Reactions of the dichloroboryl complex of osmium, Os(BCl2)Cl(CO)(PPh3)2, with water, alcohols, and amines

Exchange of boryl ligand substituents in Os[B(OEt)2]Cl(CO)(PPh3)2

“…An interesting class of reactions, which some metal-boryl complexes undergo, is substitution of the boryl substituents without interference with the M-B bond. Such reactions have been observed for chloro-boryl ligands [2][3][4][5]. In organoboron chemistry, borate esters, B(OR) 3 , readily undergo exchange reactions with other alcohols.…”

“…Such reactions have been observed for chloro-boryl ligands [2][3][4][5]. In organoboron chemistry, borate esters, B(OR) 3 , readily undergo exchange reactions with other alcohols. Interestingly, this exchange process has not been reported for L n M-B(OR) 2 complexes and indeed, we have recently described that Os[B(OEt) 2 ]Cl(CO)(PPh 3 ) 2 can be recrystallised unchanged from methanol and is not hydrolysed by moist solvents [3].…”

“…In organoboron chemistry, borate esters, B(OR) 3 , readily undergo exchange reactions with other alcohols. Interestingly, this exchange process has not been reported for L n M-B(OR) 2 complexes and indeed, we have recently described that Os[B(OEt) 2 ]Cl(CO)(PPh 3 ) 2 can be recrystallised unchanged from methanol and is not hydrolysed by moist solvents [3]. The availability of this simple and thoroughly characterised bis(ethoxy)boryl complex, led us to explore conditions under which exchange processes might occur.…”

Recent developments in the chemistry of 1,3,2-diazaborolines-(2,3-dihydro-1H-1,3,2-diazaboroles)

“…Orange crystalline benzodiazaboroline, which is functionalized at boron by an osmium complex fragment resulted from the condensation of the dichloroboryl osmium complex 66 with 2 equiv. of N,N -dimethyl-o-phenylene diamine in benzene (Scheme 19) [32]. Compounds 71-73 where two 1,3,2-benzodiazaboroline units are linked by a phenylene spacer are available by the cyclocondensation of the 2,5-bis(hexyloxy)-1,4-phenylene diboronic acid 68 with 2 equiv.…”

Boryl‐Based Pincer Systems: New Avenues in Boron Chemistry

“…Moreover, boryl species flanked by nitrogen-based groups are stronger s donors than their oxygen analogues. [9] Boryl species BR 2 are very strong s donors (and allow significant tuning by side-group modification) as a result of the electropositive nature of boron (also with respect to carbon), and therefore they exhibit a strong trans effect as well. This effect was studied both experimentally [10a] and theoretically [10b,c] on Pt complexes, among others.…”