29743-03-1Relevant academic research and scientific papers
Equilibrium studies of phosphine and amine substitution reactions of tungsten carbonyl
Angelici, Robert J.,Ingemanson, Carol M.
, p. 83 - 86 (1969)
Equilibrium constants, K, have been determined for the reaction (Am)W(CO)5 + L ? (L)W(CO)5 + Am. For a given L group, K values increase for different amines, Am, in the order: p-CH3OC6H4NH2 3C6H4NH2 6H5NH2 6H4NH2. This trend is interpreted to mean that the strength of the W-Am bond decreases with decreasing basicity of the amine. For a given Am group, K decreases with different L groups as follows: P(n-C4H9)3 ～ P(C6H11)3 ≥ P(OCH2)3CC2H5 > P(SCH2)3CCH3 ≥ P(O-n-C4H9)3 > P(C6H5)3 > As(C6H5)3 > Sb(C6H5)3 ～ P(OC6H5)3 ～ p-CH3OC6H4NC > Bi(C6H5)3. Since this is essentially the order of decreasing basicity of the phosphorus donor ligands, the results suggest that σ bonding, not π bonding, is largely responsible for the strength of the W-L bond. Enthalpies and entropies have been determined for some of these reactions, and they support the above conclusions.
Crystal Structures of , and (M = Mo or W): A Comparative Study of Structure and Bonding in Complexes (E = P, As or Sb; M = Cr, Mo or W)
Aroney, Manuel J.,Buys, Irmi E.,Davies, Murray S.,Hambley, Trevor W.
, p. 2827 - 2834 (2007/10/02)
Crystal structures have been determined for , and (M = Mo or W) as part of a systematic study of a series of nine complexes (M = Cr, Mo or W; E = P, As or Sb).Trends in bond lengths and angles are rationalised in terms of streric and electronic interactions between the bonded M(CO)5 and EPh3 fragments.Comparison is made between the solid-state geometry of the free and co-ordinated EPh3.Torsion angles defining the disposition of the EPh3 groups in relation to M(CO)5 show little variation within the series.For all nine complexes the EPh3 groups have propeller geometry with small deviations from symmetric C3 structures.The studies were extended to include other related complexes.Trends in the strutural parameters of 29 such compounds are related to the steric behaviour and ?-acceptor capacity of the ligands L.It is shown that M-P bond dimensions are not adequately explained by hybridisation changes of the phosphorus atom in the ligand L.
Conformational studies of EPh3M(CO)5 complexes (E = P, As or Sb; M = Cr, Mo or W)
Davies, M. S.,Allen, G. W.,Aroney, M. J.,Hambley, T. W.,Pierens, R. K.
, p. 81 - 92 (2007/10/02)
Studies are reported of the electro-optical Kerr effect, electric dipole moments and IR carbonyl stretching frequencies of the nine EPh3(CO)5 complexes (E = P, As or Sb and M = Cr, Mo or W).The experimental results are applied in conjuction with molecular
