Using internal electrostatic fields to manipulate the valence manifolds of copper complexes
作者:Alexander B. Weberg、Samuel P. McCollom、Laura M. Thierer、Michael R. Gau、Patrick J. Carroll、Neil C. Tomson
DOI:10.1039/d0sc06364a
日期:——
density functional theory (DFT) studies revealed atypical valence manifold configurations, resulting from strongly σ-donating phosphinimine moieties in the xy-plane that destabilize 2e (dxy/dx2−y2) orbital sets and uniquely stabilized a1 (dz2) orbitals. Support is provided that the a1 stabilizations result from intramolecular electrostatic fields (ESFs) generated from cationic character on the phosphinimine
开发了一系列四齿三(膦亚胺)配体(R3 P 3 tren)并结合到Cu I上,形成了三角锥,C 3v对称的亚铜络合物[ R3 P 3 tren-Cu] [BAr F 4 ](1 PR3)(PR 3 = PMe 3,PMe 2 Ph,PMePh 2,PPh 3,PMe 2(NEt 2),BAr F 4 = B(C 6 F 5)4)。Cu I的电化学研究进行了复合,发现全甲基化的类似物1 PMe3具有前所未有的阴极Cu I / Cu II氧化还原电位(-780 mV对异丁腈中的Fc / Fc +)。通过密度泛函理论(DFT)研究阐明了1 PR3 的电子结构,揭示了非典型价歧管构型,这是由于xy平面中强烈σ供体的膦亚胺部分使2 e不稳定(d xy / d x 2 - y 2)轨道集和唯一稳定的1(d z 2)个轨道。提供了a 1稳定化的源于分子内静电场(ESF),该分子内静电场是由R3 P 3
KINASE INHIBITORS
申请人:Brown Jason W.
公开号:US20120252761A1
公开(公告)日:2012-10-04
Compounds are provided for use with kinases that comprise a compound selected from the group consisting of:
wherein the variables are as defined herein. Also provided are pharmaceutical compositions, kits and articles of manufacture comprising such compounds; methods and intermediates useful for making the compounds; and methods of using said compounds.
The present invention relates to metal complexes in accordance with formula (1), to use thereof in electronic devices and to electronic devices, particularly organic electroluminescent devices, containing said metal complexes.
An Improved Synthesis of <sup>Me4</sup>PCP and DMPE
作者:Travis T. Lekich、Phoebe G. Askelson、Ryan K. Burdick、D. Michael Heinekey
DOI:10.1021/acs.organomet.7b00780
日期:2018.1.22
We present a new synthetic method for the bis(dimethyl)phosphines (PCP)-P-Me4 (C6H4-2,6-(CH2P(CH3)(2))(2)) and DMPE ((CH3)(2)PCH2CH2P(CH3)(2)) that starts from an aminophosphine, Et2NPMe2. Two equivalents of Et2NPMe2 react with the corresponding bis(alkyl bromide) to afford an oxygen- and moisture-stable aminophosphonium salt. NaAlH4 selectively reduces the aminophosphonium salt to the desired phosphine. Each step is high yielding and requires minimal purification.