Si–H and Si–C Bond Cleavage Reactions of Silane and Phenylsilanes with Mo(PMe<sub>3</sub>)<sub>6</sub>: Silyl, Hypervalent Silyl, Silane, and Disilane Complexes
作者:Ashley A. Zuzek、Gerard Parkin
DOI:10.1021/ja503368j
日期:2014.6.11
Mo(PMe3)6 cleaves the Si-H bonds of SiH4, PhSiH3, and Ph2SiH2 to afford a variety of novel silyl, hypervalent silyl, silane, and disilane complexes, as respectively illustrated by Mo(PMe3)4(SiH3)2H2, Mo(PMe3)4(κ(2)-H2-H2SiPh2H)H, Mo(PMe3)3(σ-HSiHPh2)H4, and Mo(PMe3)3(κ(2)-H2-H2Si2Ph4)H2. Mo(PMe3)4(κ(2)-H2-H2SiPh2H)H and Mo(PMe3)3(κ(2)-H2-H2Si2Ph4)H2 are respectively the first examples of complexes
New developments in the organometallic chemistry of the group IV-VII transition metals
作者:M. L. H. Green
DOI:10.1351/pac198456010047
日期:1984.1.1
shifts in tungstenocene derivatives has led to a widening study of tungstenocene—related chemistry. Many new compounds are described which were designed as tungstenocene precursor analogues and their ability to undergo thermally or photgchemically induced C—H activation has been explored. Simple d titanium—alkyls are described in which C—H groups of the alkyl ligand form covalent, three—centered two—electron
The syntheses and structures of coordinatively unsaturated aryloxy-hydride complexes of molybdenum, Mo(PMe3)4(OAr)H: reversible CH bond activation and comparison with their tungsten analogues
作者:Tony Hascall、Vincent J Murphy、Kevin E Janak、Gerard Parkin
DOI:10.1016/s0022-328x(02)01306-2
日期:2002.6
Mo(PMe3)4(OAr)H is in marked contrast to the cyclometalated products of CH bond activation that are obtained for the corresponding tungsten system. Deuterium labeling and magnetization transfer studies, however, demonstrate that the coordinatively unsaturated molybdenumcomplexes Mo(PMe3)4(OAr)H are in fact kinetically capable of intramolecular oxidative addition of a CH bond of the ortho substituents to
Mo(PMe3)6 reacts with ArOH (Ar=2,4,6-C6H2Me3, 2,6-C6H3Pri2) to give coordinatively unsaturated aryloxy-hydride derivatives Mo(PMe3)4(OAr)H. The formation of Mo(PMe3)4(OAr)H is in marked contrast to the cyclometalated products of CH bond activation that are obtained for the corresponding tungsten system. Deuterium labeling and magnetization transfer studies, however, demonstrate that the coordinatively
Trimethylphosphine–tungsten chemistry: hydrido, silyl, fluoro, hydroxy, and aquo derivatives: crystal structure of [W(PMe<sub>3</sub>)<sub>4</sub>H<sub>2</sub>(OH<sub>2</sub>)F]F
作者:Malcolm L. H. Green、Gerard Parkin、Chen Mingqin、Keith Prout
DOI:10.1039/c39840001400
日期:——
The compounds W(PMe3)4H2X2(X = H, F, SiH3), [W(PMe3)4H2(OH)2]2+[BF4â]2, and [W(PMe3)4H2(OH2)F]F, whose crystal structure has been determined, are described; W(PMe3)4(η2-CH2PMe2)H reacts with ethylene giving inter alia W(η-C4H6)2(PMe3)2.
Trinuclear, tetranuclear and octanuclear chalcogenido clusters of molybdenum and tungsten supported by trimethylphosphine ligands
作者:Aaron Sattler、Gerard Parkin
DOI:10.1016/j.poly.2014.06.019
日期:2014.12
Abstract A variety of trinuclear, tetranuclear and octanuclear chalcogenido compounds of molybdenum and tungsten that are supported by PMe3 ligands has been synthesized and structurally characterized by X-ray diffraction. For example, the tetranuclear sulfido cluster, Mo4S6(SH)2(PMe3)6, has been obtained by reaction of Mo(PMe3)6 with H2S, while the trinuclear selenido and tellurido compounds, Mo3Se5(PMe3)6
摘要合成了由PMe3配体负载的钼和钨的三核,四核和八核硫属元素化合物,并通过X射线衍射对其结构进行了表征。例如,四环硫基团簇Mo4S6(SH)2(PMe3)6是通过Mo(PMe3)6与H2S反应获得的,而三环硒基和碲化合物Mo3Se5(PMe3)6和Mo3Te5(PMe3)可以分别通过热分解Mo(PMe 3)4 Se 2和Mo(PMe 3)4 Te 2来获得图6所示的结构。与形成类似于Mo3E5(PMe3)6(E = Se,Te)的三核化合物相反,钨配合物W(PMe3)4S2的热分解产生八核硫化物簇W8S16(PMe3)10。在这些化合物中,Mo4S6(SH)2(PMe3)6和W8S16(PMe3)10具有1的M:S化学计量比: