78134-33-5Relevant academic research and scientific papers
Di-tert-butoxybis(arylimido)molybdenum(VI) compounds, [Mo(O-t-Bu)2(NAr)(μ-NAr)]2, where Ar = phenyl and p-tolyl
Chisholm,Folting,Huffman,Ratermann
, p. 978 - 982 (2008/10/08)
Mo2(O-t-Bu)6 (M≡M) reacts in hydrocarbon solvents with aryl azides, ArN3 (≥4 equiv), where Ar = phenyl and p-tolyl, to give [Mo(O-t-Bu)2(NAr)2]2 compounds along with N2 and tert-butoxy radicals. No intermediates have been detected in this reaction which brings about oxidative cleavage of the molybdenum-to-molybdenum triple bond. A single-crystal structural determination of the p-tolylimido compound revealed unsymmetrically bridged imido ligands of the type recently noted by Nugent and Harlow. Each molybdenum atom is five-coordinate, and the central Mo2O4N2N′2 skeleton may be viewed as two trigonal-bipyramidal units fused along a common equatorial-axial edge through the agency of a pair of bridging imido ligands. The other pair of imido ligands occupies axial positions and has short Mo-N distances, 1.74 (1) ? (averaged), and near-linear Mo-N-C angles. The bridging imido ligands form alternately short (equatorial) 1.84 (1) ? and long (axial) 2.30 (2) ? (averaged) bonds to molybdenum, with the latter being trans to the terminal imido ligands. An interesting structural comparison is made with the Mo2(O-i-Pr)8 and [Mo(O-i-Pr)3NO]2 molecules. Crystal data for [Mo(O-t-Bu)2(N-p-tolyl)2]2 at -170°C were a = 10.789 (2) ?, b = 25.904 (6) ?, c = 13.007 (3) ?, α = 73.11 (1)°, β = 81.34 (1)°, and γ = 91.25 (1)°, with space group P1.
