Sharma Mahendra K, Weinert Hanns M, Wölper Christoph, Schulz Stephan
Institute of Inorganic Chemistry, University of Duisburg-Essen, Universitätsstraße 5-7, D-45141, Essen.
Center for Nanointegration Duisburg-Essen (CENIDE), University of Duisburg-Essen, Carl-Benz-Straße 199, D-47057, Duisburg.
Chemistry. 2024 Mar 25;30(18):e202400110. doi: 10.1002/chem.202400110. Epub 2024 Feb 2.
Gallaphosphene L(Cl)GaPGaL 1 (L=HC[C(Me)N(Ar)]; Ar=2,6-iPrCH) reacts with N-heterocyclic carbenes NHC (NHC=[CMeN(R)]C; R=Me, iPr) to NHC-coordinated phosphinidenes NHC→PGa(Cl)L (R=Me 2 a, iPr 2 b) and with isonitriles RNC (R=iPr, Cy) to 1,3-phosphaazaallenes L(Cl)GaP=C=N-R (R=iPr 3 a, Cy 3 b), respectively. Quantum chemical calculations reveal that 2 a/2 b possess two localized lone pair of electrons, whereas 3 a/3 b only show one localized lone pair as was reported for gallaphosphene 1. 2 b reacts with 2.5 equivalents of a borane (THF ⋅ BH) to the NHC-stabilized phosphinidene-borane complex NHC→P(BH) 4 with concomitant formation of LGa(H)Cl 5. 2-5 are characterized by heteronuclear (H, C{H}, P{H}) NMR and IR spectroscopy, elemental analysis, and single crystal X-ray diffraction (sc-XRD).
镓磷烯L(Cl)GaPGaL 1（L = HC[C(Me)N(Ar)]；Ar = 2,6-iPrCH）与氮杂环卡宾NHC（NHC = [CMeN(R)]C；R = Me，iPr）反应生成NHC配位的磷烯NHC→PGa(Cl)L（R = Me 2 a，iPr 2 b），并分别与异腈RNC（R = iPr，Cy）反应生成1,3-磷氮丙二烯L(Cl)GaP=C=N-R（R = iPr 3 a，Cy 3 b）。量子化学计算表明，2 a/2 b具有两个定域孤对电子，而3 a/3 b如镓磷烯1报道的那样仅显示一个定域孤对电子。2 b与2.5当量的硼烷（THF ⋅ BH）反应生成NHC稳定的磷烯-硼烷配合物NHC→P(BH) 4，同时生成LGa(H)Cl 5。2 - 5通过异核（H，C{H}，P{H}）核磁共振和红外光谱、元素分析以及单晶X射线衍射（sc-XRD）进行表征。
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