Stereoselective oxidative-addition reaction of molecular iodine and mercury(II) halides to rhodium dithiolate compounds. Crystal structure of [Rh2{µ-S(CH2)2S}Cl2(CO)2(PPh3)2]
- 1 January 1994
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 3,p. 385-389
- https://doi.org/10.1039/dt9940000385
Abstract
The binuclear complexes [Rh2{µ-S(CH2)2S}(L2)2][L2= cycloocta-1,5-diene (cod)1, L2=(CO)22] and [Rh2{µ-S(CH2)2S}(CO)2(PR3)2](R = Ph 3 or OPh 4) have been prepared and oxidative addition of the electrophiles I2 and HgX2(X = Cl or I) investigated. Compounds 3 and 4 undergo stepwise addition of molecular iodine to yield the symmetrical complexes [Rh2{µ-S(CH2)2S}In(CO)2(PR3)2][n= 2, R = Ph 5, R = OPh 6; n= 4, R = Ph 7, R = OPh 8]. However, interaction of 3 with HgX2(X = Cl or I) affords the unsymmetrical compounds [Rh2{µ-S(CH2)2S}X2(CO)2(PPh3)2](X = Cl 9 or I 10). The crystal structure of 9 has been determined by X-ray diffraction methods.Keywords
This publication has 25 references indexed in Scilit:
- A flexible framework obtained from oxidative additions upon the binuclear complex [Ir2(µ-pz)(µ-SBut)(CO)2{P(OMe)3}2]: preparation and X-ray structures of [Ir2(µ-pz)(µ-SBut)(µ-L)(CO)2{P(OMe)3}2] and [Ir2(µ-pz)(µ-SBut)(µ-L)I2(CO)2-{P(OMe)3}2](Hpz = pyrazole, L = dimethyl acetylenedicarboxylate)J. Chem. Soc., Dalton Trans., 1990
- Binuclear ‘oxidative isomerization’ as a model for surface reactions. Intramolecular character and kinetic profile of iodomethyldi-iridium(II): µ-methylenedi-iridium(III) conversion that follows di-iodomethane addition to [Ir(CO)(PPh3)(µ-pz)]2(Hpz = pyrazole)Journal of the Chemical Society, Chemical Communications, 1989
- Co-operativity effects between adjacent metal sites—kinetics of methyl iodide addition to pyrazolyl-bridged iridium dimers: argument for a concerted mechanism in the reversible two-fragment, two-centre oxidative addition to the cyclo-octa-1,5-diene di-iridium(I) complex [Ir(COD)(µ-pz)]2Journal of the Chemical Society, Chemical Communications, 1989
- Binuclear complexes of rhodium and iridium bridged by some new bifunctional anionic ligandsOrganometallics, 1988
- Synthesis and hydroformylation reaction of dinuclear rhodium(I) complexes with mixed bridging ligands. X-Ray structure of [Rh2(µ-pz)(µ-SBut)(CO)2{P(OMe)3}2]J. Chem. Soc., Dalton Trans., 1988
- Synthesis and characterization of an unusual heterobridged di-rhodium complex. X-ray molecular structure of [Rh2(μ-pz)2I2(CO)2(μ-dppm)]Inorganica Chimica Acta, 1985
- Orthometallation reaction at a binuclear pyrazolyl(pz) bridged rhodium compound: synthesis and crystal structure determination of Rh2(µ-pz)2[µ-P(C6F4)Ph2]Br(CO)(pcBr), pcBr = P(o-BrC6F4)Ph2Journal of the Chemical Society, Chemical Communications, 1985
- Pyrazolate A-frame rhodium complexes. Crystal structures of [Rh2(µ-dmpz)(CO)2(µ-dppm)2][ClO4] and [Rh2(µ-dmpz)I2(CO)2(µ-dppm)2][ClO4]J. Chem. Soc., Dalton Trans., 1985
- Organometallic Aspects of the Fischer‐Tropsch SynthesisAngewandte Chemie International Edition in English, 1982
- Pyrazolyl-bridged iridium dimers. 2. Contrasting modes of two-center oxidative addition to a bimetallic system and reductive access to the starting complex: three key diiridium structures representing short nonbonding and long and short bonding metal-metal interactionsJournal of the American Chemical Society, 1982