title: A tungstenVI nitride having a W2(mu-N)2 core.
abstract: The tungsten nitrido species, [W(mu-N)(CH2-t-Bu)(OAr)2]2 (Ar = 2,6-diisopropylphenyl), has been prepared in a reaction between the alkylidyne species, W(C-t-Bu)(CH2-t-Bu)(OAr)2, and organonitriles. The dimeric nature of the nitride was established in the solid state through an X-ray study and in solution through a combination of 15N NMR spectroscopy and vibrational spectroscopy. Reaction of the nitride with trimethylsilyl trifluoromethanesulfonate afforded the monomeric trimethylsilyl imido species, W(NSiMe3)(CH2-t-Bu)(OAr)2(OSO2CF3), which was also characterized crystallographically. The W2N2 core can be reduced by one electron electrochemically or in bulk with metallocenes to afford the radical anion, {n-Bu4N}{[W(mu-N)(CH2-t-Bu)(OAr)2]2}. Density functional theory calculations suggest that the lowest-energy allowable transition in [W(mu-N)(CH2-t-Bu)(OAr)2]2 is from a highest occupied molecular orbital consisting largely of ligand-based lone pairs into what is largely a metal-based lowest unoccupied molecular orbital.
authors.affiliation: Department of Chemistry 6-331, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
authors.forename: Zachary J
authors.initials: ZJ
authors.lastname: Tonzetich
authors.forename: Richard R
authors.initials: RR
authors.lastname: Schrock
authors.forename: Keith M
authors.initials: KM
authors.lastname: Wampler
authors.forename: Brad C
authors.initials: BC
authors.lastname: Bailey
authors.forename: Christopher C
authors.initials: CC
authors.lastname: Cummins
authors.forename: Peter
authors.initials: P
authors.lastname: Müller