Synthesis, Photophysics, Electrochemistry, and Excited-State Redox Properties of Trinuclear Copper(I) Acetylides with Bis(diphenylphosphino)alkylamines and -arylamines as Bridging Ligands
摘要:
A series of soluble trinuclear copper(I) complexes containing bicapped mu(3)-eta(1) acetylides, [Cu-3(mu-PNP)(3)(mu(3)-eta(1)-C=CR')(2)](+) [PNP = [(C6H5)(2)P](2)NR, R = Pr-n, C6H5, C6H4-CH3-p, C6H4-F-p] have been synthesized and shown to exhibit rich photoluminescent behavior at room temperature. The electrochemistry and excited-state redox properties of [Cu-3(mu-(PrPNP)-Pr-n)(3)-(mu(3)-eta(1)-C=CPh)(2)](+) have been investigated.
围绕刚性Fe(PNP)基序(PNP =(C 6 H 5)2 PN(R)P(C 6 H 5)2)构建的五配位羰基铁羰基配合物得到合成,并在结构和光谱上进行了表征。这些复合物允许使用各种类型的接头和官能团轻松地定制第二配体球。新的[Fe(S 2 C 6 H 4)(PNP)(CO)]配合物在弱酸性条件下(相对于Pt而言)在0.09–0.21 V的过电势下(在0.28至3.51 s -1的活度下)显示出二氢产生电催化)。最具活性的化合物在相对于Pt的过电势仅为0.15 V时表现出3.51 s -1的转换频率(TOF)。活动趋势将进一步分析。发现(a)过电势的降低与PNP胺取代基的吸电子强度强烈相关,并且(b)脂族取代基给出的TOF比芳族取代基的TOF高。通过初步还原Fe II金属中心并提议形成Fe III氢化物中间体,可以显示出一种EC型机理。合成和表征了类似的钴化合物,但发现在翻转条件下在酸性介
Facile Buchwald–Hartwig coupling of sterically encumbered substrates effected by PNP ligands
作者:Neha Kathewad、Anagha M. C.、Nasrina Parvin、Sneha Parambath、Pattiyil Parameswaran、Shabana Khan
DOI:10.1039/c9dt00159j
日期:——
We employed Ph2PN(Ar)PPh2 ligands for the palladium catalyzed C–N cross coupling of a variety of sterically demanding substrates and isolated very good yield of coupling products.