THE CHEMISTRY OF HETERO-ALLENE AND -ALLYLIC DERIVATIVES WITH RHODIUM AND IRIDIUM. II. RHODIUM(I)- AND IRIDIUM(I)-PHOSPHINE COMPLEXES OF HETERO-ALLYLIC LIGANDS OF THE TYPE - (X = S, NR, O) AND - (Q = S, O). SYNTHESIS AND 31P-NMR

Article abstract of DOI:10.1016/S0022-328X(00)93336-9

Some known and new hetero-allylic derivatives ^- (X = S, NR, O) and ^- (Q = S, O) have been shown to react with rhodium(I)- and iridium(I)-phosphine compounds to give stable complexes M(PPh3)2 (A) and M(PPh3)2 (B) (M = Rh, Ir) in which the ligands are bidentate.P, S(P) and O(P) are always coordinated and the coordination preference of the other atoms is: S > NR > O.A and B react with carbon monoxide to give M(PPh3)(CO) and M(PPh3)(CO), respectively, in which CO is preferentially found trans to the chelate donor atom with the lowest trans-influence. A correlation between and ²J(P₁-P₂)_cis of 0.946 was found; and even better correlation with r = 0.988 gave the equation; ²J(P₁-P₂)_cis = 0.43 - 0.072/¹J(Rh-P₁) - ¹J(Rh-P₂)/ - 30.8 Hz.A similar correlation was shown by a number of asymmetric cis-Pt⁰-bis-phosphine (η²-ligand) complexes and trans- and cis-WLL'-(CO)4 complexes reported in the literature.