Department of Chemistry, 6-335, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139-4307, United States.
Inorg Chem. 2010 Dec 6;49(23):10759-61. doi: 10.1021/ic101968s. Epub 2010 Nov 4.
Low-coordinate first-row metal complexes of d(0) [vanadium(V)], d(1) [chromium(V)], and d(2) [chromium(IV)] assume the unusual ligand field of a pseudotetrahedron when supported by a tripodal tBu(2)(Me)CO(-) alkoxide framework. Structural, spectroscopic, and reactivity studies, supported by density functional theory calculations, indicate that the d electrons in the chromium(V) and -(IV) oxo complexes reside in metal-oxygen antibonding orbitals, engendering disparate reactivity of the metal-oxo, depending on the number of d electrons present.
当三脚（叔丁基）（甲氧基）酮（tBu(2)(Me)CO(-)）烷氧基配体支撑 d(0) [钒(V)]、d(1) [铬(V)]和 d(2) [铬(IV)]的低配位数的第一过渡金属配合物时，它们采用了一个拟四面体的不寻常配体场。结构、光谱和反应性研究，以及密度泛函理论计算的支持，表明铬（V）和（IV）氧配合物中的 d 电子位于金属-氧反键轨道中，这导致了金属-氧的反应性不同，具体取决于存在的 d 电子数。
