Pnictogen-Hydride Activation by (silox)<sub>3</sub>Ta (silox = <sup>t</sup>Bu<sub>3</sub>SiO); Attempts to Circumvent the Constraints of Orbital Symmetry in N<sub>2</sub> Activation
作者:Elliott B. Hulley、Jeffrey B. Bonanno、Peter T. Wolczanski、Thomas R. Cundari、Emil B. Lobkovsky
DOI:10.1021/ic101147x
日期:2010.9.20
Activation of N2 by (silox)3Ta (1, silox = tBu3SiO) to afford (silox)3Ta═N−N═Ta(silox)3 (12-N2) does not occur despite ΔG°cald = −55.6 kcal/mol because of constraints of orbital symmetry, prompting efforts at an independent synthesis that included a study of REH2 activation (E = N, P, As). Oxidative addition of REH2 to 1 afforded (silox)3HTaEHR (2-NHR, R = H, Me, nBu, C6H4-p-X (X = H, Me, NMe2); 2-PHR
N个激活2由(SILOX)3 TA(1,SILOX =吨卜3的SiO),得到(SILOX)3 Ta═N-N═Ta(SILOX)3(1 2 -N 2)不尽管Δ发生ģ ° CALD = -55.6千卡/摩尔,因为轨道对称性的约束,促使在一个独立的合成,其中包括的研究努力的REH 2活化(E = N,P,As)的。氧化加成REH的2至1,得到(SILOX)3 HTaEHR(2 -NHR,R = H,Me中,Ñ卜,C 6ħ 4 - p -X(X = H,Me中,NME 2); 2 -PHR,R = H,Ph;2 -AsHR,R = H,PH),其经历1,2--H 2在剔除,以形成(SILOX)3 Ta═NR(1 = NR; R = H,Me中,Ñ卜,C 6 H ^ 4 - p -X(X = H(X射线)中,Me,NME 2,CF 3)),(SILOX)3 Ta═PR(1 ═PR; R = H,PH),和(SILOX)3