163929-89-3Relevant academic research and scientific papers
Dinitrogen cleavage by three-coordinate molybdenum(III) complexes: Mechanistic and structural data
Laplaza, Catalina E.,Johnson, Marc J. A.,Peters, Jonas C.,Odom, Aaron L.,Kim, Esther,Cummins, Christopher C.,George, Graham N.,Pickering, Ingrid J.
, p. 8623 - 8638 (1996)
The synthesis and characterization of the complexes Mo[N(R)Ar]3 (R = C(CD3)2CH3, Ar = 3,5-C6H3Me2), (μ-N2){Mo[N(R)Ar]3}2, (μ-15N2){Mo[N(R)Ar]3}2, NMo[N(R)Ar]3, 15NMo[N(R)Ar]3, Mo[N(t-Bu)Ph]3, (μ-N2){Mo[N(t-Bu)Ph]3}2, and NMo[N(t-Bu)Ph]3 are described. Temperature-dependent magnetic susceptibility data indicate a quartet ground state for Mo[N(R)Ar]3. Single-crystal X-ray diffraction studies for Mo[N(R)Ar]3 and NMo[N(t-Bu)Ph]3 are described. Extended X-ray absorption fine structure (EXAFS) structural studies for Mo[N(R)AR]3, (μN2){Mo[N(R)Ar]3}2, and NMo[N(R)AR]3 are reported. Temperature-dependent kinetic data are given for the unimolecular fragmentation of (μ-N2){Mo[N(R)Ar]3}2 to 2 equiv of NMo[N(R)Ar]3 and for the fragmentation of (μ-15N2){Mo[N(R)AR]3}2 to 2 equiv of 15NMo[N(R)AR]3. The temperature dependence of the 15N2 isotope effect for the latter N2 cleavage process was fitted to a simple harmonic model, leading to a prediction for the difference in NN stretching frequencies for the two isotopomers. The latter prediction was consistent with the Raman spectroscopic data for (μ-N2){Mo[N(R)Ar]3}2 and (μ-15N2){Mo[N(R)Ar]3}2. The Raman spectroscopic data and EXAFS results are both consistent with an NN bond order of approximately 2 in (μ-N2){Mo[N(R)Ar]3}2. Temperature-dependent magnetic susceptibility data consistent with a triplet ground state are given for (μ-N2){Mo[N(t-Bu)Ph]3}2.
