Molybdenum chalcogenobenzimidato complexes: radical synthesis and nitrile extrusion via beta-EPh (E = S, Se, and Te) elimination |
| |
Authors: | Mendiratta Arjun Cummins Christopher C Kryatova Olga P Rybak-Akimova Elena V McDonough James E Hoff Carl D |
| |
Institution: | Department of Chemistry, Massachusetts Institute of Technology, Room 2-227, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, USA. |
| |
Abstract: | Molybdenum chalcogenobenzimidates of formula (PhPhE]C=N)Mo(Nt-Bu]Ar)(3) (Ar = 3,5-C(6)H(3)Me(2)) have been obtained by treatment of Mo(Nt-Bu]Ar)(3) sequentially with benzonitrile and 0.5 equiv of PhEEPh (E = S, Se, and Te). Molecular structure determinations have been carried out for the S and Se variants. The Te variant extrudes PhCN forming structurally characterized (PhTe)Mo(Nt-Bu]Ar)(3) with facility assessed via stopped-flow kinetic measurements, while the Se and S analogues exhibit increasing stability. Quantum chemical calculations and solution calorimetry have been employed as an aid to interpretation of the PhCN extrusion reaction. |
| |
Keywords: | |
本文献已被 PubMed 等数据库收录! |
|