Contrasting Bonding Extremes in Two [Ge6]n- Complexes: A Wadian Polyhedron (n = 2) versus a Hydrocarbon-like 2c-2e Polygermanide (n = 12)

Ai-Min Li; Yi Wang; Peter Y Zavalij; Yu-Sheng Chen; Alvaro Muñoz-Castro; Bryan W Eichhorn

doi:10.1021/acs.inorgchem.1c01799

Contrasting Bonding Extremes in Two [Ge₆]^n- Complexes: A Wadian Polyhedron (n = 2) versus a Hydrocarbon-like 2c-2e Polygermanide (n = 12)

Inorg Chem. 2021 Oct 4;60(19):14697-14705. doi: 10.1021/acs.inorgchem.1c01799. Epub 2021 Sep 23.

Authors

Ai-Min Li¹, Yi Wang¹, Peter Y Zavalij¹, Yu-Sheng Chen², Alvaro Muñoz-Castro³, Bryan W Eichhorn¹

Affiliations

¹ Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, United States.
² ChemMatCARS, Center for Advanced Radiation Sources, The University of Chicago, 9700 South Cass Avenue, Argonne, Illinois 60439, United States.
³ Laboratorio de Química Inorgánica y Materiales Moleculares, Facultad de Ingeniería, Universidad Autonoma de Chile, Llano Subercaseaux 2801, San Miguel, Santiago Chile.

PMID: 34555280
DOI: 10.1021/acs.inorgchem.1c01799

Abstract

[Nb(η⁶-C₆H₃Me₃)₂] reacts with ethylenediamine (en) solutions of K₄Ge₉ in the presence of 18-crown-6 to give [(η⁶-C₆H₃Me₃)NbHGe₆]^2- (1) and [(η⁶-C₆H₃Me₃)NbGe₆Nb(η⁶-C₆H₃Me₃)]^2- (2) as their corresponding [K(18-crown-6)]⁺ salts. The crystalline solids are dark brown, air-sensitive, and sparingly soluble or insoluble in most solvents. The [K(18-crown-6)]⁺ salts of cluster ions 1 and 2 have been characterized by energy-dispersive X-ray (EDX) analysis, NMR studies, single-crystal X-ray diffraction, and electrospray ionization time-of-flight (ESI-TOF) mass spectrometry studies. Cluster ions 1 and 2 have markedly different [Ge₆] moieties: an electron-deficient carborane-like subunit in 1 and a two-center, two-electron cyclohexane-like subunit in 2.