Organosilicon chemistry. Part XII. Stability and catalytic activity of some chlorohydridobis(phosphine)(silyl)rhodium(III) complexes
- 1 January 1974
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 21,p. 2311-2315
- https://doi.org/10.1039/dt9740002311
Abstract
New complexes of the type [L2RhH(SiR3)Cl] have been prepared [L = Ph2(tol)P, Ph2(cy)P, Ph(cy)2P, or Ph2PriP; R = OEt, Me, or Et; tol =p-tolyl; cy = cyclohexyl]. Evidence for similar complexes with L = Ph2EtP and Ph2MeP has been obtained by ligand-exchange studies. The stability to dissociation of complexes of this type increases in the orders SiMe3 < SiMe2Cl < SiMeCl2 < SiCl3, SiPh3 < SiEt3 < Si(OEt)3 < SiCl3, (cy)3P < Ph(cy)2P < Ph2(cy)P ≲ Ph2(tol)P ≈ Ph3P, Ph2MeP < Ph2EtP < Ph2PriP ≈ Ph3P, and Ph3As < Ph3P. The dependence of stability on the neutral ligand reflects a combination of steric and electronic effects. The rate of addition of triethylsilane to hex-1-ene, catalysed by the complexes [L3RhCl], increases in the order L =(cy)3P Ph2MeP < Ph(cy)2P ≈ Ph3P < Ph2(cy)P ≈ Ph2EtP.Keywords
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