Molybdenum Chalcogenobenzimidato Complexes: Radical Synthesis and Nitrile Extrusion via β-EPh (E = S, Se, and Te) Elimination

Arjun Mendiratta, Christopher C. Cummins, Olga P. Kryatova, Elena V. Rybak-Akimova, James E. McDonough, Carl Hoff

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

Molybdenum chalcogenobenzimidates of formula (Ph[PhE]C=N)-Mo(N[t-Bu]Ar)3 (Ar = 3,5-C6H 3Me2) 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.

Original languageEnglish
Pages (from-to)8621-8623
Number of pages3
JournalInorganic Chemistry
Volume42
Issue number26
DOIs
StatePublished - Dec 29 2003

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Nitriles
Molybdenum
nitriles
Calorimetry
Molecular structure
molybdenum
Extrusion
elimination
Kinetics
synthesis
molecular structure
heat measurement
analogs
kinetics
benzonitrile

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Molybdenum Chalcogenobenzimidato Complexes : Radical Synthesis and Nitrile Extrusion via β-EPh (E = S, Se, and Te) Elimination. / Mendiratta, Arjun; Cummins, Christopher C.; Kryatova, Olga P.; Rybak-Akimova, Elena V.; McDonough, James E.; Hoff, Carl.

In: Inorganic Chemistry, Vol. 42, No. 26, 29.12.2003, p. 8621-8623.

Research output: Contribution to journalArticle

Mendiratta, Arjun ; Cummins, Christopher C. ; Kryatova, Olga P. ; Rybak-Akimova, Elena V. ; McDonough, James E. ; Hoff, Carl. / Molybdenum Chalcogenobenzimidato Complexes : Radical Synthesis and Nitrile Extrusion via β-EPh (E = S, Se, and Te) Elimination. In: Inorganic Chemistry. 2003 ; Vol. 42, No. 26. pp. 8621-8623.
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abstract = "Molybdenum chalcogenobenzimidates of formula (Ph[PhE]C=N)-Mo(N[t-Bu]Ar)3 (Ar = 3,5-C6H 3Me2) 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.",
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