1248801-79-7Relevant articles and documents
Chemistry of the phosphorus-nitrogen ligands. Multiple isomeric transformations of the diphosphinohydrazine bearing 8-quinolyl substituent: P→C, P→N, and P→P migrations caused by different factors
Kornev, Alexander N.,Belina, Natalia V.,Sushev, Vyacheslav V.,Panova, Julia S.,Lukoyanova, Olga V.,Ketkov, Sergey Y.,Fukin, Georgy K.,Lopatin, Mikhail A.,Abakumov, Gleb A.
experimental part, p. 9677 - 9682 (2011/01/12)
The reaction of 8-quinolylhydrazine with 2 equiv of Ph2PCl in the presence of Et3N gives 8-[(Ph2P)2NNH]-Quin (1) (Quin = quinolyl) in 84% yield. The heating of 1 at 130 °C for 1 h in toluene results in migration of the [Ph2PNPPh2] group to a carbon atom of the quinolyl fragment to form an isomer, 7-(Ph 2P-N=PPh2)-8-NH2-Quin (2). The same migration is caused by the addition of LiN(SiMe3)2 to 1. On the contrary, lithiation of 1 with n-BuLi followed by the addition of ZnI 2 (1:1) affords the aminoquinolyl-phosphazenide dinuclear complex [ZnI(8-Quin-NPPh2dN-PPh2)-κ3N,N,P] 2 (4), which is a result of P→N migration. Compound 1 itself reacts with ZnI2 in THF to form 4 and protonated molecule 1 · HI, which rearranges to the more stable iminobiphosphine salt (Ph 2P-PPh2dN-NH-Quin-8)3HI. Zinc iodide reacts with 2 equiv of the lithium salt of 1 without rearrangement, to form homoleptic aminoquinolyl zinc complex Zn[{(Ph2P)2NN-Quin-8}-κ2N, N]2 (6). Solutions of 4 and 2 in dichloromethane show luminescence at 510 and 460 nm (quantum yields are 45% and 7%, respectively). DFT calculations were provided for possible isomers and their complexes.
