The five-coordinate ruthenium boryl complexes, Ru(BR2)Cl(CE)(PPh3)(2) (E = O, BR2 = BO2C6H4 (1a); E = O, BR2 = BO2C10H6 (1b); E = O, BR2 = B(NH)(2)C6H4 (1d); E = O, BR2 = B(NH)SC6H4 (1e); E = S, BR2 BO2C6H4 (2a); E = S, BR2 = B(NH)SC6H4 (2e); E = N-p-tolyl, BR2 = BO2C6H4 (3a)), result from the reactions of RuHCl(CE)(PPh3)3 with the appropriate borane. Related osmium compounds, Os(BR2)Cl(CE)(PPh3)(2) (E = O, BR2 = BO2C6H4 (4a); E = O, BR2 = BO2C6H3CH3 (4C); E = O, BR2 = B(NH)(2)C6H4 (4d); E = O, BR2 = B(NH)SC6H4 (4e); E = S, BR2 = BO2C6H4 (5a)), cannot be prepared from the hydrides but are formed from reactions between Os(Ph)Cl(CE)(PPh3)(2) and the appropriate borane. A boryl complex of ruthenium of formula Ru(BO2C6H4)Cl(PPh3)(2) . H2O (6) results from reaction of RuHCl(PPh3)(3) with HBO2C6H4 (catecholborane). IR, H-1 NMR, and C-13 NMR data for the new boryl complexes are reported.