Synthesis, structure, and reactions of chiral rhenium vinylidene and acetylide complexes of the formula [(.eta.5-C5H5)Re(NO)(PPh3)(X)]n+. Vinylidene complexes that are formed by stereospecific C.beta. electrophilic attack, exist as two Re=C=C geometric isomers, and undergo stereospecific C.alpha. nucleophilic attack
作者:Dwayne R. Senn、Andrew. Wong、Alan T. Patton、Marianne. Marsi、Charles E. Strouse、J. A. Gladysz
DOI:10.1021/ja00226a026
日期:1988.8
(a) high-yield syntheses of chiral rhenium vinylidenecomplexes ((/eta//sup 5/-C/sub 5/H/sub5/)Re(NO)(PPh/sub3/)(/emdash/C/emdash/CRR/prime/))/sup +/X/sup /minus// and acetylide complexes (/eta//sup 5/-C/sub 5/H/sub5/)Re(NO)(PPh/sub3/)(C/identical to/CR), (b) the first observation of M/emdash/C/emdash/C geometric isomerism in vinylidenecomplexes, (c) the thermal and photochemical interconversion
Rh or Ir; R = Me or Ph) with HPF6 affords crystalline salts [M(η3-RCHCHCHCH2COOMe)(η5-C5J5)]+ PF6− in which the acyl CO group is coordinated to the metal. Base-catalysed hydrolysis of the η4-ester complexes affords the dienoic acid derivatives [M(η4-RCHCHCHCHCOOH)(η5-CH3CH; CHCHCHCOCH3)(η5-C5H5)] with HPF6 proceeds similarly. The 1H NMR spectra of the compounds are reported.
A general method for the selective binding and activation of one aldehyde enantioface. Synthesis and reactivity of rhenium aldehyde complexes [(.eta.5-C5H5)Re(NO)(PPh3)(.eta.2-RCHO)]+ PF6-
作者:Jesus M. Fernandez、Kenneth. Emerson、Raymond H. Larsen、J. A. Gladysz
DOI:10.1021/ja00286a030
日期:1986.12
aldehydes to chiral alcohols of high optical purity would be of immense utility in organic synthesis. Numerous catalytic and stoichiometric reactions have been described that effect such transformations with varying degrees of generality and success. They now report that the easily generated, chiral rhenium Lewis acid ((eta/sup 5/-C/sub 5/H/sub 5/)Re(NO)(PPh/sub 3/))/sup +/ selectively binds on aldehyde
Dihydride Complexes of the Cobalt and Iron Group Metals: An Investigation of Structure and Dynamic Behavior
作者:D. M. Heinekey、Mirjam van Roon
DOI:10.1021/ja962702n
日期:1996.1.1
simulated at all temperatures using a simple site permutation model after taking into consideration the opposite signs of the cis and trans H−P couplingconstants. Partial deuteration of the hydride ligands in the rhodium and cobalt complexes is achieved by exposure to D2. In the partially deuterated samples, no evidence is found for a bound dihydrogen ligand, but the involvement of a dihydrogen species
The reactions of acids and alkyl iodides with [Fe<sub>2</sub>(η-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>(CNMe)<sub>4</sub>] and related complexes
作者:A. R. Manning、Paul Murray
DOI:10.1039/dt9860002399
日期:——
[Fe2(η-C5H5)2(CO)(CNMe)3] and [Fe2(η-C5H5)2(CNR)4][R = Me (black isomer) or Et] is illustrated by their ability to react with R′I (R′= Me, Et, or Prn) to give in turn [Fe2(η-C5H5)2L(CNR)(µ-CNR)µ-CN(R)R′}]I and [Fe2(η-C5H5)2L(CNR)µ-CN(R)R′}2]I2(L = CO or CNR). The strong acid HPF6·Et2O gives [Fe2(η-C5H5)2(CNR)2µ-CN(R)H}2][PF6]2 which with [Fe2(η-C5H5)2(CNR)4] forms [Fe2(η-C5H5)2(CNR)2(µ-CNR)µ-CN(R)H}][PF6]