SYNTHESIS AND CHARACTERIZATION OF NEW SQUARE-PLANAR IRIDIUM COMPLEXES [TRANS-IR(CO)L(2)X] (L=PCY(3), X=OH OR OCH3 L=P(P-TOLYL)(3), X=OCH2C6H5 OR O(P-C6H4CH3)) - CRYSTAL AND MOLECULAR-STRUCTURES OF TRANS-IR(CO)(OH)(PCY(3))(2), TRANS-IR(CO)(OCH2C(6)H(5))(P(P-TOLYL)(3))(2), AND TRANS-IR(CO)(O-P-C6H4CH3)(P(P-TOLYL)(3))(2)

Three new Ir(I) complexes have been prepared, characterized and studied by X-ray crystallography. No evidence is found for pi-donation from an alkoxy (Ir(CO)(OCH2C6H5)(P(p-tolyl)(3))(2)) Or an aryloxy (Ir(CO)(O-p-C6H4CH3)(P(P-tolyl)(3))(2)) to iridium. The phenylmethoxy complex Ir(CO)(OCH2C6H5)(P(p-tolyl)(3))(2) crystallizes in the triclinic space group P ($) over bar 1 with a = 10.5187(16), b = 12.8320(15), c = 17.4940(19)Angstrom, alpha 71.447(8), beta = 84.907(11), gamma = 72.407(11)degrees, V = 2133.8(5)Angstrom(3) and Z = 2. The structure was solved and refined to R = 2.48% for 4567 reflections with F-0 > 6(F-0). Interatomic distances of note are Ir-P = 2.306(2) and 2.334(2), Ir-CO = 1.806(6) and Ir-O = 2.022(4)Angstrom. The p-cresolate derivative crystallizes as the p-cresol adduct Ir(CO)(OC6H4CH3)(P(p-tolyl)(3))(2).CH3C6H4OH in the monoclinic space group P2(1)/c with a = 21.1172(28), b = 12.0167(15), c = 22.5658(31)Angstrom, P 117.180(10)degrees, V = 5094.0(12)Angstrom(3) and Z = 4. The structure was refined to R = 4.26% for 3296 reflections with F-0 > 6 sigma(F-0). Interatomic distances include Ir-P = 2.322(4) and 2.330(4), Ir-CO = 1.781(13) and Ir-O = 2.067(7)Angstrom. The hydroxy derivative Ir(CO)(OH)(PCy(3))2 crystallizes in the triclinic space group P ($) over bar 1 with a = 9.916(3), b = 10.305(4), c 10.825(4)Angstrom, alpha 114.16(3), beta 109.55(3), gamma = 90.14(3)degrees, V = 938.6(5)Angstrom(3) and Z = 1. This structure is disordered with a scrambled image of the carbonyl and hydroxide ligands. Distances of note are Ir-P = 2.331(1), Ir-CO = 1.887(13) and Ir-OH = 1.978(12)Angstrom; the Ir-CO and Ir-OH distances may suffer from systematic errors due to disorder.