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.

Triphosphiranes as phosphinidene-transfer agents – synthesis of regular and chelating NHC phosphinidene adducts

“…53 Note that the WBI in the IDip 2 -adduct of the phosphinogallane Cl 2 Ga-PPh 2 is considerably higher at 0.78. 55 There is also an additional lone pair of electrons (LP) at each phosphorus atom with sp-hybrid character, which is minimally delocalized into the imidazolin-2-ylidene unit. The P-C NHC bonds are σ-bonds polarized towards C NHC and a WBI of ca.…”