Panova Yulia, Khristolyubova Alexandra, Zolotareva Natalia, Sushev Vyacheslav, Galperin Vadim, Rumyantcev Roman, Fukin Georgy, Kornev Alexander
G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Science 49 Tropinin str., 603137 Nizhny Novgorod, Russia.
Dalton Trans. 2021 May 4;50(17):5890-5898. doi: 10.1039/d1dt00747e.
Treatment of 3a,6a-diaza-1,4-diphosphapentalene (DDP) with an excess of PhBCl2 yields the corresponding bis(borane) adduct DDP(PhBCl2)2 (14), demonstrating the availability of two lone pairs on the phosphorus center. The reaction between DDP and B(C6F5)3 yields (1 : 1) phosphino-borane complex 16. The free lone electron pair on the pyramidal P atom in 16 participates in the intramolecular non-covalent interactions P(1)F(1) and P(1)F(6) giving additional 3.9 and 2.8 kcal mol-1, respectively, for stabilization of the complex. This through-space interaction appears in the 31P NMR spectrum as large spin-spin coupling constants of 271 and 219 Hz. The addition of water to 16 (1 : 1) leads to the formation of the insertion product 17 having -H2P-O-B(C6F5)3 moiety. The reaction of DDP with BH3·SMe2 proceeds in several stages, which include the insertion of the masked phosphinidene into the B-H and P-H bonds of the intermediate compounds followed by the dehydrocoupling step and formation of diphosphine 18. The last compound exists in solution as a set of stereoisomers.
用过量的PhBCl₂处理3a,6a - 二氮杂 - 1,4 - 二磷杂戊搭烯（DDP）可得到相应的双（硼烷）加合物DDP(PhBCl₂)₂（14），这表明磷中心存在两个孤对电子。DDP与B(C₆F₅)₃之间的反应生成（1∶1）膦基 - 硼烷配合物16。16中锥形P原子上的自由孤电子对参与分子内非共价相互作用P(1)F(1)和P(1)F(6)，分别为配合物的稳定化额外提供3.9和2.8 kcal mol⁻¹。这种空间相互作用在³¹P NMR谱中表现为271和219 Hz的大自旋 - 自旋耦合常数。向16中加入水（1∶1）会导致形成具有 -H₂P - O - B(C₆F₅)₃部分的插入产物17。DDP与BH₃·SMe₂的反应分几个阶段进行，包括将掩蔽的磷烯插入中间化合物的B - H和P - H键中，随后进行脱氢偶联步骤并形成二膦18。最后一种化合物在溶液中以一组立体异构体的形式存在。
