Collect. Czech. Chem. Commun. 2010, 75, 1139-1148
Published online 2010-11-09 12:23:50

Cyclopentadienyl ruthenium complexes with tricarbollide ligands

Dmitry S. Perekalina, Evgeniya A. Trifonovaa, Ivan V. Glukhova, Josef Holubb and Alexander R. Kudinova,*

a A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 119991 Moscow GSP-1, Russian Federation
b Institute of Inorganic Chemistry, Academy of Sciences of the Czech Republic, v.v.i., 250 68 Řež, Czech Republic


Reaction of the tricarbollide anion [7,8,9-C3B8H11] (1a) with the naphthalene complex [CpRu(C10H8)]+ under visible light irradiation in CH2Cl2 gives the 12-vertex closo-ruthenacarborane 1-Cp-1,2,3,5-RuC3B8H11 (2; 87% yield). This complex was also obtained by reaction of 1a with CpRu(cod)Cl (97%). Upon heating at 80 °C in toluene 2 rearranges into isomer 1-Cp-1,2,4,10-RuC3B8H11 (3; 63%). Irradiation of 1a with [CpRu(C10H8)]+ in acetone gives the 11-vertex closo-1-Cp-1,2,3,4-RuC3B7H10 (4; 32%). The latter was also prepared by reaction of 1a with [CpRu(MeCN)3]+ (59%). Compound 2 slowly undergoes cage contraction in acetone giving 4. Irradiation of 1a with [Cp*Ru(C10H8)]+ affords the isomeric 12-vertex closo-ruthenacarboranes 1-Cp*-1,2,3,5-RuC3B8H11 and 1-Cp*-1,2,4,10-RuC3B8H11 (2.2:1 ratio; 56%). Reaction of the amino-substituted tricarbollide anion [7-tBuNH-7,8,9-C3B8H10] with [(C5R5)Ru(C10H8)]+ (R = H, Me) selectively gives 12-vertex closo-ruthenacarboranes 1-(C5R5)-12-tBuNH-1,2,4,12-RuC3B8H10 (ca. 50%). The structures of 2 and 4 were confirmed by X-ray diffraction.

Keywords: Boron; Metallacarborane; Ruthenium; Tricarbollide; Polyhedral rearrangement.

References: 44 live references.