Access to Metal Complexes of the Elusive Imidobis(phosphaalkene) Anion by N-Si Bond Cleavage of a N-Silylimino-Bridged Bis(phosphaalkene)

作者：Birzoi Roxana M; Bugnariu Delia; Gimeno Rafael Guerrero; Riecke Antje; Daniliuc Constantin; Jones Peter G; Konczol Laszlo; Benko Zoltan; Nyulaszi Laszlo; Bartsch Rainer; du Mont Wolf W^*

来源：European Journal of Inorganic Chemistry, 2010, 2010(1): 29-33.

DOI：10.1002/ejic.200900982

• Bis(phosphaalkenes)
• PNP ligands
• pi-conjugation
• Gold
• Rhodium
• DFT calculations

Metalation of the aminophosphaalkene (iPrMe(2)Si)(2)C=PN(H)SiMe(3) (2) with lithium diisopropylamide (LDA) in THIF solution, followed by the reaction of the lithium salt 3 with the P-chlorophosphaalkenes (RMe(2)Si)(2)C=PCl (1a, R = Me; 1b, R = iPr; 1c, R = Ph), furnishes the first N-silylimmo-bridged bis(phosphaalkenes) [(iPrMe(2)Si)(2)C=P](2)NSiMe(3) (4a) and [(iPrMe(2)Si)(2)C=P][(RMe(2)Si)(2)C=P]NSiMe(3) (4b, R = Me; 4c, R = Ph). The N-Si bond cleavage of 4a under very mild conditions with AuCl(THT) and with [RhCl(COD)](2) provides binuclear Au(1) and Rh(1) complexes 5, 6 of the P, P'-coordinated imidobis(phosphaalkene) anion [(iPrMe(2)Si)(2)C=P](2)N(-), the first case of elusive P=C-unsaturated congeners of the "classic" bis(phosphanyl)amide ligands. Solid 4a exists in a helically distorted S-shaped structure with two inequivalent P=C groups, but (31)P-NMR reveals the equivalence of both P=C groups in solution at the NMR time scale. The P=C and P-N bonds distances in 4a do not indicate significant conjugation within the C=P-N-P=C moieties whereas in complexes 5 and 6 the W-shaped CPNPC heteropentadienide anion exhibits strong 5-center-6-pi conjugation according to DFT calculations and to the experimental P=C and P=N bond lengths.

• 出版日期2010-1