1,2,3-Triphenylphosphirene is prepared from its P→W(CO)5 complex by a two step decomplexation procedure involving iodine and 1-methylimidazole; its X-raycrystalstructure analysis shows a very strained ring (< CPC = 41.8°) with no electronic delocalization.
Phosphepines: Convenient Access to Phosphinidene Complexes
作者:Mark L. G. Borst、Rosa E. Bulo、Christiaan W. Winkel、Danièle J. Gibney、Andreas W. Ehlers、Marius Schakel、Martin Lutz、Anthony L. Spek、Koop Lammertsma
DOI:10.1021/ja050817y
日期:2005.4.1
o-diethynylbenzene with transition metal-complexed primary phosphines gives in a single base-induced step stable phosphepine complexes as confirmed by X-ray data. At 75-80 degrees C these phosphepines undergo clean cheletropic elimination of naphthalene to give transient carbene-like phosphinidene complexes that can be trapped in high yield by alkenes, alkynes, and alcohols.
X 射线数据证实,邻二乙炔苯与过渡金属络合的伯膦反应在单一的碱诱导步骤中得到稳定的膦配合物。在 75-80 摄氏度时,这些磷化氢会经历萘的清洁螯合消除,以产生瞬态的卡宾状磷化烯配合物,这些配合物可以被烯烃、炔烃和醇以高产率捕获。
An η<sup>2</sup>transition state for the insertion of M(PR<sub>3</sub>)<sub>2</sub>fragments (M = Pd or Pt) into the phosphorus–carbon bonds of pentacarbonyl(phosphirane)tungsten complexes
作者:Duncan Carmichael、Peter B. Hitchcock、John F. Nixon、François Mathey、Louis Ricard
DOI:10.1039/dt9930001811
日期:——
4S*)-(±)-, (2S*3R*4R*)-(±)- and (2S*,3S*,4R*)-(±)-[(Ph3P)2Pt(CHPhCHPhPPh)W(CO)5]; and trans-(2S*,3S*,4R*)-(±)-[(Ph3P)(OC)Pt-(CHPhCHPhPPh)W(CO)5]. The crystal and molecularstructures of (Z)-[W(CO)5([graphic omitted]HPh)], (2R*,3S*,4R*)-(±)- and (R*,3S*,4S*)-(±)-[(dppe)Pd(CHPhCHPhPPh)W(CO)5] have been determined. The configurations of the products are interpreted in terms of a transitionstate in which
(E)-和(Z)-[W(CO)5([HP]])与[M(PR 3)2(C 2 H 4)] [M = Pd,(PR 3)2 = dppe(Ph 2 PCH 2 CH 2 PPh 2); 已研究了M = Pt,PR 3 = PPh 3,并已通过NMR光谱法充分表征了以下产物[由M(PR 3)2蛙类插入到膦环中得到的结果]:(2 R *,3 S *,4 S*)-(±)-,(2 R *,3 S *,4 R *)-(±)-和(2 R *,3 S *,4 R *)-(±)-[(dppe)Pd (CHPhCHPhPPh)W(CO)5 ];(2 S *,3 S *,4 S *)-(±)-,(2 S * 3 R * 4 R *)-(±)-和(2 S *,3 S *,4 R *)- (±)-[(Ph 3 P)2 Pt(CHPhCHPhPPh)W(CO)5 ];和反式-(2 S *,3 S *,4 R *)-(±)-[(Ph
Novel insertion of [M(PR<sub>3</sub>)<sub>2</sub>] fragments (M = Pd, Pt) into the strained phosphorus–carbon bond of the phosphirene complex [W(CO)<sub>5</sub>(PhPC<sub>2</sub>Ph<sub>2</sub>)]. Crystal and molecular structure of [PtW(CO)<sub>5</sub>(PEt<sub>3</sub>)<sub>2</sub>(PhPC<sub>2</sub>Ph<sub>2</sub>)]
作者:Duncan Carmichael、Peter B. Hitchcock、John F. Nixon、François Mathey、Alan Pidcock
DOI:10.1039/c39860000762
日期:——
The striain phosphirene ring in [W(CO)5(PhPC2Ph2)] readily undergoes insertion of [M(PR3)2] fragments (M = Pd, Pt) to give complexes in which phosphorus bridges two different metal atoms.