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New Experimental Insight into the Nature of Metal−Metal Bonds in Digallium Compounds: J Coupling between Quadrupolar Nuclei
Author(s) -
Kobera Libor,
Southern Scott A.,
Rao Gyandshwar Kumar,
Richeson Darrin S.,
Bryce David L.
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201600999
Subject(s) - gallium , atomic orbital , chemistry , spin (aerodynamics) , context (archaeology) , metal , chemical bond , coupling constant , crystallography , resonance (particle physics) , boron , coupling (piping) , main group element , chemical physics , computational chemistry , atomic physics , transition metal , materials science , physics , organic chemistry , nuclear physics , thermodynamics , quantum mechanics , paleontology , biology , metallurgy , catalysis , electron
Multiple bonding between atoms is of ongoing fundamental and applied interest. Here, we report a multinuclear ( 1 H, 13 C, and 71 Ga) solid‐state magnetic resonance spectroscopic study of digallium compounds which have been proposed, albeit somewhat controversially, to contain single, double, and triple Ga−Ga bonds. Of particular relevance to the nature of these bonds, we have carried out two‐dimensional 71 Ga J / D ‐resolved NMR experiments which provide a direct measurement of J ( 71 Ga, 71 Ga) spin–spin coupling constants across the gallium−gallium bonds. When placed in the context of clear‐cut experimental data for analogous singly, doubly, and triply bonded carbon spin pairs or boron spin pairs, the 71 Ga NMR data clearly support the notion of a different bonding paradigm in the gallium systems. Our findings are consistent with an increasing role across the purported gallane–gallene–gallyne series for classical and/or slipped π‐type bonding orbitals.