The coordination properties of [(2-O-3,5-tBu2C6H2)3P]3−([O3P]3−) as a potential tetradentate trianionic phosphorous aryloxide ligand towards the synthesis of low-coordinate and highly reactive Gallium Lewis acids complexes have been explored. Here, we report the synthesis and spectroscopic characterization of a series of cage-shaped gallium complexes GaX[O3PY] (X= Cl, Et), (Y= H, O), which were obtained through the reaction of GaX3 (X= Cl, Et) with tripodal phosphorous ligand H3[O3P] and its oxidized form H3[O3PO] at room temperature. The reaction between GaCl3 with H3[O3P] in THF resulted in the formation of the zwitterionic molecule GaCl[O3PH]. Additionally, it was found that crude GaCl[O3PH] will form [HP(OH)3][GaCl4] upon crystallization in toluene at -20 oC over a period of six days. Furthermore, two different approaches to synthesize the GaEt[O3PH] are described in this report. H3[O3PO] was found to form [(GaEt)2OPO(OH)2] when it coordinates with GaEt3 at 25 oC, where [OPO(OH)2] is a facially tridentate monophenolate phosphine ligand tethering a P-O bound phenol pendant. Characterization of these previously unreported compounds has been accomplished using NMR and IR spectrometry, mass spectrometry, and single-crystal X-ray diffraction.

Synthesis and structural elucidation of caged shaped gallium phosphorous aryloxide complexes

ACS Spring Meeting 2021

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