SYNTHESIS AND CHARACTERIZATION OF FAC-TRIS(TRIMETHYLPHOSPHINO)IRIDIUM(III) SILANE COMPLEXES

The synthesis and characterization of iridium(III) silyl complexes of the form IrHX(PMe(3))(3)-SiRR'(2) (X = H or D; R = H, D, Cl, or Ph; R' = Ph or t-Bu) are described. The complexes are prepared by the oxidative addition of SiXRR'(2) to IrH(PMe(3))(4) with the loss of PMe(3). Three of the complexes have been characterized by single-crystal X-ray diffraction techniques: IrH2(PMe(3))(3)(SiHPh(2)), triclinic, space group P ($) over bar 1, a = 9.793(2) Angstrom, b = 16.385(2) Angstrom, c = 16.807(4) Angstrom, alpha = 88.32(2)degrees, beta = 99.70(2)degrees, gamma = 94.72(2)degrees, V = 2649.0(10) Angstrom(3), Z = 4; IrH2(PMe(3))(3)(SiCl(tBu)(2)), orthorhombic, space group Pbca, a = 18.519(3) Angstrom, b = 15.264(2) Angstrom, c = 18.982(3) Angstrom, V = 5635.6(15) Angstrom(3), Z = 8; and IrH2(PMe(3))(3)(SiPh(3)), C2/c, a = 34.011(7) Angstrom, b = 9.779(2) Angstrom, c = 18.733(4) Angstrom, beta = 105.46(3)degrees, V = 5998(2) Angstrom(3), Z = 8. Refinement to convergence gave the conventional and weighted agreement factors R = 0.038 and R(W) = 0.042, R = 0.037 and R(W) = 0.040, and R = 0.061 and R(W) = 0.075 for each structure, respectively.