Synthesis of silyl iron hydride <i>via</i> Si–H activation and its dual catalytic application in the hydrosilylation of carbonyl compounds and dehydration of benzamides
The hydrido silyl iron complex (o-Ph2PC6H4SiMe2)Fe(PMe3)3H (2) was obtained via the activation of the Si–H bond of the bidentate silyl ligand o-Ph2P(C6H4)SiMe2H (1) by Fe(PMe3)4. 2 showed good to excellent catalytic activity in both the reduction of aldehydes/ketones and the dehydration of benzamide. In addition, with complex 2 as a catalyst, α,β-unsaturated carbonyls could be selectively reduced to
氢化硅烷基铁络合物(o -Ph 2 PC 6 H 4 SiMe 2)Fe(PMe 3)3 H(2)是通过激活双齿甲硅烷基配体o -Ph 2 P(C)的Si–H键而获得的Fe(PMe 3)4形成6 H 4)SiMe 2 H(1)。图2在醛/酮的还原和苯甲酰胺的脱水中均显示出良好至优异的催化活性。另外,带复数2作为催化剂,α,β-不饱和羰基可以选择性地还原为相应的α,β-不饱和醇。提出了2的形成机理和催化脱水过程,并进行了部分实验验证。
Hydrosilylation of aldehydes and ketones catalyzed by hydrido iron complexes bearing imine ligands
作者:Zhenyu Zuo、Hongjian Sun、Lin Wang、Xiaoyan Li
DOI:10.1039/c4dt00944d
日期:——
Two new hydrido ironcomplexes (2 and 4) were synthesized by the reactions of (4-methoxyphenyl)phenylketimine ((4-MeOPh)PhCNH) with Fe(PMe3)4 or FeMe2(PMe3)4. The molecular structures of complexes 2 and 4 were confirmed by X-ray single crystal diffraction. Using hydrido ironcomplexes (1–4) as catalysts, the hydrosilylations of aldehydes and ketones were investigated. The four complexes were effective
(5)], were used as catalysts to study the effects of pyridine N-oxide and the electronic properties of [PSiP]-ligands on the catalytic hydrosilylation of carbonyl compounds. It was proved for the first time that this catalytic process could be promoted with pyridine N-oxide as the initiator at 30 °C because the addition of pyridine N-oxide is beneficial for the formation of an unsaturated hydrido iron
五个[PSiP]钳制铁氢化物1-5,[(2-Ph 2 PC 6 H 4)2 HSiFe(H)(PMe 3)2(1),(2-Ph 2 PC 6 H 4)2 MeSiFe( H)(PMe 3)2(2),(2-Ph 2 PC 6 H 4)2 PhSiFe(H)(PMe 3)2(3),(2-(iPr)2 PC 6 H 4)2 HSiFe(高)(PMe3)( 4)和(2-(iPr) 2 PC 6 H 4) 2 MeSiFe(H)(PMe 3) 2( 5)]用作催化剂,研究吡啶-N-氧化物和电子[PSiP]-配体对羰基化合物催化氢化硅烷化反应的影响 首次证明在30°C下以吡啶N-氧化物为引发剂可以促进该催化过程,因为添加吡啶N-氧化物有利于形成不饱和氢化铁络合物,这是关键催化机制中的中间体。复杂4作为最好的催化剂表现出优异的催化性能。在五个复合物,复合物3是新的,复杂的分子结构3通过单晶X射线衍射来确定。讨论了一种建议的机制。
Syntheses of hydrido selenophenolato iron(II) complexes and their catalytic application in hydrosilylation of aldehydes and ketones
for this process. Furthermore, α,β-unsaturated alcohols could be obtained from the selective reduction reactions of the corresponding α,β-unsaturatedcarbonyls catalyzed by hydrido iron(II) complex 5. This catalytic system has good tolerance for some common groups but it is easy to reduce the nitro group to an amino group. The experiments indicate that the chemoselectivity for this catalytic system is
三种新颖的硒代酚醛氢化铁(II)配合物[顺式-(H)(SeAr)Fe(PMe 3)4 ](4–6)(Ar = C 6 H 5(4),p -MeOC 6 H 4(5)和ö -MeC 6 ħ 4(6))至铁(PME的反应制备3)4与selenophenols ArSeH(1-3经由硒-H活化)。铁络合物氢基4,5和6可以催化醛和酮的氢化硅烷化。其中络合物5是该方法的最佳催化剂。此外,由氢化铁(II)配合物5催化的相应α,β-不饱和羰基的选择性还原反应可以得到α,β-不饱和醇。该催化体系对某些常见基团具有良好的耐受性,但易于将硝基还原为氨基。实验表明,该催化体系的化学选择性为CHO> NO 2 > C(O)CH 3。通过X射线衍射确定6的晶体结构。
Synthesis and Catalytic Activity of Iron Hydride Ligated with Bidentate N-Heterocyclic Silylenes for Hydroboration of Carbonyl Compounds
We report the synthesis of a novelbidentate N-heterocyclic silylene (NHSi) ligand, N-(LSi:)-N-methyl-2-pyridinamine (1) (L = PhC(NtBu)2), and the first bischelate disilylene iron hydride, [(Si,N)(Si,C)Fe(H)(PMe3)] (2), and monosilylene iron hydride, [(Si,C)Fe(H)(PMe3)3] (2′), through Csp2–H activation of the NHSi ligand. Compounds 1 and 2 were fully characterized by spectroscopic methods and single-crystal