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Titolo:
Divinyldisiloxane and divinylsilane complexes of rhodium(I)
Autore:
Cardin, CJ; Hitchcock, PB; Lappert, MF; MacBeath, C; Warhurst, NJW;
Indirizzi:
Univ Reading, Dept Chem, Reading RG6 6AD, Berks, England Univ Reading Reading Berks England RG6 6AD eading RG6 6AD, Berks, England Univ Sussex, Sch Chem Phys & Environm Sci, Chem Lab, Brighton BN1 9QJ, E Sussex, England Univ Sussex Brighton E Sussex England BN1 9QJ BN1 9QJ, E Sussex, England
Titolo Testata:
JOURNAL OF ORGANOMETALLIC CHEMISTRY
fascicolo: 2, volume: 584, anno: 1999,
pagine: 366 - 375
SICI:
0022-328X(19990723)584:2<366:DADCOR>2.0.ZU;2-R
Fonte:
ISI
Lingua:
ENG
Soggetto:
TRIS(ALKENE)NICKEL(0) COMPLEX; STEREOCHEMICAL NONRIGIDITY; PLATINUM(0);
Keywords:
tetramethyldivinyldisiloxane; divinyldimethylsilane; rhodium(I); dynamic processes; hydrosilylation;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
16
Recensione:
Indirizzi per estratti:
Indirizzo: Lappert, MF Univ Reading, Dept Chem, Reading RG6 6AD, Berks, England Univ Reading Reading Berks England RG6 6AD AD, Berks, England
Citazione:
C.J. Cardin et al., "Divinyldisiloxane and divinylsilane complexes of rhodium(I)", J ORGMET CH, 584(2), 1999, pp. 366-375

Abstract

Reaction of the tetrakis(cyclooctene)rhodium(I) complex [{Rh(C8H14-c)(2)(mu-Cl)}(2)] with the appropriate divinyldisiloxane molecules (ViSiR(2))(2)O (R = Me or Ph) yields, by displacement of the cycloctene ligands, the complexes [{Rh(ViSiR(2))(2)O(mu-Cl)}(2)] (R = Me (1) or Ph (2)). These react further with a tertiary phosphine PR3 to give cis-[Rh{(ViSiR(2))(2)O}(PR3')Cl](R' = Ph or C6H4Me-p). The complex cis-[{Rh(Vi(2)SiMe(2))(mu-Cl)}(2)] (7) was similarly prepared by the displacement of ethylene from [{Rh(C2H4)(2)(mu-Cl)}(2)] by the divinyldimethylsilane Vi(2)SiMe(2). X-ray molecular structures of the crystalline complexes 1, 2 and 7 show a distorted square planar Rh(I) environment, the CH2=CH groups being orthogonal to this plane; 1 and 2 have the Rh-(ViSiR(2))(2)O metallacycle in the chair conformation, but differ in the nature of the central Rh(Cl)RhCl core, which is planar for 1 and puckered for 2, but each of 1 and 2 is the rac-diastereoisomer, whereas7 has the meso-configuration. In solution 1 and 2 exist as a mixture of isomers, probably the rac- and meso-pairs as established by multinuclear NMR spectral studies. A series of saturation transfer NMR spectroscopic experiments showed that the divinyldisiloxane ligands in [{Rh(ViSiPh(2))(2)O(mu-Cl)}(2)] underwent a dynamic process involving the dissociation, rotation andthen reassociation of the vinyl groups. (C) 1999 Elsevier Science S.A. Allrights reserved.

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Documento generato il 29/11/20 alle ore 03:25:46