Side-on coordination of boryl and borylene complexes to cationic coinage metal fragments†
Holger Braunschweig,Krzysztof Radacki,Rong Shang
Chemical Science Pub Date : 03/10/2015 00:00:00 , DOI:10.1039/C5SC00211G
Abstract

The M-(η2-BMn) complex [(η5-C5H5)(OC)2Mn{μ-B(Cl)(tBu)Au(PPh3)}] (2) can be functionalized via halide substitution reactions to afford isostructural complexes [(η5-C5H5)(OC)2Mn{μ-B(R)(tBu)Au(PPh3)}] (R = Ph, CCPh and NCS). It also reacts with coinage metal complexes [MCl(PPh3)] (M = Au, Ag and Cu) in the presence of halide abstraction reagents to afford borylene-bridged heteromultinuclear complexes [{(η5-C5H5)(OC)2Mn}22-B(tBu)}2M][BArx4] (M = Au, Ag and Cu; Arx = 3,5-C6H3Cl2, 3,5-C6H3(CF3)2). 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.

Graphical abstract: Side-on coordination of boryl and borylene complexes to cationic coinage metal fragments