Synthesis of bimetallic rhodium phosphinine complexes with enhanced catalytic activity towards alkyne hydrosilylation
作者:Clarence Tan、Hendrik Tinnermann、Vanessa Wee、Shaun Tan、Simon Sung、Qingyang Wang、Rowan D. Young
DOI:10.1016/j.jorganchem.2023.122617
日期:2023.2
that bimetallic complexes 3a-c show enhanced activity to monometallic and monocationic analogues (i.e. 2d) with improved yields of up to 13 times and reaction rates of over 4 times for the same rhodium concentration. We show that the dicationic monometallic η3-benzo-λ5-phosphinine rhodium complex 2e also displays enhanced activity and that the higher activity in bimetallic complexes 3a-c likely arises
炔烃与 PC卡宾P 络合物1(具有亚烷基锚定钳形配体)的反应导致 η 3 -苯并-λ 5 -膦铑络合物2的形成。将两个当量的1与二炔反应可以轻松获得双金属 η 3 -苯并-λ 5 -膦铑配合物3。使用这种方法,化合物2a-c、e和3a-c被合成和表征。测试这些化合物作为炔烃氢化硅烷化的催化剂表明双金属配合物3a-c对单金属和单阳离子类似物(即2d)显示出增强的活性,对于相同的铑浓度,收率提高了 13 倍,反应速率提高了 4 倍以上。我们表明,双阳离子单金属 η 3 -苯并-λ 5 -膦铑配合物2e也表现出增强的活性,双金属配合物3a-c中较高的活性可能源于它们的双阳离子性质。