Boryl and bridged borylene complexes of iron and ruthenium

The reactivity of aminodihaloboranes R2NBX2 (R = Me, SiMe3; X = Cl, Br) tow ards transition metal complexes of the type Na[(eta(5)-C5R5')M(CO)(2))] (M = Fe, Ru; R' = H, Me) was investigated. In the case of Me2NBBr2 and M = Fe the borylcomplexes [(eta(5)-C5R5')(CO)(2)Fe{BBr(NMe2)}] (C5R5' = C5H5 9a; C 5R5' = C5H4Me 9b; C5R5' = C5Me5 10) were obtained. The compounds 9a and Sb were formed together with the corresponding bridged borylene complexes [mu- BNMe2(mu-Co){(eta(5)-C5R5')Fe(CO)}(2)](C5R5' = C5H5 11a; C5R5' = C5H4Me 11b ) in a 1:1 ratio, the latter, however, could be isolated from these mixture s as pure materials. In addition the novel boryl and borylene ruthenium com plexes [(eta(5)-C5H5)(CO)(2)Ru{BX(NMe2)}] (X = Cl 12a; X = Br 12b), [(eta(5 )-C5H5)(CO)(2)Ru{BCl{NSiMe3{BClN(SiMe3)(2)}}}] (13) and [mu-BN(SiMe3)(2)(mu -Co){(eta(5)-C5H5)Ru(CO)}(2)] (14) were obtained by similar methods. All co mpounds were characterized by multinuclear NMR and IR spectroscopy. The str ucture of 13 in the solid state was determined by a single-crystal X-ray di ffraction study.