ISSN:
0009-2940
Keywords:
Vinylidenerhodium complexes, γ1-functionalized, generation from alkynols and their derivatives
;
(Vinylvinylidene)1- and allenylidenerhodium complexes, formation by HX elimination
;
Alkynyl(hydrido)1- rhodium(III) complexes, preparation from alkyne or vinylidene precursors
;
Rhodium complexes, cyclopentadienyl, with vinylvinylidene ligands
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Vinylidene Transition Metal Complexes, XXII[1]. - Alkyne, Alkynyl(hydrido)1-, Vinylidene-, and Vinylvinylidene Complexes of Rhodium from OH-, NH2-, and Cl-Functionalized Alkynes
Notes:
The reaction of [RhCl(PiPr3)2]n with γ1-functionalized 1-alkynes HC≡C-CRR′X (X=OH, OMe, Cl, NH2) at room temperature leads to the formation of either alkyne-, alkynyl(hydrido)1-, or vinylidenerhodium complexes. The alkyne and alkynyl-(hydrido) derivatives rearrange thermally or in the presence of deactivated Al2O3 to the isomeric vinylidenerhodium compounds in almost quantitative yield. On treatment of the γ1-functionalized vinylidenerhodium complexes trans-[RhCl(=C=CH-CRR′X)(PiPr3)2] with Al2O3 or traces of acids, elimination of HX occurs and (for R=H, CH3; R′=CH3; X=OH, Cl, NH2) the (vinylvinylidene)rhodium compounds trans-[RhCl(=C=CH-CR=CH2)(PiPr3)2] are formed. In contrast, the reaction of trans-[RhCl(=C=CHCPh2OH)(PiPr3)2] with either Al2O3 or acid gives the allenylidene complex trans-[RhCl(=C=C=CPh2)(PiPr3)2]. The 1-hexyne derivatives HC≡C[CH2]3CH2X (X=OH, Cl) react with [RhCl(PiPr3)2]n to give alkyne-, alkynyl(hydrido)1-, and vinylidenerhodium compounds; attempts to form the cyclic vinylidene complex trans- by HX elimination from trans-[RhCl(=C=C=CH[CH2]3CH2X)(PiPr3)2] (X=OH, Cl) failed. The half-sandwich-type (vinylvinylidene)rhodium compounds [C5H5Rh(=C=CH-CR=CH2)(PiPr3)] (R=H, Me) are obtained from [RhH(C≡C-CR=CH2)Cl(py)(PiPr3)2] and NaC5H5.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19931260318
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