Synthesis and X-ray crystal structure of the novel Mo—Cu complex, (Ph2PCH2CH2PPh2)2Cu+[(HBpz″3)Mo(CO)3]2Cu−(where pz″ = 3,5-dimethylpyrazolyl, N2C5H7)

Abstract

The novel complex, (Ph2PCH2CH2PPh2)2Cu+[(HBpz″3)Mo(CO)3]2Cu− (where pz″ = 3,5-dimethylpyrazolyl), has been synthesized by reacting the (HBpz″3)Mo(CO)3− anionic ligand with CuI in the presence of a stoichiometric amount of Ph2PCH2CH2PPh2. Crystals of (Ph2PCH2CH2PPh2)2Cu+[(HBpz″3)Mo(CO)3]2Cu−•3.5C6H6•CH2Cl2 are triclinic, a = 13.421(1), b = 14.931(3), c = 28.523(5) Å, α = 90.41(2), β = 90.19(1), γ = 104.65(1)°, Z = 2, space group [Formula: see text] The structure was solved by heavy atom methods and was refined by full-matrix least-squares procedures to R = 0.047 and Rw = 0.049 for 8779 reflections with I ≥ 3σ(I). The crystal structure consists of (Ph2PCH2CH2PPh2)2Cu+ cations having irregular tetrahedral coordination geometry about the copper atom (Cu—P = 2.263(2)–2.304(2) Å and P—Cu—P = 88.30(7)–134.62(8)°) and novel [(HBpz″3)Mo(CO)3]2Cu− anions having exact Ci and approximate D3d symmetry. The central Cu atom of the anion is bonded to two Mo atoms in a linear fashion and also interacts with six semi-bridging carbonyl ligands, three from each (HBpz″3)Mo(CO)3− ligand. Average bond lengths and angles for the anion are Mo–Cu = 2.565, Mo—C = 1.955, Mo—N = 2.256, Cu—C = 2.309, C—O = 1.174 Å, Mo—C—O = 171.7° and Cu—C—O = 114.7°.