Electron and bromine transfer reactions between metal carbonyl anions and metal carbonyl bromides. Crystal and molecular structure of dimeric indenyl molybdenum tricarbonyl

Article abstract of DOI:10.1021/om00035a028

Reactions of metal carbonyl anions with metal carbonyl halides proceed by two separate paths. When the reactant anion is a strong nucleophile, the halogen is transferred, resulting in a new metal carbonyl halide and a new metal carbonyl anion as intermediates. The ultimate products, in this case, are the homobimetallic complexes. In cases where the reactant metal carbonyl anion is a poor nucleophile, a single electron transfer occurs, leading to the two homobimetallic complexes and to the heterobimetallic complex. Halide effects and possible indenyl effects are examined. The complex [Mo(indenyl)(CO)₃]₂ crystallizes in the noncentrosymmetric orthorhombic space group P2₁2₁2₁ (No. 19) with a = 7.3572(7) ?, b = 14.4539(12) ?, c = 19.983(2) ?, V = 2125.0(4) ?³, and Z = 4. Diffraction data were collected on a Siemens R3m/V diffractometer for 2θ = 5-45° (Mo Kα), and the structure was solved and refined to R = 3.21% and R_w = 3.23% for all 2786 independent reflections (R = 2.26% and R_w = 2.81% for those 2314 reflections with |F_o|> 6σ(|F_o|). The complex is held together by a Mo-Mo single bond (Mo(1)-Mo(2) = 3.251(1) ?), and has Mo-CO distances ranging from 1.956(6) to 1.988(7) ?, averaging 1.970 ± 0.016 A. Molybdenum-carbon distances to the η⁵-indenyl rings range from 2.300(7) to 2.427(6) ? for Mo(1) and 2.306(7) to 2.430(6) ? for Mo(2).