Abstract Cyclic gallaphosphene L (PCO) GaPGaL 1 (L = HCC (Me) NAr 2 ; Ar = 2, 6‐ i ‐Pr 2 ‐C 6 H 3) selectively reacts with NH 3 and H 2 O at ambient temperature with twofold N─H and O─H bond activation and formation of compounds LGa (μ‐PH) (μ‐NHC (O) PH) GaL 2 and LGa (μ‐PH) (μ‐OC (O) PH) GaL 3. Both nucleophilic P atoms of 1 are protonated in these reactions, while the electrophilic carbon atom of the bridging PCO unit binds to the remaining NH group / O atom. The formation of heterocycles 2 and 3, which were characterized by heteronuclear NMR (1 H, 13 C 1 H, 31 P 1 H) and IR spectroscopy, elemental analysis, and single‐crystal X‐ray diffraction (sc‐XRD), is only possible due to a beneficial interplay between the polar Ga─P double bond and the electrophilic nature of the C center in the bridging PCO unit. The reaction mechanism and energetics of the NH 3 reaction was investigated in detail by quantum chemical calculations, which also highlight the importance of bimolecular reaction processes with the involvement of an additional NH 3 molecule.
Sharma et al. (Fri,) studied this question.
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