Pseudotetrahedral d(0), d(1), and d(2) metal-oxo cores within a tris(alkoxide) platform.
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.
Department of Chemistry, 6-335, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139-4307, United States.
Stanislav
S
Groysman
Dino
D
Villagrán
Daniel G
DG
Nocera