Transition Metal−Boryl Compounds:  Synthesis, Reactivity, and Structure

Chemistry of Group 13 element-transition metal linkage — the platinum- and palladium-catalyzed reactions of (alkoxo)diborons

“…The addition has a strong tendency to occur at the internal double bond, but steric hindrance in both allenes and phosphine ligands forces the addition towards the terminal double bond. Thus, the reaction of monosubstituted allenes with a less bulky ligand PPh 3 preferentially produces the internal adducts (14a) and the bulky and electron-donating ligand (c-Hex) 3 …”

A borylcopper species generated from bis(pinacolato)diboron and its additions to α,β-unsaturated carbonyl compounds and terminal alkynes

“…Tetra(alkoxo)diborons such as bis(catecholato)diboron and bis(pinacolato)diboron are versatile reagents for borylation of unsaturated organic compounds and organic halides [1][2][3][4]. Diborons can be oxidatively added to a low-valent transition metal with B-B bond cleavage, thus allowing the catalyzed addition of diborons to unsaturated C-C reaction in the presence of KOAc; for example, CuI (52%), CuBr (50%), and CuCl (67%), and CuCN (44%).…”

Phosphine-Substituted Diborane(4)yl Complexes of Tungsten

“…Reaction of 1,2-diaminodihalodiboranes(4) with anionic transition metal complexes has led to the first diborane(4)yl complexes [(η 5 -C 5 H 5 )(OC) n M-{B(NMe 2 )-B(NMe 2 )Cl}] [M(CO) n = Fe(CO) 2 ; M(CO) n = W(CO) 3 [4,5]], and [(η 5 -C 5 H 5 )(OC) n M-{B(NMe 2 )-B(NMe 2 )Br}] [M(CO) n = Ru(CO) 2 ; M(CO) n = Mo(CO) 3 (1) [4,6]] which were obtained via salt elimination reactions. The latter complex (1) was modified by PEt 3 /CO exchange to give the only phosphine-substituted diborane(4)yl complex [(η 5 -C 5 H 5 )(Et 3 P)(OC) 2 Mo-{B(NMe 2 )-B(NMe 2 )Br}] (2) [4,6] (eq.…”