N,N鈥?Fused Bisphosphole: Heteroaromatic Molecule with Two-Coordinate and Formally Divalent Phosphorus. Synthesis, Electronic Structure, and Chemical Properties

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• 作者：Alexander N. Kornev ; Vyacheslav V. Sushev ; Yulia S. Panova ; Olga V. Lukoyanova ; Sergey Yu. Ketkov ; Evgenii V. Baranov ; Georgy K. Fukin ; Mikhail A. Lopatin ; Yulia G. Budnikova ; Gleb A. Abakumov
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：March 17, 2014
• 年：2014
• 卷：53
• 期：6
• 页码：3243-3252
• 全文大小：603K
• 年卷期：v.53,no.6(March 17, 2014)
• ISSN：1520-510X

文摘

The reduction of 6,12-dichloro-1,2,3,4,7,8,9,10-octahydro-6H,12H-[1,2,3]benzodiazaphospholo[2,1-a][1,2,3]benzodiazaphosphole (3) by metallic magnesium in tetrahydrofuran (THF) affords the N,N鈥?fused bisphosphole 1 in 92% yield. The compound reveals a novel type of 10蟺-electron heteroaromatic system [NICS(0) = 鈭?1.4], containing a two-coordinate and formally divalent phosphorus atom. Compound 1 possesses a much higher coordination activity than many other diazaphospholes. This is caused by a novel type of complexation to a metal ion wherein the lone phosphorus pairs are not involved in metal coordination. Instead, the 10蟺-electron heteroaromatic system provides two electrons for P 鈫?M bond formation. Polarization of the ligand results in the formation of extended molecular associates or cluster compounds. Complexes of 1 with mercury dichloride [{(1)₃HgCl}₂(渭₆-Cl)]⁺Cl^{鈥?/sup> (7) and tin dichlorides [1路SnCl₂(PhMe solvate)] (8a) and [1路SnCl₂] (8b) are, in fact, supramolecular in nature, containing multiple intermolecular short contacts. Crystals of complex 8a containing short Sn路路路Sn packing interactions were converted reversibly to metallic tin after workup with THF. The simple mixing of 1 and 3 (1:1) gave a P鈥揚 bridging dimeric species prone to easy dissociation. The addition of GeCl₂(diox) to the equimolar mixture of 1 and 3 shifted the equilibrium to the formation of a poorly soluble salt-like dimer 6, which is, in fact, a stacked 18蟺-electron dication having a through-space delocalization of 蟺 electrons.}