具有合成可寻址和半稳定性活性位点的氧化还原活性多金属平台是模拟酶辅因子对多电子转换的反应性的有吸引力的合成目标。为此,通过酰氨基膦配体锚定在 [Co 6 Se 8 ] 多金属载体上的具有三个边缘金属位点的三元簇是一个很有前景的平台。在本报告中,我们探讨了这些配体的立体电子特性的微小变化如何改变 [Co 6 Se 8 ] 金属配体的形成,以及两个新三元簇 M 3 Co 6 Se 中的底物结合亲和力和边缘/支持相互作用的强度8L 6 (M = Zn、Fe;L (-) = Ph 2 PN (-) i Pr)。使用一系列方法广泛表征这些簇,包括单晶 X 射线衍射、电子吸收光谱和循环伏安法。底物结合研究表明,Fe 3 Co 6 Se 8 L 6抵抗较大配体如吡啶或四氢呋喃的配位,但结合较小的配体CN t Bu。此外,研究使用两种氨基膦合成新的 [Co 6 Se 8 ] 金属配体,Ph 2 PN(H)
Directed <i>Ortho</i>-Lithiation of Aminophosphazenes: An Efficient Route to the Stereoselective Synthesis of <i>P</i>-Chiral Compounds
作者:María Casimiro、Laura Roces、Santiago García-Granda、María José Iglesias、Fernando López Ortiz
DOI:10.1021/ol400971q
日期:2013.5.17
electrophilic quench is described as an efficient process for synthesizing P-chiral ortho-functionalized derivatives in high yields and diastereoselectivities. The method allows the tunable preparation of structurally diverse enantiopure P-chiral compounds including phosphinic and phosphinothioic amides, phosphinic esters, phosphine oxides, and o-aminophosphines.
Phosphino-amine (PN) Ligands for Rapid Catalyst Discovery in Ruthenium-Catalyzed Hydrogen-Borrowing Alkylation of Anilines: A Proof of Principle
作者:Lewis Marc Broomfield、Yichen Wu、Eddy Martin、Alexandr Shafir
DOI:10.1002/adsc.201500562
日期:2015.11.16
A general synthetic protocol for the synthesis of simple phosphino-amine (PN) ligands is described with 19 ligands being isolated in good yields. High-throughput ligand screening uncovered the success of two of these ligands for aromatic amine alkylations via ruthenium-catalyzedhydrogen borrowing reactions. The combination of N,N′-bis(diphenylphosphino)-N,N′-dimethylpropylenediamine with a ruthenium(II)
Nickel-based complexes and their use in a process for the transformation of olefins
申请人:IFP Energies Nouvelles
公开号:US09308528B2
公开(公告)日:2016-04-12
The invention describes a novel type of nickel-based complex and its preparation method. The invention also concerns the use of said complex in a process for the transformation of olefins.
Self-Assembled Organometallic Nickel Complexes as Catalysts for Selective Dimerization of Ethylene into 1-Butene
作者:Pierre Boulens、Emmanuel Pellier、Erwann Jeanneau、Joost N. H. Reek、Hélène Olivier-Bourbigou、Pierre-Alain R. Breuil
DOI:10.1021/acs.organomet.5b00055
日期:2015.4.13
aminophosphine ligands self-assemble to readily form active and stable nickel catalysts that are highly selective for the dimerization of ethylene to 1-butene. The self-assembled allyl-nickel complexes are zwitterionic and are stabilized by hydrogen bond interactions between the two ligands. These organometallic cis-diphosphine complexes rearrange under an ethylene atmosphere to give trans-diphosphine catalysts