Department of Chemistry and the Molecular Structure Center, Indiana University, Bloomington, Indiana 47405, USA.
J Am Chem Soc. 2010 Feb 10;132(5):1458-9. doi: 10.1021/ja908303k.
Two neutral and four-coordinate vanadium(V)-nitrido complexes have been prepared via the thermolysis of metastable vanadium(III)-azido precursors. All complexes have been fully characterized by multinuclear NMR, FT-IR, isotopic labeling, and, in most instances, single crystal X-ray diffraction. On the basis of activation parameters, N(2) extrusion to form the V[triple bond]N moiety is proposed to occur via an ordered and early transition state having three- or four-triazametallacycle frameworks. In addition, we demonstrate the nitrido ligand to undergo incomplete N-atom transfer to CO and CN{2,6-Me(2)-C(6)H(3)) to form the bent V-N=C=X (X = O, N{2,6-Me(2)-C(6)H(3)}) ligands with concomitant 2e(-) reduction at the vanadium center.
通过热解亚稳态的钒(III)-叠氮前驱物，制备了两个中性和四配位的钒(V)-亚硝酰基配合物。所有配合物均通过多核 NMR、FT-IR、同位素标记以及在大多数情况下通过单晶 X 射线衍射进行了充分的表征。基于活化参数，提出 N2 脱除形成 V[三键]N 部分是通过具有三或四氮杂金属环框架的有序和早期过渡态发生的。此外，我们证明亚硝酰配体经历不完全的 N-原子转移到 CO 和 CN{2,6-Me(2)-C(6)H(3)}，形成弯曲的 V-N=C=X（X = O，N{2,6-Me(2)-C(6)H(3)})配体，同时在钒中心发生 2e(-)还原。
