Dinitrogen Cleavage by Three-Coordinate Molybdenum(III) Complexes:  Mechanistic and Structural Data¹

Abstract

SQUID Magnetic Measurements on#1 -z+1,x-1/2,-y+1/2 Positional parameters and B(eq) for 2.62(5)2.40(5) 2.1(4) 2.4(4) 2.4(4) 2.3(4) 2.0(4) 2.0(4) 2.1(5) 2.7(6) 2.5(5) 3.2(6) 3.0(6) 3.9(7) 3.1(6) 4.3(7) 2.5(5) 3.7(6) 2.8(6) 3.1(6) 3.8(6) 3.3(6) 2.2(5) 2.2(5) 3.0(6) 2.6(5) 2.9(6) 3.5(6) 3.1(6) 3.7(7) 2.8(6) 3.3(6) 3.0(6) 2.5(5) 2.8(6) 3.0(6) 2.4(5) 2.6(5) 2.9(6) 2.5(5) 3.8(7) 3.3(6) 4.0(7) 3.7(7) 3.2(6) 3.2(6) 2.4(5) 2.9(6) 2.6(5) 0 1996 American Chemical Society J. Am. Chem. Soc. VI 18 Page8623 Laplaza Supplemental Page 9Positional parameters and B(eq) for 0.044(7) 0.038 (7 1.960 (7) 1.964 (7) 1.977 (7) 1.970 (7) 1.968 (7) 1.956 (7) 1.42 (1) 1.50(1)1.42 (1) 1.48 (1) 1.44 (1) 1.49 ( 122.8(9)122 (1) 117 ( 120 (1) 120 (1) 120 (

Highlights in the Renaissance of Amidometal Chemistry

“…[213] A comprehensive structural characterization of the violet, paramagnetic intermediate 61 or its analogous 15 N 2 complex by EXAFS [214] and Raman spectroscopy together with kinetic data on the conversion to the corresponding nitrido complex gave a detailed insight into the course of the NÀ bond cleavage. [215] The conversion of 61 into two equivalents of 62 takes place by a first-order reaction. The data of the kinetic isotope effect of the bond cleavage, Mo 2 N 2 versus Mo 2 15 N 2 , confirm that the N À N cleavage is the rate-determining step.…”

Assignment of pre-edge features in the Ru K-edge X-ray absorption spectra of organometallic ruthenium complexes

“…It has generally been assumed that the pre-edge features for second-row transition metals are due to 4d←1s transitions by analogy to first-row metals; although, in many cases, the possibility of 5p←1s transitions has not been excluded [5][6][7][8]. More detailed studies of Mo [9] and Pd [10] K-edges have provided reasonable assignment of pre-edge features for these metals as due to metal 4d←1s transitions.…”

Inner-sphere two-electron reduction leads to cleavage and functionalization of coordinated dinitrogen

“…Stoichiometric cleavage of the strong N-N bond has been observed for groups 5 and 6 metal complexes (20)(21)(22)(23)(24)(25), certain dinuclear zirconium dinitrogen complexes have been found to react with H 2 to generate N-H bonds (26)(27)(28), and terminal alkynes have been found to react with coordinated N 2 in a side-on bound dizirconium complex to generate a N-C bond (29). These processes have expanded the toolbox of fundamental reactions for coordinated dinitrogen.…”