Iminophosphonamido-Supported Plumbylenes and Plumbyliumylidenes: Synthesis and Properties
Iminophosphonamido-Supported Plumbylenes and Plumbyliumylidenes: Synthesis and Properties
复制标题
亚氨基膦酰胺基支撑的铅烯和亚铅烯：合成与性能
DOI：
10.1021/acs.inorgchem.2c02209
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发表时间：
2022
影响因子：
4.6
通讯作者：
Nakata Norio
中科院分区：
文献类型：
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作者：
Nakaya Kazuki;Takahashi Shintaro;Ishii Akihiko;Nakata Norio
合成了一系列由anN，N ' -二叔丁基磷酰胺配体负载的低价铅（II）物质，即铅烯和铅酰基烯。用相应的亚磷酰胺锂与pbcl2在THF中反应制备了氯铅[Ph2P(NtBu)2PbCl](1)。1与KN(SiMe3)2在THF中的取代反应得到相应的无色晶体形式的氨基铅烯[Ph2P(NtBu)2PbN(SiMe3)2](2)。利用多核磁共振波谱和x射线衍射分析对固体和溶液中铅烯的结构进行了详尽的表征。在结晶状态下，1通过Pb-Cl键在轴方向上采用近似线性的聚合物结构，具有交替的四元PbN2P环。在室温下，用Na[B(C6F5)4]在氟苯中进行了有效的抽氯反应，得到了铅偏二甲基[Ph2P(NtBu)2Pb:]+(3+)，分离得到气敏黄硼酸盐[B(C6F5)4]。在环境条件下，当催化剂负荷量低至0.1 mol %时，铅铍基烯三[B(C6F5)4]作为路易斯酸催化剂用于二苯甲酮和苯甲醛的硼氢化反应。并根据DFT计算结果对反应机理进行了详细讨论。
A series of low-valent lead(II) species, i.e., plumbylenes and plumbyliumylidenes supported by anN,N′-di-tert-butyliminophosphonamide ligand, have been synthesized. Chloroplumbylene [Ph2P(NtBu)2PbCl] (1) was readily prepared by the reaction of the corresponding lithium iminophosphonamide and PbCl2in THF. The substitution reaction of1with KN(SiMe3)2in THF afforded the corresponding aminoplumbylene [Ph2P(NtBu)2PbN(SiMe3)2] (2) in the form of colorless crystals. The structures of these plumbylenes in the solid state and in solution were exhaustively characterized using multinuclear NMR spectroscopy and X-ray diffraction analysis. In the crystalline state,1adopts a nearly linear polymeric structure in the direction of thecaxis via Pb–Cl bonds, with alternating four-membered PbN2P rings. The chloride-abstraction reaction of1using Na[B(C6F5)4] in fluorobenzene proceeded efficiently at ambient temperature to furnish plumbyliumylidene [Ph2P(NtBu)2Pb:]+(3+), which was isolated as the air-sensitive yellow borate salt3[B(C6F5)4]. Plumbyliumylidene3[B(C6F5)4] acts as a Lewis acid catalyst for the hydroboration of benzophenone and benzaldehyde at catalyst loadings of as low as 0.1 mol % under ambient conditions. Furthermore, the details of the reaction mechanism are discussed on the basis of the results of DFT calculations.