Metathesis of nitrogen atoms within triple bonds involving carbon, tungsten, and molybdenum.
(ButO)3Mo triple bond N and W2(OBut)6(M triple bond M) react in hydrocarbons to form Mo2(OBut)6(M triple bond M) and (ButO)3W triple bond N via the reactive intermediate MoW(OBut)6(M triple bond M). (ButO)3W triple bond N and CH3C triple bond N15 react in tetrahydrofuran (THF) at room temperature to give an equilibrium mixture involving (ButO)3W triple bond N15 and CH3C triple bond N. The (ButO)3W triple bond N compound is similarly shown to act as a catalyst for N15-atom scrambling between MeC13 triple bond N15 and PhC triple bond N to give a mixture of MeC13 triple bond N and PhC triple bond N15. From studies of degenerate scrambling of N atoms involving (ButO)3W triple bond N and MeC13 triple bond N in THF-d8 by 13C(1H) NMR spectroscopy, the reaction was found to be first order in acetonitrile and the activation parameters were estimated to be DeltaH = 13.4(7) kcal/mol and DeltaS = -32(2) eu. A similar reaction is observed for (ButO)3Mo triple bond N and CH3C triple bond N15 upon heating in THF-d8. The reaction is suppressed in pyridine solutions and not observed for the dimeric [(ButMe2SiO)3W triple bond N]2. The reaction pathway has been investigated by calculations employing density functional theory on the model compounds (MeO)3M triple bond N and CH3C triple bond N where M = Mo and W. The transition state was found to involve a product of the 2 + 2 cycloaddition of M triple bond N and C triple bond N, a planar metalladiazacyclobutadiene. This resembles the pathway calculated for alkyne metathesis involving (MeO)3W triple bond CMe, which modeled the metathesis of (ButO)3W triple bond CBut. The calculations also predict that the energy of the transition state is notably higher for M = Mo relative to M = W.
Burroughs
Beth A
BA
Department of Chemistry, The Ohio State University, Columbus, Ohio 43210, USA.
Bursten
Bruce E
BE
Chen
Shentan
S
Chisholm
Malcolm H
MH
Kidwell
Andy R
AR