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Title: Direct measurements of copper speciation in basaltic glasses: understanding the relative roles of sulfur and oxygen in copper complexation in melts
Award ID(s):
1834930 1834939 1834959 1834941
PAR ID:
10129313
Author(s) / Creator(s):
; ; ; ; ; ; ;
Date Published:
Journal Name:
Geochimica et Cosmochimica Acta
Volume:
267
Issue:
C
ISSN:
0016-7037
Page Range / eLocation ID:
164 to 178
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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  1. Odd-electron bonds have unique electronic structures and are often encountered as transiently stable, homonuclear species. In this study, a pair of copper complexes supported by Group 13 metalloligands, M[N(( o -C 6 H 4 )NCH 2 P i Pr 2 ) 3 ] (M = Al or Ga), featuring two-center/one-electron (2c/1e) σ-bonds were synthesized by one-electron reduction of the corresponding Cu( i ) ⇢ M(III) counterparts. The copper bimetallic complexes were investigated by X-ray diffraction, cyclic voltammetry, electron paramagnetic spectroscopy, and density functional theory calculations. The combined experimental and theoretical data corroborate that the unpaired spin is delocalized across Cu, M, and ancillary atoms, and the singly occupied molecular orbital (SOMO) corresponds to a σ-(Cu–M) bond involving the Cu 4p z and M n s/ n p z atomic orbitals. Collectively, the data suggest the covalent nature of these interactions, which represent the first examples of odd-electron σ-bonds for the heavier Group 13 elements Al and Ga. 
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