Sharma Mahendra K, Dhawan Pratima, Helling Christoph, Wölper Christoph, Schulz Stephan
Institute of Inorganic Chemistry, University of Duisburg-Essen, Universitätsstraße 5-7, 45141, Essen, Germany.
Center for Nanointegration Duisburg-Essen (CENIDE), University of Duisburg-Essen, Carl-Benz-Straße 199, 47057, Duisburg, Germany.
Chemistry. 2022 Apr 19;28(22):e202200444. doi: 10.1002/chem.202200444. Epub 2022 Mar 14.
Phosphaketenes are versatile reagents in organophosphorus chemistry. We herein report on the synthesis of novel bis-phosphaketenes, LM(PCO) (M=Ga 2 a, In 2 b; L=HC[C(Me)N(Ar)] ; Ar=2,6-i-Pr C H ) by salt metathesis reactions and their reactions with LGa to metallaphosphenes LGa(OCP)PML (M=Ga 3 a, In 3 b). 3 b represents the first compound with significant In-P π-bonding contribution as was confirmed by DFT calculations. Compounds 3 a and 3 b selectively activate the N-H and O-H bonds of aniline and phenol at the Ga-P bond and both reactions proceed with a rearrangement of the phosphaethynolate group from Ga-OCP to M-PCO bonding. Compounds 2-5 are fully characterized by heteronuclear ( H, C{ H}, P{ H}) NMR and IR spectroscopy, elemental analysis, and single crystal X-ray diffraction (sc-XRD).
磷杂环丁二烯是有机磷化学中用途广泛的试剂。我们在此报告通过盐复分解反应合成新型双磷杂环丁二烯LM(PCO)（M = Ga 2a，In 2b；L = HC[C(Me)N(Ar)]；Ar = 2,6-i-Pr₂C₆H₃）及其与LGa反应生成金属磷烯LGa(OCP)PML（M = Ga 3a，In 3b）。3b是第一个具有显著In-P π键贡献的化合物，这一点已通过密度泛函理论（DFT）计算得到证实。化合物3a和3b在Ga-P键处选择性地活化苯胺和苯酚的N-H键和O-H键，并且两个反应都伴随着磷乙炔醇盐基团从Ga-OCP重排为M-PCO键合。化合物2 - 5通过异核（¹H，¹³C{¹H}，³¹P{¹H}）核磁共振和红外光谱、元素分析以及单晶X射线衍射（sc-XRD）进行了全面表征。
