The high-yield product of the reaction of [RuCl 2 (dmso) 4 ] (dmso ) dimethylsulfoxide) with Na[HB(mt) 3 ] (mt ) methimazolyl) is not, as reported, the complex [RuCl(dmso) 2 {κ 3 -S,S′,S′′-HB(mt) 3 }] but rather the isomeric [RuCl(dmso) 2 {κ 3 -H,S,S′-HB(mt) 3 }], which features a three-center, two-electron B-H-Ru interaction, as also found for the complex [RuH(PPh 3 ) 2 {κ 3 -H,S,S′-H 2 B(mt) 2 }], which results from [RuHCl(PPh 3 ) 3 ] and Na[H 2 B(mt) 2 ].
Whilst frequently used for reactions of poly(methimazolyl)borates, dichloromethane is not an innocent solvent, but rather slowly forms heterocyclic salts [H(2)C(mt)(2)BR(2)]Cl, three examples of which (BR(2) = BH(2), BH(mt), 9-borabicyclononyl) have been structurally characterised to confirm the unprecedented B(NCS)(2)C connectivity.
Ruthenaboratranes of the form [Ru(CO)L{κ4-B(mt)3}] (mt = N-methimazolyl) arise via substitution of the PPh3 ligand in [Ru(CO)(PPh3){κ4-B(mt)3}] by L (L = PMe2Ph, PMe3, P(OMe)3, P(OEt)3, P(OPh)3) or reactions of [RuCl(R)(CO)Ln] (R = Ph, CHCHPh; n = 2, L = PCy3; n = 3, L = P(OMe)3, PMe2Ph) with Na[HB(mt)3].
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