Oxidative additions of I 2 and CH 3I to [Rh(quin)(CO)|P(R-C 6H 4) 3|] complexes. Crystal structure of [Rh(I)(CH 3)(quin)(CO)|P(4-CH 3-C 6H 4) 3|] · [formula omitted]Et 2O—IV

Abstract

The oxidative additions of homo- and heteronuclear molecules XI (X = I, CH 3) to the [Rh(quin)(CO)|P(R-C 6H 4) 3|] complexes [quin = 2-quinaldinate anion (C 9H 6 NCOO −), R = 4-CH 3O, 4-CH 3, 4-F, 4-Cl, 3-CH 3] were studied. Various phosphine ligands with different electronic properties and the same steric characteristics (R = 4-CH 3O, 4-CH 3, 4-F, 4-Cl) were used to determine their effect on the metal centre towards the oxidative addition reactions. Different sequences of the net electrodonation of the phosphine ligands for the square-planar rhodium(I) starting compounds and oxidated rhodium(III) products were deduced from the Δδ( 31P) values. The spectroscopic data, IR, 1H and 31P NMR, indicated that in all cases only one isomer was formed. The crystal structure of one of these species, [Rh(I)(CH 3)(quin)(CO)|P(4-CH 3C 6H 4) 3|]· 1 2 Et 2O was resolved, indicating a pseudo-octahedral environment in the rhodium atom with the methyl and iodide ligands in cis positions.