes, and 1,3‐disilacyclobutanes containing SiCH2Si structural units.
Organoamido‐ and Aryloxo‐lanthanoids, 14. Organometallic Compounds of the Lanthanoids, 106. Synthesis and Characterisation of Complexes of Lanthanoid Pyrazolates with 1,2‐Dimethoxyethane and the X‐Ray Structures of (1,2‐Dimethoxyethane‐O1:O2)(1,2‐dimethoxyethane‐O1)tris(3,5‐diphenylpyrazolato)erbium(III) and catena‐Poly[tris(3,5‐di‐tert‐butylpyrazolato)‐μ‐(1,2‐dimethoxyethane‐O1:O2)‐neodymium(III)]
Authors: Cosgriff Joanna E. , Deacon Glen B. , Fallon Gary D. , Gatehouse Bryan M. , Schumann Herbert , Weimann Roman 
Published: July 2007

AbstractThe complexes [Ln(Ph2pz)3 (DME)2] and [Ln(tBu2pz)3 (DME)] (Ln = La, Nd, Er; Ph2pzH = 3,5‐diphenylpyrazole; tBu2pzH = 3,5‐di‐tert‐butylpyrazole; DME = 1,2‐dimethoxyethane) have been prepared by reaction of the lanthanoid metal with bis(pentafluorophenyl)mercury and the pyrazole in DME. The molecular structures of [Er(Ph2pz)3 (DME)2] (3) and [Nd(tBu2pz)3 (DME)]∞ (5) have been determined by X‐ray diffraction. Complex 3 has nine‐coordinate Er with three chelating Ph2pz ligands and one chelating and one η1‐bound DME. There is a trigonal prismatic arrangement of the oxygen donors and the centres of the N – N bonds. 5 was found to be a linear polymer with transoid DME ligands bridging Nd(tBu2pz)3 units in a novel manner. The centres of the N – N bonds (which are essentially coplanar with Nd), and the oxygen donor atoms adopt an arrangement intermediate between trigonal‐bipyramidal and square‐pyramidal [O – Nd – O 153.5(2)°].
Copper Coordination Polymers with Infinite Chloride Ion Channels and Different Directions of the Jahn‐Teller Distortion, Built from Tris(1,2,4‐triazolyl)borate as a Modified Tris(pyrazolyl)borate Ligand
Authors: Janiak Christoph , Scharmann Tobias G. , Günther Wulf , Hinrichs Winfried , Lentz Dieter 
Published: July 2007

Abstract[Co{HB(C2H2N3)3}2] reacts with an excess of CuCl2 in hot water with formation of ∞2[Cu2Cl2{μ3‐HB(C2H2N3)3}2 · 2 H2O] (7) or ∞3{[Cu2{μ4‐HB(C2H2N3)3} (μ‐OH)2]Cl · 6 H2O} (8), depending on the reaction time. 8 can also be obtained from [Cu{HB(C2H2N3)3}2] and CuCl2 in aqueous ammonia. The 2‐D double‐layer‐type coordination polymer 7 crystallizes in the orthorhombic space group P212121. The two different Cu(II) centers in the lattice are distinguished only be the direction of the Jahn‐Teller distortion. The following corresponding distances for the CuClN5 coordination sphere were found Cu1/Cu2–Cl = 2.572(2)/2.328(2), Cu1/Cu2–N = 2.585(5)/2.077(4); 2.000(4)/1.979(5); 2.100(5)/2.734(5); 2.005(4)/1.994(4); 2.024(5)/2.369(5). In the 3‐D coordination polymer 8 one of the two different Cu centers is chelated by the three endodentate nitrogen donors, while the other Cu center is coordinated by three exodentate nitrogen atoms. The coordination sphere is completed in both cases by two hydroxo bridges to symmetry‐related Cu centers. The metal‐ligand connectivity creates infinite channels with helical walls which contain the solvated chloride anions.
Synthesis and Structure of Mononuclear Titanium Complexes Containing ansa‐Aminopyridinato Ligands
Authors: Oberthür Markus , Arndt Perdita , Kempe Rhett 
Published: July 2007

