Synthesis, Structure, and Bonding Analysis of Lewis Base and Lewis Acid/Base‐Stabilized Phosphanylgallanes

Abstract

Phosphanylgallane with hydrogen and halogen substituents (RXGa PHR, R=organic substituent, X=halogen/hydrogen) are regarded as putative suitable precursors for accessing Ga=P doubly bonded species. Herein, we report on the synthesis, structure, and bonding analysis of a series of Lewis base- and Lewis acid/base-stabilized phosphanylgallane bearing P H and Ga Cl/H substitution. To avoid oligomerization, the treatment of IDip.GaCl3 and (IDip)GaH2Cl (IDip=1,3-bis(2,6-diisopropylphenyl) imidazole-2-ylidene) with LiPHR or LiPHR(BH3) (R=Ph, Tip, Mes, NiPr2, NCy2) affords the corresponding Lewis base and Lewis acid/base coordinated H,Cl-functionalized monomeric phosphanylgallane, respectively. The structure of these derivatives were determined by spectroscopic and X-ray crystallographic analyses. The observed Ga P bond lengths are comparable to those previously reported phosphanylgallane analogues. The nature of the CIDip-Ga coordination bond was assessed with Energy Decomposition Analysis, suggesting a relatively stable adduct. Reactions of the phosphanylgallane with Brønsted bases were investigated.