报道了新型受阻三足膦配体P(CH 2 CH 2 CH 2 P i Pr 2)3(P 3 P 3 i Pr)(1)的合成与表征,以及钌氯和氢化物的合成与表征1的配合物。络合物[RuCl(P 3 P 3 i Pr)] [BPh 4 ](2 [ BPh 4 ]),RuH 2(P 3 P 3 i Pr)(3)和[Ru(H 2)(H)(P 3 P 3 i Pr)] [BPh 4 ](4 [ BPh 4 ])的特征在于晶体学。配合物2在溶液中是流动的,配合物的低温NMR光谱与两个动态过程密切相关,即立体异构体之间的交换和其中一种立体异构体中更快的旋转门类型交换。
报道了新型受阻三足膦配体P(CH 2 CH 2 CH 2 P i Pr 2)3(P 3 P 3 i Pr)(1)的合成与表征,以及钌氯和氢化物的合成与表征1的配合物。络合物[RuCl(P 3 P 3 i Pr)] [BPh 4 ](2 [ BPh 4 ]),RuH 2(P 3 P 3 i Pr)(3)和[Ru(H 2)(H)(P 3 P 3 i Pr)] [BPh 4 ](4 [ BPh 4 ])的特征在于晶体学。配合物2在溶液中是流动的,配合物的低温NMR光谱与两个动态过程密切相关,即立体异构体之间的交换和其中一种立体异构体中更快的旋转门类型交换。
New Superhindered Polydentate Polyphosphine Ligands P(CH<sub>2</sub>CH<sub>2</sub>P<sup><i>t</i></sup>Bu<sub>2</sub>)<sub>3</sub>, PhP(CH<sub>2</sub>CH<sub>2</sub>P<sup><i>t</i></sup>Bu<sub>2</sub>)<sub>2</sub>, P(CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>P<sup><i>t</i></sup>Bu<sub>2</sub>)<sub>3</sub>, and their Ruthenium(II) Chloride Complexes
作者:Ryan Gilbert-Wilson、Leslie D. Field、Mohan M. Bhadbhade
DOI:10.1021/ic2027169
日期:2012.3.5
The synthesis and characterization of the extremely hindered phosphine ligands, P((CH2CH2PBu2)-Bu-t)(3) ((PP3tBu)-P-2, 1), PhP((CH2CH2PBu2)-Bu-t)(2) (PhP(2)p(2)(tBu), 2), and P((CH2CH2CH2PBu2)-Bu-t)(3) ((PP3tBu)-P-3, 3) are reported, along with the synthesis and characterization of ruthenium chloro complexes RuCl2((PP3tBu)-P-2) (4), RuCl2((PhPP2tBu)-P-2) (5), and RuCl2((PP3tBu)-P-3) (6). The bulky (PP3tBu)-P-2 (1) and (PP3tBu)-P-3 (3) ligands are the most sterically encumbered PP3-type ligands so far synthesized, and in all cases, only three phosphorus donors are able to bind to the metal center. Complexes RuCl2((PhPP2tBu)-P-2) (5) and RuCl2((PP3tBu)-P-3) (6) were characterized by crystallography. Low temperature solution and solid state P-31H-1} NMR were used to demonstrate that the structure of RuCl2((PP3tBu)-P-3) (4) is probably analogous to that of RuCl2((PP3tBu)-P-3) (5) which had been structurally characterized.