Abstract
The reaction of trans-Mo(C 2H 4) 2(PMe 3) 4 with PhCCCOOEt affords (PhCCCOOEt) 3(PMe 3) ( 1). The molecular structure of 1 has been determined by means of X-ray analysis. NMR studies have shown that 1 undergoes a dynamic process in solution due to the alkyne rotation. The related energy barrier is experimentally determined to be 15.1 kcal mol −1. The well established EHMO theoretical arguments, which uniquely explain the chemical bonding in these complexes, are extended to interpret the nature of the barrier and its dependence on the π-donor or π-acceptor capability of the axial ligand. The conceptual continuity between the chemical bonding of d 6 metal species coordinated by at least two alkyne molecules (e.g. M(alkyne) 2L 4, M(alkyne) 2L 2 and M(alkyne) 3L) is highlighted.
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