868611-08-9Relevant academic research and scientific papers
Reactions of ruthenium-aminophosphane complexes with diynes: P-N bond activation and formation of novel phosphaallyl, azaallyl, and aminocarbene complexes
Pavlik, Sonja,Jantscher, Florian,Dazinger, Georg,Mereiter, Kurt,Kirchner, Karl
, p. 1006 - 1021 (2007/10/03)
The aminophosphane complexes [RuCp(PPh2NRR′2)- (CH3CN)2]+ and [RuCp*(PPh 2NRR′2)(CH3CN)2]+ (NRR′ = NHnPr, NEt2, NC5H5) react with 1,6-heptadiyne and 1,7-octadiyne to yield novel η3-phosphaallyl- η2-vinylamine complexes of the types [RuCp{η3-(P, C,C)-PPh2CH=C-(CH2)n-η2-(C,C)-C= CHNRR′2}]+ and [RuCp*{η3-(P,C, C)-PPh2CH=C-(CH2)n-η2-(C,C)-C= CHNRR′2}]+ (n = 3, 4). These complexes are the kinetic products but eventually form the η1-phosphaallyl- η3-azaallyl complexes [RuCp{η1-(P)-PPh 2CH=C-(CH2)n-η3-(C,C,N)- CCHNRR′2}]+ and [RuCp*{η1-(P)- PPh2CH=C-(CH2)n-η3-(C,C,N)- CCHNRR′2}]+, respectively. With n = 3 elevated temperatures are required, while with n = 4 this conversion takes places already at room temperature. The only exception is [RuCp*(PPh2NHnPr) (CH3CN)2]+ where amido butadiene complexes [RuCp*{η1-(N)-NnPrPPh2-η4-CH= C(CH2)nCH=CH2}]PF6 (n = 3, 4) are obtained instead. In the case of [RuCp{η1-(P)-PPh 2CH=C-(CH2)3-η3-(C,C,N)- CCHNRR′2}]+ with NRR′ = NEt2 and NC5H5, a further rearrangement took place at elevated temperatures affording the aminocarbenes [RuCp{=C(NRR′)η2- (C,C)-C(CH2)3C-CH2-(η1-(P)- PPh2)}]+. Representative X-ray structures are presented. Moreover, conceivable mechanisms for all these reaction sequences are established by means of DFT/B3LYP calculations. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
Ruthenium-mediated insertion of an unsaturated C4 unit into the P-N bond of an aminophosphine ligand
Pavlik, Sonja,Jantscher, Florian,Mereiter, Kurt,Kirchner, Karl
, p. 4899 - 4901 (2008/10/09)
The reactions of 1,6-heptadiyne and 1,7-octadiyne with [RuCp(PPh 2NEt2)(CH3CN)2]+ afford the η3-phosphaallyl-η2-vinylamine complexes [RuCp(η3-(P,C,C)-PPh2CH
