Inorganic Chemistry, Vol.34, No.1, 111-115, 1995
Oxidative Addition-Reactions to Novel Heterotrinuclear Iridium Complexes with Mixed Bridging Ligands - Crystal-Structure of ((Ir(Mu-Pz)(Mu-S(T)Bu)I-2(Co)(P(OMe)(3)))Pd-2)
The formation and properties of trinuclear heterobridged complexes of general formula [{Ir(mu-pz)(mu-S(t)Bu)L(2)}(2)-Pd] [L(2) = cycloocta-1,5-diene 1, (CO)(2) 2, (CO)[P(OMe)(3)] 3; pz = pyrazolate] are reported. Complex 3 reacts with methyl iodide or mercury(II) iodide to give compounds [{Ir-2(mu-pz)(2)(mu-S(t)Bu)(2)I(X)(CO)(2)[P(OMe)(3)](2)}Pd] [X = Me (4) I (5)]. Compound 5 undergoes a further oxidative addition with I-2 to form [{Ir(mu-pz)(mu-S(t)Bu)-I-2(CO)[P(OMe)(3)]}Pd-2], 6. Compound 6 can be also obtained by direct addition of iodine to complex 3 in a 2:1 molar ratio. The molecular structure of compound 6 has been determined by X-ray diffraction methods. The complex crystallizes in the triclinic system,space group P ($) over bar 1, with a = 8.763(1) Angstrom, b = 12.023(2) Angstrom, c = 12.713-(2) Angstrom, alpha = 102.086(6)degrees, beta = 94.108(7)degrees, gamma = 109.174(8)degrees, and Z = 1. Refinement by full-matrix least-squares techniques gave final R = 0.0322. Complex 6 is trinuclear with two octahedral "IrI2(CO)[P(OMe)(3)]" moieties symmetrically connected to a central square-planar Pd atom bridged through the nitrogens of a pyrazolate group and the S atom of a 2-methyl-2-propanethiolate ligand.