Work

A Crystalline NiX 6 Complex

Year: 2024

Type: article

Abstract: High Resolution Image Download MS PowerPoint Slide High-valent nickel species are implicated as intermediates in industrially relevant chemical transformations and in the catalytic cycles of metalloenzymes. Although a small number of tetravalent NiX 4 complexes have been crystallographically characterized, higher nickel valence states have not been identified. Here we report a stable, crystalline NiX 6 complex, Ni(BeCp) 6 ( 1; cyclopentadienyl anion (Cp)), formed by the insertion of zerovalent nickel into three Be–Be bonds. This 16-electron species features an inverted ligand field, is diamagnetic, and exhibits C 3 v symmetry, on account of the lifting of Ni 4 p -orbital degeneracy in this molecular geometry. Single-crystal X-ray diffraction and quantum chemical calculations both reveal a toroidal band of electron density perpendicular to the C 3 axis of the complex, which may be attributed to delocalized, multicenter aromatic NiBe 6 bonding.

Source: Journal of the American Chemical Society

DOI: 10.1021/jacs.4c12125

Authors: Josef T. Boronski, Agamemnon E. Crumpton, Simon Aldridge

Institutions: University of Oxford, Imperial College London

Language: English

Topic: Organometallic Complex Synthesis and Catalysis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,500

Funders: Royal Society of Chemistry, Engineering and Physical Sciences Research Council, St. John's College, University of Oxford, John Fell Fund, University of Oxford