CARBONYLATION OF IRIDIUM(I) AND IRIDIUM(III) COMPLEXES, TRANS-IR(CO)(R)(P(P-TOLYL)(3))(2) (R=ME, OME, OCH(2)PH, OC(6)H(4)ME, OH) AND IR(CO)(ME) (SO4)(P(P-TOLYL)(3))(2), AND FACILE ELIMINATION OF HARD LIGANDS -CRYSTAL AND MOLECULAR-STRUCTURES OF IR(CO)(ME)(SO4)(P(P-TOLYL)(3))(2)AND [IR(CO)(3)(P(P-TOLYL)(3))(2)][HSO4]

Carbonylation of several iridium(I) complexes, trans-Ir(CO)(R)(P(p-tol yl)(3))(2) lead to products Ir(Co)(2)(C(O)R)(P(p-tolyl)(3))(2), R = Me , OCH(2)Ph; and Ir-2(CO)(6)(P(p-tolyl)(3))(2), R = OH, OMe, and OC(6)H (4)Me) that depend on the nature of the R group. Carbonylation of the iridium(III) complex, Ir(CO)(Me)(SO4)(P(p -tolyl)(3))(2) leads to two iridium products, [Ir(CO)(3)(P(p-tolyl)(3))(2)(+)] and Ir(CO)(3)(C(O)M e)(P(p-tolyl)(3))(2) by two different pathways. Structures of Ir(CO)(M e)(SO4)- (P(p-tolyl)(3))(2) and [Ir(CO)(3)(P(p-tolyl)(3))(2)][HSO4] we re determined to assist in the interpretation. The complex Ir(CO)(Me)( SO4)(P(p-tolyl)(3))(2) crystallizes in the orthorhombic space group Pb cn with a = 18.237(3), b = 12.572(2), c = 18.584(2) Angstrom, V = 4260 .9(11) Angstrom(3) and Z = 4. The structure was refined to R = 1.98% f or 1640 reflections with F > 6 sigma(F). The molecule lies on a site o f Ct symmetry, necessitating a disorder of carbonyl and methyl ligands . Bond distances around the octahedral iridium(III) center include Ir- CO = 1.823(13), Ir-CH3 = 2.127(14), Ir-P = 2.398(1) and Ir-O(SO4)= 2.1 19(4) Angstrom. The species [Ir(CO)(3)(P(p-tolyl)(3))(2)][HSO4] crysta llizes in the monoclinic space group P2(1)/n with a = 11.490(2), b = 1 2.255(3), c = 30.873(7) Angstrom, beta = 92.826(17)degrees, V = 4342.0 (15) Angstrom(3) and Z = 4. The structure was refined to R = 6.09% for 2591 reflections with F > 6 sigma(F). The Ir(CO)(3)P-2 core of the ca tion has a geometry slightly distorted from D-3h symmetry, with Ir-P = 2.363(5) and 2.374(5) Angstrom and Ir-CO = 1.921(21)-2.012(28) Angstr om. The HSO4- anion undergoes substantial librational motion (or is di sordered) and is associated with S-O distances ranging from 1.31(4) th rough 1.49(3) Angstrom.