Nitrogen-bridged bidentate phosphaalkene ligands

作者：du Mont Wolf Walther^*; Gimeno Rafael Guerrero; Lungu Daniela; Birzoi Roxana M; Daniliuc Constantin G; Goers Christine; Riecke Antje; Bartsch Rainer

来源：Pure and Applied Chemistry, 2013, 85(4): 633-647.

DOI：10.1351/PAC-CON-12-09-02

• ligand properties
• molecular rearrangements
• organophosphorus chemistry
• palladium
• platinum
• rhodium, X-ray structure

Nitrogen-bridged bidentate phosphaalkenes reveal several exceptional properties as a new class of P=C-unsaturated diphosphinoamine (PNP) ligands: N-Si bond cleavage of the first N-silylimino-bridged bis-phosphaalkene (R2C=P)(2)NSiMe3 (R = iPrMe(2)Si) with chlorides of Ag-I, Au-I, and Rh-I leads to complexes of the 5c-6 pi-heteropentadienide imidobisphosphaalkene anion; double Cl- transfer from PtCl2 and PdCl2 to coordinated phosphaalkene phosphorus atoms of P-diphenylphosphanylamino phosphaalkenes R2C=PN(R')PPh2 (R' = Me3Si or iPrMe(2)Si; R = tBu, 1-Ada) furnishes unprecedented bis-chelate P-chloroylid complexes M[R2CP(Cl)N(R')PPh2](2) (M = Pd, Pt); CO- and Rh-I-induced coupling of two P-diphenylphosphanylamino phosphaalkenes under disilylketene elimination provides trigonal-bipyramidal Rh-III complexes with novel tetradentate dianionic "PNP-C-PNP" ligands R2C[P(-)N(R')PPh2](2).

• 出版日期2013