Reactions of di-µ-chloro-bis[cyclo-octa-1,5-dienerhodium(I)] with carbon mono-oxide and mono-, di-, or tri-tertiary phosphines, or 1,2-bis(diphenylarsino) ethane

Abstract

Reactions of [Rh₂(cod)₂Cl₂](cod = cyclo-octa-1,5-diene) with CO and PXPh₂(X = Et or Cl), Ph₂P[CH₂]_nPPh₂(n= 1–4), 4,5-bis(diphenylphosphinomethyl)-2,2-dimethyl-1,3-dioxoiane (bdmo), cis-Ph₂PCH:CHPPh₂, Ph₂As[CH₂]₂AsPh₂, (Ph₂PCH₂)₃CMe, or P(CH₂CH₂PPh₂)₂Ph, give trans-[Rh(CO)Cl(PXPh₂)₂], [{Rh(CO)Cl(Ph₂P[CH₂]_nPPh₂)}_m](m= 1, n= 2; m= 2, n= 1, 3, or 4). or related complexes. Under different conditions, a complex of Ph₂P[CH₂]₂PPh₂ with co-ordinated diene has been obtained. An excess of Ph₂P[CH₂]_nPPh₂ gives [{Rh(Ph₂P[CH₂]_nPPh₂)₂}Cl](n= 2) or [{Rh(CO)(Ph₂P[CH₂]_nPPh₂)₂}Cl](n= 3 or 4). Reactions of these complexes of Rh^I with Cl₂, HCl, or Mel normally give the corresponding rhodium(III) complexes. Assignments of i.r. and ³¹P n.m.r. spectral parameters have been made by internal comparisons or by comparison with the bromo-complexes, prepared by halogen-exchange reactions.