硼基和硼烯配合物与阳离子铜族金属片段的侧基配位。
Side-on coordination of boryl and borylene complexes to cationic coinage metal fragments.
作者信息
Braunschweig Holger, Radacki Krzysztof, Shang Rong
机构信息
Institut für Anorganische Chemie , Julius-Maximilians-Universität Würzburg , Am Hubland , 97074 Würzburg , Germany . Email:
出版信息
Chem Sci. 2015 May 1;6(5):2989-2996. doi: 10.1039/c5sc00211g. Epub 2015 Mar 10.
The M-(η-BMn) complex [(η-CH)(OC)Mn{μ-B(Cl)(Bu)Au(PPh)}] () can be functionalized halide substitution reactions to afford isostructural complexes [(η-CH)(OC)Mn{μ-B(R)(Bu)Au(PPh)}] (R = Ph, CCPh and NCS). It also reacts with coinage metal complexes [MCl(PPh)] (M = Au, Ag and Cu) in the presence of halide abstraction reagents to afford borylene-bridged heteromultinuclear complexes [{(η-CH)(OC)Mn}{μ-B(Bu)}M][BArx4] (M = Au, Ag and Cu; Ar = 3,5-CHCl, 3,5-CH(CF)). Experimental characterization as well as computational studies revealed that these complexes are best viewed as transition metal borylene complexes side-on coordinated to monovalent coinage metal cations, thus representing the first boron analogs of Stone's alkylidyne-bridged multinuclear complexes.
M-(η-BMn) 配合物 [(η-CH)(OC)Mn{μ-B(Cl)(Bu)Au(PPh)}] () 可通过卤化物取代反应进行官能化，以得到同构配合物 [(η-CH)(OC)Mn{μ-B(R)(Bu)Au(PPh)}] (R = Ph、CCPh 和 NCS)。它还在卤化物抽取试剂存在下与铸币金属配合物 [MCl(PPh)] (M = Au、Ag 和 Cu) 反应，得到硼桥联异多核配合物 [{(η-CH)(OC)Mn}{μ-B(Bu)}M][BArx4] (M = Au、Ag 和 Cu；Ar = 3,5-CHCl、3,5-CH(CF))。实验表征以及计算研究表明，这些配合物最好被视为与单价铸币金属阳离子侧基配位的过渡金属硼烯配合物，因此代表了斯通的亚烷基桥联多核配合物的首个硼类似物。
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