CYCLOPENTADIENYL RUTHENIUM COMPLEXES WITH TRICARBOLLIDE LIGANDS

摘要

Reaction of the tricarbollide anion [7,8,9-C^sub 3^B^sub 8^H^sub 11^]^sup -^ (1a) with the naphthalene complex [CpRu(C^sub 10^H^sub 8^)]^sup +^ under visible light irradiation in CH^sub 2^Cl^sub 2^ gives the 12-vertex closo-ruthenacarborane 1-Cp-1,2,3,5-RuC^sub 3^B^sub 8^H^sub 11^ (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-RuC^sub 3^B^sub 8^H^sub 11^ (3; 63%). Irradiation of 1a with [CpRu(C^sub 10^H^sub 8^)]^sup +^ in acetone gives the 11-vertex closo-1-Cp-1,2,3,4-RuC^sub 3^B^sub 7^H^sub 10^ (4; 32%). The latter was also prepared by reaction of 1a with [CpRu(MeCN)^sub 3^]^sup +^ (59%). Compound 2 slowly undergoes cage contraction in acetone giving 4. Irradiation of 1a with [Cp*Ru(C^sub 10^H^sub 8^)]^sup +^ affords the isomeric 12-vertex closo-ruthenacarboranes 1-Cp*-1,2,3,5-RuC^sub 3^B^sub 8^H^sub 11^ and 1-Cp*-1,2,4,10-RuC^sub 3^B^sub 8^H^sub 11^ (2.2:1 ratio; 56%). Reaction of the amino-substituted tricarbollide anion [7-tBuNH-7,8,9-C^sub 3^B^sub 8^H^sub 10^]- with [(C^sub 5^R^sub 5^)Ru(C^sub 10^H^sub 8^)]^sup +^ (R = H, Me) selectively gives 12-vertex closo-ruthenacarboranes 1-(C^sub 5^R^sub 5^)-12-tBuNH-1,2,4,12-RuC^sub 3^B^sub 8^H^sub 10^ (ca. 50%). The structures of 2 and 4 were confirmed by X-ray diffraction. [PUBLICATION ABSTRACT]