V. I. Meshcheryakov

Polysubstituted derivatives of 3-(η5-Cp)-4-SMe2-3,1,2-FeC2B9H10. X-ray structure of 3-(η5-Cp)-4-SMe2-7,8-(CF3COO)2-12-HgCl-3,1,2-FeC2B9H7

Abstract The electrophilic mercuration of 3-(η 5 -Cp)-4-SMe 2 -3,1,2-FeC 2 B 9 H 10 ( 1 ) was investigated. The reaction of 1 with the excess of mercury trifluoroacetate in dichloromethane at 20xa0°C gives complexes containing from two to four substituents depending on the ratio of reagents. All new compounds were separated and characterized by elemental analysis and NMR spectra. The positions of substitution were established by 11 B-NMR and 11 B- 11 B COSY NMR spectra. X-ray structure of 3-(η 5 -Cp)-4-SMe 2 -7,8-(CF 3 COO) 2 -12-HgCl-3,1,2-FeC 2 B 9 H 7 was determined.

π-complexes of monoanionic carborane ligand [9-(Me2S)-7,8-C2B9H10]− with [η-C5R5Fe]+ (R=H, Me) and [η-C4Me4Co]+ cationic fragments

Compounds (η-C5R5)Fe[η-9-(Me2S)-7,8-C2B9H10] (R=H, Me) and (η-C4Me4)Co[η-9-(Me2S)-7,8-C2B9H10] were synthesized by the reactions of Na[9-(Me2S)-7,8-C2B9H10] with complexes [(η-C5H5)Fe(MeCN)3]PF6, [(η-C5Me5)Fe(MeCN)3]BF4, and [(η-C4Me4)Co(MeCN)3]PF6, respectively.

Synthesis of the first metallacarborane triple-decker complexes with a central cyclopentadienyl ligand

The previously unknown metallacarboranes (η-C5R5)Ru(η-9-Me2S-7,8-C2B9H10) (R=H or Me) and (η-C5H5)Ni(η-9-Me2S-7,8-C2B9H10) were prepared and used in the synthesis of the first metallacarborane triple-decker complexes with a central cyclopentadienyl ligand, viz., [(η-C5R5)Ru(μ-η:η-C5Me5)Ru(η-9-Me2S-7,8-C2B9H10)]PF6 (R=H or Me), [(η-9-Me2S-7,8-C2B9H10)Ni(μ-η:η-C5H5)Ni(η-9-Me2S-7,8-C2B9H10)]PF6, and [(η-C5H5)Ni(μ-η:η-C5H5)Ni(η-9-Me2S-7,8-C2B9H10)]BF4.

Reaction of ruthenacarborane with trifluoroacetoxymercuroferracarborane

The reaction of exo-nido-ruthenacarborane exo-nido-5,6,10-[Cl(Ph3P)2Ru]-5,6,10-(μ-H)3-10-H-7,8-C2B9H8 (1) with the 8-trifluoroacetoxymercury derivative of ferracarborane 3-(η5-Cp)-4-SMe2-8-CF3COOHg-3,1,2-FeC2B9H9 (2) was studied. It was demonstrated for the first time that metallacarborane 2 can be used as a mercurating agent. The reaction afforded 5,6,10-exo-nido-[Cl(Ph3P)2Ru]-5,6,10-(μ-H)3-10-{3-(η5-Cp)-4-SMe2-3,1,2-FeC2B9H9-8-Hg}-7,8-C2B9H8 (3) existing as two isomers. The structure of trans isomer 3a was established by X-ray diffraction analysis.

Electrophilic substitution reactions of ferracarborane 3-(η5-Cp)-4-SMe2-3,1,2-FeC2B9H10

Mercuration and bromination reactions of ferracarborane 3-(η5-Cp)-4-SMe2-3,1,2-FeC2B9H10 (1) were investigated. Mercuration of 1 under mild conditions (mercury trifluoroacetate in dichloromethane) results in 8-monosubstituted mercury derivative as the only reaction product. Depending on the reaction conditions, bromination of 1 results in 8-mono- or 7,8-disubstituted bromo derivatives. The structures of the monomercury and dibromo derivatives of 1 were established by X-ray analysis.

Synthesis of rhodacarborane halide complexes [(η-9-Me2S-7,8-C2B9H10)RhX2]2 (X=Cl, Br, or I)

The reactions of the complex (η-9-Me2S-7,8-C2B9H10)Rh(η-cod) (cod is 1,5-cyclo-octadiene) with HX acids (X=Cl, Br, or I) in acetone afforded rhodacarborane halide complexes [(η-9-Me2S-7,8-C2B9H10)RhX2]2, which are carborane analogs of cyclopentadienyl halide rhodium complexes [(η-C5R5)RhX2]2.