hydridocarbonylchlorotris(triphenylphosphine)osmium(II) 、 bis(2-(diisopropylphosphanyl)ethyl)ether 以
not given 为溶剂,
生成 carbonyl(chloro)hydrido(bis(2-diisopropylphosphanyl)ethyl)ether)osmium(II)
参考文献:
名称:
用于醇脱氢的for和钌催化剂
摘要:
合成了一系列Os和Ru的钳型配合物,并在催化醇脱氢中进行了研究。氢化物OsHCl(CO)[HN(C 2 H 4 P i Pr 2)2 ]和OsH 2(CO)[HN(C 2 H 4 P i Pr 2)2 ]具有良好的空气,湿气和热稳定性,并且是用于伯醇的杰出通用型脱氢催化剂,用于转移氢化,脱氢偶联和胺烷基化反应。
Substituents Effects in POP Pincer Complexes of Ruthenium
作者:Quinn Major、Alan J. Lough、Dmitry G. Gusev
DOI:10.1021/om050053v
日期:2005.5.1
Reactions of [RuCl2(p-cymene)](2) with ((Bu2PCH2CH2)-Bu-t)(2)O (POP-Bu-t) and (Pr2PCH2CH2)(2)O (POP-Pr-i) afforded RuCl2(POP-Bu-t) (1) and [Ru-2(mu-Cl)(3)(POP-Pr-i)(2)]Cl (2 center dot Cl), respectively. The POP ligand is coordinated in a mer fashion in complex 1, whose crystal structure revealed a gamma-agostic C-H center dot center dot center dot Ru interaction of one Bu-t group. Spectroscopic evidence indicated that this agostic interaction is retained in 1 in solution. A related compound, [Ru(N-2)Cl(POP-Bu-t)]BPh4 (4), which also showed agostic bonding of a Bu-t group, was obtained by substitution of N-2 for Cl- in 1, in the presence of NaBPh4. Compound 2 center dot Cl readily underwent ion exchange with LiBPh4 or LiPF6 to give 2 center dot BPh4 or 2 center dot PF6 salts, respectively. A crystallographic analysis of 2 center dot PF6 established a co-facial bioctahedral geometry of the [Ru-2(mu-Cl)(3)(POP-Pr-i)(2)](+) cation containing two POP ligands coordinated in a fac fashion. Reactions of 1 and 2 with H-2 afforded the dihydrogen complexes cis,trans-Ru(H-2)Cl-2(POP-Bu-t) (3) and cis,cis-Ru(H-2)Cl-2(POP-Pr-i) (5), respectively. The H-H bond distances are very similar in both compounds, r(H-H) = 1.0 +/- 0.1 angstrom, based on the T-1min and J(HD) data and results of DFT calculations. Reaction of 2 with N-2 gave the dinitrogen complex cis,cis-Ru(N-2)Cl-2(POP-Pr-i) (6), but solutions of 1 under a nitrogen atmosphere showed no evidence of an analogous compound. The different steric requirements of the phosphorus substituents of the POP ligands were identified as the source of the differences in the coordination properties of the POP-Bu-t and POP-iPr complexes 1-6.
Osmium and Ruthenium Catalysts for Dehydrogenation of Alcohols
作者:Marcello Bertoli、Aldjia Choualeb、Alan J. Lough、Brandon Moore、Denis Spasyuk、Dmitry G. Gusev
DOI:10.1021/om200437n
日期:2011.7.11
of pincer-type complexes of Os and Ru have been synthesized and investigated in catalytic alcohol dehydrogenation. The hydrides OsHCl(CO)[HN(C2H4PiPr2)2] and OsH2(CO)[HN(C2H4PiPr2)2] possess good air, moisture, and thermal stability and are outstanding versatile dehydrogenation catalysts for primary alcohols for reactions of transfer hydrogenation, dehydrogenative coupling, and amine alkylation.
合成了一系列Os和Ru的钳型配合物,并在催化醇脱氢中进行了研究。氢化物OsHCl(CO)[HN(C 2 H 4 P i Pr 2)2 ]和OsH 2(CO)[HN(C 2 H 4 P i Pr 2)2 ]具有良好的空气,湿气和热稳定性,并且是用于伯醇的杰出通用型脱氢催化剂,用于转移氢化,脱氢偶联和胺烷基化反应。