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Updated: Jun 7, 2026

Synthesis of Single-Crystalline Core-Shell Metal-Organic Frameworks
Published on: February 10, 2023
Pseudotetrahedral d(0), d(1), and d(2) metal-oxo cores within a tris(alkoxide) platform
Stanislav Groysman1, Dino Villagrán, Daniel G Nocera
1Department of Chemistry, 6-335, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139-4307, United States.
Abstract:
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.
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