Sterically hindered electron-withdrawing ligands: the reactions of N-carbazolyl phosphines with rhodium and palladium centres
作者:Andrew D. Burrows、Mary F. Mahon、Maurizio Varrone
DOI:10.1039/b408841g
日期:——
[PdCl(2)(NCMe)(2)] instead of [PdCl(2)(cod)] resulted in the formation of the complexes [PdCl(2)(L1)(2)] 7 from L1, the cyclometallated complex [Pd(mu-Cl)[P(NC(12)H(8))(2)(NC(12)H(7))-kappa(2)P,C]](2) 8 from L3 , and a mixture of [PdCl(2)(L2)(2)] 9 and [Pd(mu-Cl)[PPh(NC(12)H(8))(NC(12)H(7))-kappa(2)P,C]](2) 10 from L2 . The reaction of L3 with [Pd(OAc)(2)] produced the cyclometallated complex [Pd(mu-O(2)CCH(3))
已使用BuLi合成了一系列N-咔唑基膦PPh(3-n)(NC(12)H(8))(n)(n = 1,L1; n = 2,L2; n = 3,L3)生成N-咔唑基锂盐,然后与适当的氯膦反应。[Rh(mu-Cl)(CO)(2)](2)与四个当量的L1或L2之间的反应给出[RhCl(CO)(L1)(2)] 1和[RhCl(CO)(L2) (2)] 2,尽管尝试使用L3合成类似的配合物,却导致了[Rh(mu-Cl)(CO)(L3)](2)3的形成。L3不能裂解氯桥可能与它相当大的空间要求有关。通过比较[Rh(acac)(CO)(L1-3)]配合物4-6的nu(CO)值来评估L1-3的电子性质。磷原子上N-咔唑基取代基数量的增加导致σ供体的减少和pi受体特性的增加,顺序为L1
A new series of N–PSe resonance-based fluorescent molecules were developed and used for the detection of hypochlorousacid (HClO) with rapid response and high selectivity. These Se-containing molecules can selectively detect trace amounts of HClO in nM, showing significantly strengthened fluorescence due to the enhanced resonance variation with an increased distance between the fluorophore and Se.
Electrochemical oxidative N–H/P–H cross-coupling with H<sub>2</sub> evolution towards the synthesis of tertiary phosphines
作者:Yong Yuan、Xue Liu、Jingcheng Hu、Pengjie Wang、Shengchun Wang、Hesham Alhumade、Aiwen Lei
DOI:10.1039/d1sc07248j
日期:——
Tertiaryphosphines(III) find widespread use in many aspects of synthetic organic chemistry. Herein, we developed a facile and novel electrochemical oxidative N–H/P–H cross-coupling method, leading to a series of expected tertiaryphosphines(III) under mild conditions with excellent yields. It is worth noting that this electrochemical protocol features very good reaction selectivity, where only a 1 : 1
叔膦( III )在合成有机化学的许多方面都有广泛的用途。在此,我们开发了一种简便且新颖的电化学氧化N-H/P-H交叉偶联方法,在温和的条件下以优异的产率产生了一系列预期的叔膦( III )。值得注意的是,该电化学方案具有非常好的反应选择性,反应中仅需要胺和磷化氢的比例为1:1。此外,该电化学协议被证明是实用且可扩展的。机理分析表明 P 自由基参与了该反应。