Transition Metal Boryl Complexes

Monohaloboryls (BHX−) as Bridging Ligands: Observable Dinuclear σ‐(Halo)boranyl Intermediates in the Synthesis of Metalloborylenes

“…The dichloroboryl compound crystallized in the orthorhombic space group Fdd2 and showed a staggered arrangement of the [Re(CO) 5 ] fragment with respect to the BCl 2 ligand (Cl1-B-Re-CO cis 32.65 (10)8), thus minimizing steric repulsion in the solid state. It is noteworthy that complexes with electron-precise ReÀB bonds are very scarce, and those that have been reported are restricted to a small number of boryl complexes [17] and one bridged borylene species, [16b] none of which have been structurally characterized by X-ray diffraction. Thus, the Re À B distance (2.189 (16) ) for compound 4 appears to be the first determined for an electron-precise 2c-2e bond between these two elements, and is significantly shorter than those reported earlier for metallaboranes, such as arachno-2-[Re(CO) 2 - [18] (dppf = 1,1'-bis(diphenylphosphino)ferrocene; ReÀB 2.432(4) ), where boron and rhenium were part of an electron-deficient cluster core.…”

Structure and bonding analysis of dimethylgallyl complexes of cobalt, rhodium and iridium [Me(PMe3)2(Me3GaCl)M(GaMe2)] (M = Co, Rh, Ir) and [Me(PMe3)2ClIr(GaMe2)]: A theoretical study

“…Coordination chemistry of boryl ligand has blossomed, leading to an in-depth understanding of both electronic structure and reactivity during the last two decades [1,2]. Transition metal-boryl as well as borylene complexes are key compounds in the metalmediated borylation of unsaturated organic substrates and synthesis of p-conjugated boron-based material with potential application in optoelectronic or sensor device [3].…”

Easy access to nucleophilic boron through diborane to magnesium boryl metathesis

“…Although transition metal boryl chemistry and the transition metal-catalysed borylation of organic substrates have been areas of study for over half a century23456, the reactivity of boron is most commonly defined by its Lewis acidity and its reactivity as an electrophile. The realization of the first nucleophilic boryllithium reagents (for example, 1 , Fig.…”