Hu Dandan, Lu Bo, Song Chao, Zhu Bifeng, Wang Lina, Bernhardt Eduard, Zeng Xiaoqing
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China.
Department of Chemistry, Fudan University, Shanghai, 200433, China.
Dalton Trans. 2021 Mar 9;50(9):3299-3307. doi: 10.1039/d1dt00261a.
Two phosphorous(iii) isocyanates, ClP(NCO)2 and P(NCO)3 were isolated as neat substances and characterized with IR (gas-phase and Ne-matrix), Raman (solid), and 31P NMR spectroscopy. Their vibrational spectra were analyzed in terms of a single conformer with the aid of quantum chemical computations at the B3LYP/6-311+G(3df) level of theory. In line with the theoretically computed favorable syn-configuration of the NCO ligands with the sterically active lone-pair electrons on the central phosphorous atom (nP), low-temperature single-crystal X-ray diffraction (XRD) of solid ClP(NCO)2 reveals a Cs symmetric syn-configuration for both NCO ligands with weak CO (r = 2.9692(4) Å) van der Waals (vdW) interactions. In the binary isocyante P(NCO)3, all the three NCO ligands adopt similar syn-configuration with nP, leading to a propeller-shaped structure with slightly distorted C3v symmetry due to steric repulsion of the NCO ligands and the PO vdW interactions (r = 3.1901(1) Å) in the solid state.
两种磷（III）异氰酸酯，ClP(NCO)₂ 和 P(NCO)₃ 被分离为纯净物，并通过红外光谱（气相和氖基质）、拉曼光谱（固态）和³¹P核磁共振光谱进行表征。借助理论水平为B3LYP/6 - 311 + G(3df)的量子化学计算，依据单一构象对它们的振动光谱进行了分析。与理论计算得出的NCO配体与中心磷原子（nP）上具有空间活性孤对电子的顺式构型相符，固态ClP(NCO)₂ 的低温单晶X射线衍射（XRD）显示两个NCO配体均为Cs对称顺式构型，存在较弱的CO（r = 2.9692(4) Å）范德华（vdW）相互作用。在二元异氰酸酯P(NCO)₃ 中，所有三个NCO配体与nP均采用相似的顺式构型，由于NCO配体的空间排斥以及固态中PO的范德华相互作用（r = 3.1901(1) Å），形成了具有略微扭曲C₃v对称性的螺旋桨状结构。
