ELECTRON AND BROMINE TRANSFER-REACTIONS BETWEEN METAL-CARBONYL ANIONSAND METAL-CARBONYL BROMIDES - CRYSTAL AND MOLECULAR-STRUCTURE OF DIMERIC INDENYL MOLYBDENUM TRICARBONYL
Ws. Striejewske et al., ELECTRON AND BROMINE TRANSFER-REACTIONS BETWEEN METAL-CARBONYL ANIONSAND METAL-CARBONYL BROMIDES - CRYSTAL AND MOLECULAR-STRUCTURE OF DIMERIC INDENYL MOLYBDENUM TRICARBONYL, Organometallics, 12(11), 1993, pp. 4413-4419
Reactions of metal carbonyl anions with metal carbonyl halides proceed
by two separate paths. When the reactant anion is a strong nucleophil
e, the halogen is transferred, resulting in a new metal carbonyl halid
e and a new metal carbonyl anion as intermediates. The ultimate produc
ts, in this case, are the homobimetallic complexes. In cases where the
reactant metal carbonyl anion is a poor nucleophile, a single electro
n transfer occurs, leading to the two homobimetallic complexes and to
the heterobimetallic complex. Halide effects and possible indenyl effe
cts are examined. The complex [Mo(indenyl)(CO)3]2 Crystallizes in the
noncentrosymmetric orthorhombic space group P2(1)2(1)2(1) (No. 19) wit
h a = 7.3572(7) angstrom, b = 14.4539(12) angstrom, c = 19.983(2) angs
trom, V = 2125.0(4) angstrom3, and Z = 4. Diffraction data were collec
ted on a Siemens R3m/V diffractometer for 2theta = 5-45-degrees (Mo Ka
lpha), 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)\ > 6sigma(\F(o)\). The co
mplex is held together by a Mo-Mo single bond (Mo(1)-Mo(2) = 3.251(1)
angstrom), and has Mo-CO distances ranging from 1.956(6) to 1.988(7) a
ngstrom, averaging 1.970 +/- 0.016 angstrom. Molybdenum-carbon distanc
es to the eta5-indenyl rings range from 2.300(7) to 2.427(6) angstrom
for Mo(1) and 2.306(7) to 2.430(6) angstrom for Mo(2).