ISSN:
0948-5023
Keywords:
Keywords Metathesis, Homogeneous catalysis, Density functional calculations, Reaction mechanisms
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
Abstract Gradient-corrected density-functional computations (BP86/ECP1 level) confirm the viability of the recently proposed reaction pathway for imine metathesis with imidomolybdenum(VI) species [Mo(NR)2Lx] (e.g., Lx = Cl2, DME; R = tBu). In addition to a Chauvin-type [2+2] addition-elimination mechanism, model calculations for the [MoCl2(NH)2] + NH3 + CH2NH system corroborate the suspected involvement of amido intermediates such as [MoCl2(NH)(NH2)2] and . Several catalytic cycles are characterised that differ in the stereochemistry of the ligands about Mo. The lowest computed rate-determining barriers are only a few kcal mol-1 higher than that obtained for the Chauvin-type mechanism in the [MoCl2(NH)2] + CH2NH system via , provided the necessary H-atom transfers are catalysed efficiently by traces of base.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/s0089400060112
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