Divinyldisiloxane and divinylsilane complexes of rhodium(I)

Cardin, C. J. ORCID: https://orcid.org/0000-0002-2556-9995, 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 doi: 10.1016/S0022-328X(99)00180-1

Abstract/Summary

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
URI	https://reading-clone.eprints-hosting.org/id/eprint/23749
Item Type	Article
Refereed	Yes
Divisions	Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
Uncontrolled Keywords	Tetramethyldivinyldisiloxane; Divinyldimethylsilane; Rhodium(I); Dynamic processes; Hydrosilylation
Publisher	Elsevier
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