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Updated: May 28, 2025

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Synthesis and Reactivity of Germyl-Substituted Gallapnictenes
Yuanyuan Wang1, Harsha S Karnamkkott2, Jicheng Wang1
1Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Key Laboratory of Light Energy Conversion Materials of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, China.
Abstract:
Decarbonylation of the phospha- and arsaketenyl germylenes (L)GeECO (E = P, As; L = CH[C(Me)NAr]2, Ar = 2,6-iPr2C6H3) in the presence of the Ga(I) precursor (L)Ga afforded the corresponding germyl-substituted gallaphosphene 1 and gallaarsene 3, respectively. Both 1 and 3 are examples of unsaturated chains with heavier group 13/15/14 elements. The germylene center and the polarized Pn = Ga (Pn = P or As) double bond provide multiple sites for small-molecule activation. For example, gallaarsene 3 reacted with adamantyl azide in a formal [3 + 2]-cyclization to give 4 containing a GaAsN3 heterocycle, clearly underlining the analogy between the As = Ga and C-C multiple bonds. By contrast, the reaction of 3 with Me-I afforded the 1,3-addition product 5, which indicates frustrated Lewis pair character in 3. DFT calculations indicate that the Ga-P/As bonds are highly polarized toward the pnictogen center. EDA-NOCV calculations further support this description and additionally shed light on ambiguous bonding scenarios in 4 and 5. These calculations prove that orbital interactions are outweighed by electrostatic interactions, resulting in polar bonds with significant ionic character.
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