TY - JOUR
T1 - Beyond transition block metals
T2 - exploring the reactivity of phosphine PTA and its oxide [PTA(O)] towards gallium(iii)
AU - Guerriero, Antonella
AU - Ienco, Andrea
AU - Hicks, Thomas
AU - Cilibrizzi, Agostino
N1 - Publisher Copyright:
© 2024 The Royal Society of Chemistry
PY - 2024/7/4
Y1 - 2024/7/4
N2 - The water-soluble cage-like phosphine PTA (1,3,5-triaza-7-phosphaadamantane) and its phosphine oxide derivative [PTA(O)] (1,3,5-triaza-7-phosphaadamantane-7-oxide) were used to explore their reactivity towards two gallium(iii)-halide precursors, namely GaCl3 and GaI3, for the first time. By using various reaction conditions, a series of N-mono-protonated phosphine salts with [GaCl4]− or [I]− as counterions were obtained in all cases, while the formation of coordinated Ga-PTA and Ga-[PTA(O)] complexes was not observed. All compounds were characterized in solution using multinuclear NMR spectroscopy (1H, 13C{1H}, 31P{1H} and 71Ga) and in the solid state using FT-IR spectroscopy and X-ray crystal diffraction. The new Ga-phosphine salts resulted stable and highly soluble in aqueous solution at room temperature. Density functional theory (DFT) calculations were also performed to further rationalize the coordination features of PTA with Ga3+ metal ion, highlighting that the phosphorus-gallium bond is about twice weaker than the phosphorus-metal bond commonly established by PTA with transition metals such as gold. Furthermore, the mono-protonation of PTA (or [PTA(O)]) makes the formation of ionic gallium-PTA coordination complexes thermodynamically unstable, as confirmed experimentally by the formation of Ga-phosphine salts reported herein.
AB - The water-soluble cage-like phosphine PTA (1,3,5-triaza-7-phosphaadamantane) and its phosphine oxide derivative [PTA(O)] (1,3,5-triaza-7-phosphaadamantane-7-oxide) were used to explore their reactivity towards two gallium(iii)-halide precursors, namely GaCl3 and GaI3, for the first time. By using various reaction conditions, a series of N-mono-protonated phosphine salts with [GaCl4]− or [I]− as counterions were obtained in all cases, while the formation of coordinated Ga-PTA and Ga-[PTA(O)] complexes was not observed. All compounds were characterized in solution using multinuclear NMR spectroscopy (1H, 13C{1H}, 31P{1H} and 71Ga) and in the solid state using FT-IR spectroscopy and X-ray crystal diffraction. The new Ga-phosphine salts resulted stable and highly soluble in aqueous solution at room temperature. Density functional theory (DFT) calculations were also performed to further rationalize the coordination features of PTA with Ga3+ metal ion, highlighting that the phosphorus-gallium bond is about twice weaker than the phosphorus-metal bond commonly established by PTA with transition metals such as gold. Furthermore, the mono-protonation of PTA (or [PTA(O)]) makes the formation of ionic gallium-PTA coordination complexes thermodynamically unstable, as confirmed experimentally by the formation of Ga-phosphine salts reported herein.
UR - http://www.scopus.com/inward/record.url?scp=85198227564&partnerID=8YFLogxK
U2 - 10.1039/d4ra02877e
DO - 10.1039/d4ra02877e
M3 - Article
AN - SCOPUS:85198227564
SN - 2046-2069
VL - 14
SP - 21139
EP - 21150
JO - RSC Advances
JF - RSC Advances
IS - 29
ER -