AbstractA series of siloxane‐bridged bis(2‐aminopyridines) were synthesized from dichlorosiloxanes and 2‐aminopyridines in the presence of a base via nucleophilic substitution reactions. They were used, after deprotonation, as dianionic (ansa‐aminopyridinato) ligands to stabilize mononuclear titanium complexes with unusual coordination geometries. An X‐ray crystal structure analysis of one of the ligands and of a titanium complex proved mononuclearity and provided information about the binding mode of this novel type of ligands. Ethylene polymerization studies showed low activity, remarkable differences between structurally related complexes, and broad molecular weight distributions. Sterically less demanding substituents and a high basicity of the ligand increase polymerization activity.
Diboran(4)yl Groups as Ligands to Transition Metals
Authors: Braunschweig Holger , Ganter Beate , Koster Margot , Wagner Trixie 
Published: July 2007

AbstractReaction of Na[(Cp)Fe(CO)2] and Na[(Cp)W(CO)3] with B2(NMe2)2Cl2 yields the first transition metal‐substituted diboranes [Cl(Me2N)B–B(NMe2)M(Cp)(CO)n] [M(Cp)(CO)n  Fe(Cp)(CO)2, W(Cp)(CO)3] (1a, b). The compounds were characterized in solution by NMR methods and in the crystal by X‐ray structural determination.
Reaktionen des Tripod‐Co‐Templats CH3C(CH2PPh2)3Co(II) mit funktionalisierten Hydrazinen
Authors: Körner Volkmar , Vogel Sabine , Huttner Gottfried , Zsolnai Laszlo , Walter Olaf 
Published: July 2007

AbstractThe coordination behaviour of ligands having the same basic constitution RN=NC(=X)R′ (X  O, NR″, S) in their tripod cobalt derivatives has been analyzed. The ligands themselves may be considered as neutral heterodiene compounds and are in this respect vinylogues to diazenes RNNRy′. Two‐ electron reduction of these neutral species results in dianionic heterosubstituted heteroolefins RN‐ ‐NC(X‐)R′. Due to their redox ambiguity the oxidation state of the metal M in chelate complexes is not a priori evident. Compounds tripod [5: X, R′  O, Ph; 6; (X, R′)  (py); 7: X, R′  S, NH2] are best described as containing low‐spin Co(III) and dianionic ligands. Co(II) species are obtained with diethyl azodicarboxylate EtOOCNNCOOEt as the ligand. In the mononuclear compound, with only one nitrogen and one carbonyl oxygen of the ligand acting as donor groups, the neutral ligand is coordinated to give the high‐spin cobalt(II) species tripod (8). In the dinuclear compound 9 with both of the nitrogen atoms and carbonyl groups involved in coordination the dianionic ligand bridges two high‐spin cobalt(II) centers to give tripod (9) as a derivative with two fused five‐membered chelate rings. In addition to the conventional analytical techniques X‐ray structure analyses, cyclovoltametric measurements, magnetic susceptibility and ESR data are used to characterize the compounds.
Crystal Structures and Preparation of K2AgVS4 and Rb2AgVS4 by Using the Molten Flux Method: Low‐Dimensional Materials with Infinite Metal‐Ion‐Centered Tetrahedra Chains
Authors: Bensch Wolfgang , Dürichen Peter 
Published: July 2007

AbstractThe quaternary sulfides K2AgVS4 and Rb2AgVS4 crystallize as dark violet needle‐like crystals with a metallic lustre. Infinite Ag‐ and V‐centered tetrahedra sharing common edges are running parallel to the crystallographic a axis. The chains are separated by K+ or Rb+ ions which are in an eightfold environment. The tetrahedra are occupied in an ordered fashion. The Ag–V interatomic distances amount to 2.904(1) and 2.910(1) A, respectively, which is significantly larger than the sum of the ionic radii of Ag+ and V5+. Whereas the V–S distances are in the normal range, the average (Ag–S) distances are the shortest reported so far indicating strong covalent bonding between monovalent Ag+ and S2–. In addition, the title compounds represent very rare examples of AgS4 polyhedra with equidistant Ag–S bonds. The geometrical parameters within the tetrahedra chains are only slightly affected when K+ is replaced by the larger Rb+ demonstrating the rigidity of the bonding properties within the tetrahedra. The compounds are isotypic with the quaternary copper sulfide K2CuVS4 and the selenides K2CuMSe4 (M=Nb, Ta).
A Palladium‐Catalyzed Domino Coupling Process Leading to Annelated Pentafulvenes
Authors: Dyker Gerald , Nerenz F. , Siemsen P. , Bubenitschek P. , Jones Peter G. 
Published: July 2007

