Homoleptic seven-coordinate Ti(0) and Zr(0) through a new stabilization mode

Antsiburov I, Bühler R, Stephan J, Erdyakov M, Gemel C, Kahlal S, Cador O, Guizouarn T, Saillard JY, Meyer K, Fischer RA (2026)

Publication Type: Journal article

Publication year: 2026

Journal

Chemical Science Royal Society of Chemistry

DOI: 10.1039/d6sc00226a

Abstract

The stabilization of zero oxidation state group (IV) metal centers in readily accessible compounds on a preparative scale remains a significant challenge. Substituting hydrocarbon ligands in the precursor complexes [Ti(η6-toluene)2] and [Zr(η6-cycloheptatriene)2] with monovalent GaTMP (TMP = 2,2,6,6-tetramethylpiperidinyl) yields the first homoleptic seven-coordinate Ti0 and Zr0 complexes, [Ti(GaTMP)7] (1) and [Zr(GaTMP)7] (2), which are exclusively coordinated by metalloligands. The bonding situation of 1 and 2 was rationalized through DFT calculations, revealing the critical importance of tangential Ga⋯Ga covalent interactions for stabilizing the compounds. Oxidation of 2 leads to the formation of [Zr(GaTMP)8]2+ (5), showcasing a similar bonding situation. These Ga⋯Ga interactions arise from significant π-backbonding from the Ti0 and Zr0 centers into the constructive combinations of the diffuse 4p orbitals of the Ga(i) centers. This unique cooperative feature of the all-Ga metalloligand sphere marks a clear distinction from the bonding properties of formally isolobal carbonyls, phosphines, or N-heterocyclic carbenes.

Authors with CRIS profile

Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Technische Universität München (TUM) DE Germany (DE) Université de Rennes 1 / University of Rennes 1 FR France (FR)

How to cite

APA:

Antsiburov, I., Bühler, R., Stephan, J., Erdyakov, M., Gemel, C., Kahlal, S.,... Fischer, R.A. (2026). Homoleptic seven-coordinate Ti(0) and Zr(0) through a new stabilization mode. Chemical Science. https://doi.org/10.1039/d6sc00226a

MLA:

Antsiburov, Ivan, et al. "Homoleptic seven-coordinate Ti(0) and Zr(0) through a new stabilization mode." Chemical Science (2026).

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