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

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 RhI 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.