AbstractAnnelated pentafulvenes 2, 10, 13, and 14 are efficiently accessible by a palladium‐catalyzed domino coupling process of aryl substituted vinylic bromides 1, 9, 11, and 12, 5‐Membered palladacycles 3 are discussed as key intermediates.
Organmetallic Selenolates, IV. Reactions of MSeW(CO)3cp (M=Li, Na) with Organodi‐ and ‐tetrahalides – X‐ray Crystal Structures of C6H5CH2W(CO)3(η5‐C5H 5), μ‐[m‐C6H4{CH2SeW(CO)3(η5‐C5H5)}2], μ‐[p‐C6H4{CH2SeW(CO)3‐ (η5‐C5H5)}2], and C6H5CH[SeW(CO)3(η5‐C5H5)]2
Authors: Eikens Wolfgang , Jäger Stefan , Jones Peter G. , Laube Jörg , Th öne Carsten 
Published: July 2007

AbstractOrganotungsten‐selenolato complexes were prepared in moderate yields by insertion of selenium into the alkali metaltungsten bonds of MSeW(CO)3cp (M = Li, Na) and subsequent reactions with the organohalides o‐, m‐, and p‐ C6H4(CH2Br)2, C6H5CHBr2, m‐C6H4(CHBr2)2 and C6H5CCl3. The 77Se‐NMR data of the new complexes are discussed and compared with those of related complexes derived from organomonohalides. Moreover, the X‐ray crystal structures of C6H5CH2W(CO)3cp (1), μ‐[m‐C6H4{CH2SeW(CO)3cp}2] (3), μ‐[p‐C6H4{CH2SeW(CO)3cp}2] (4), and C6H5CH[SeW‐(CO)3cp]2 (5) were determined. In complex (1), the W–CH2 bond length is 2.374 Å; the W–Se bond lengths in the complexes 3, 4 and 5 are all in the range 2.625–2.655 Å, corresponding to W–Se single bonds.
Reactions of Lactams with Titanocene‐ and Zirconocene‐Alkyne Complexes as Elemental Steps in Catalytic Anionic Ring‐Opening Polymerization of Lactams
Authors: Arndt Perdita , Lefeber Claudia , Kempe Rhett , Tillack Annegret , Rosenthal Uwe 
Published: July 2007

AbstractDepending on the nature of the metal and the ring size, lactams react with titanocene and zircocene complexes of bis‐(trimethylsilyl)acetylene Cp2Ti(Me3SiC2SiMe3) and Cp2Zr‐(L)(Me3SiC2SiMe3) (L = Py, THF) to yield different products. In the reaction of Cp2Zr(Py)(Me3SiC2SiMe3) with N‐methyl‐€‐caprolactam a simple ligand exchange reaction occurs and the complex Cp2Zr(Me3SiC2SiMe3)[OH2)5] (1) was isolated. With β‐propiolactam the alkenyl‐amido complex Cp2)(SiMe3)][–NH2] (2) was obtained, which indicates that an agostic metal‐hydrogen interaction has taken place. The reaction of Cp2Ti(Me3‐SiC2SiMe3) with €‐caprolactam gives after elimination of the alkyne and molecular hydrogen the first early transition metal complex with a deprotonated coordinated €‐caprolactam in a η2‐amidate bonding fashion (3). The obtained complexes were characterized by NMR spectra (1, 2) and crystal structure analysis (1–3) and discussed as elemental steps in anionic ring‐opening polymerization of lactams catalyzed by metallocene‐alkyne complexes.
Suzuki‐Coupling of Cp*Ru(para‐C6H4Br2) with Phenyl Boronic Acid: A Model Reaction for the Synthesis of Organometallic Polymers
Authors: Harre Kathrin , Enkelmann Volker , Schulze Margit , Bunz Uwe H. F. 
Published: July 2007

AbstractThe synthesis of a terphenyl derivative complexed by the cationic moiety Cp*Ru+ by Suzuki coupling of [Cp*Ru(BrC6H4Br)]OTf with phenyl boronic acid under catalysis of Pd(PPh3)4 in a DME‐water mixture at 85°C in quantitative yield is reported. The stable coupling product 3 was characterized by X‐ray crystal structure analysis.