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Divinyldisiloxane and divinylsilane complexes of rhodium(I)

Cardin, C. J., Hitchcock, P. B., Lappert, M. F., MacBeath, C. and Warhurst, N. J. W. (1999) Divinyldisiloxane and divinylsilane complexes of rhodium(I). Journal of Organometallic Chemistry, 584 (2). p. 366. ISSN 0022-328X

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To link to this item DOI: 10.1016/S0022-328X(99)00180-1


Reaction of the tetrakis(cyclooctene)rhodium(I) complex [{Rh(C8H14-c)2(μ-Cl)}2] with the appropriate divinyldisiloxane molecules (ViSiR2)2O (R=Me or Ph) yields, by displacement of the cycloctene ligands, the complexes [{Rh(ViSiR2)2O(μ-Cl)}2] (R=Me (1) or Ph (2)). These react further with a tertiary phosphine PR3 to give cis-[Rh{(ViSiR2)2O}(PR′3)Cl] (R′=Ph or C6H4Me-p). The complex cis-[{Rh(Vi2SiMe2)(μ-Cl)}2] (7) was similarly prepared by the displacement of ethylene from [{Rh(C2H4)2(μ-Cl)}2] by the divinyldimethylsilane Vi2SiMe2. 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–(ViSiR2)2O 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, whereas 7 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(ViSiPh2)2O(μ-Cl)}2] underwent a dynamic process involving the dissociation, rotation and then reassociation of the vinyl groups.

Item Type:Article
Divisions:Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:23749
Uncontrolled Keywords:Tetramethyldivinyldisiloxane; Divinyldimethylsilane; Rhodium(I); Dynamic processes; Hydrosilylation

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