title: Molybdenum chalcogenobenzimidato complexes: radical synthesis and nitrile extrusion via beta-EPh (E = S, Se, and Te) elimination.
abstract: Molybdenum chalcogenobenzimidates of formula (Ph[PhE]C=N)Mo(N[t-Bu]Ar)(3) (Ar = 3,5-C(6)H(3)Me(2)) have been obtained by treatment of Mo(N[t-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(N[t-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.
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology, Room 2-227, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, USA.
authors.forename: Arjun
authors.initials: A
authors.lastname: Mendiratta
authors.forename: Christopher C
authors.initials: CC
authors.lastname: Cummins
authors.forename: Olga P
authors.initials: OP
authors.lastname: Kryatova
authors.forename: Elena V
authors.initials: EV
authors.lastname: Rybak-Akimova
authors.forename: James E
authors.initials: JE
authors.lastname: McDonough
authors.forename: Carl D
authors.initials: CD
authors.lastname: Hoff