Sergey V. Timofeev

Mercury derivatives of exo-nido-ruthenacarborane

Abstract Symmetrical mercury derivative of exo - nido -ruthenacarborane was prepared by two routes: mercuration of exo - nido -5,6,10-[Cl(Ph 3 P) 2 Ru]-5,6,10-(μ-H) 3 -10-H-7,8-C 2 B 9 H 8 ( 1 ) and interaction of Ru(PPh 3 ) 3 Cl 2 with [10,10′-Hg-(7,8-C 2 B 9 H 11 ) 2 ]Cs 2 . Using o -carboran-9-ylmercury trifluoroacetate for mercuration of 1 leads to an unsymmetrical mercury compound with 9- o -carboranyl and exo - nido -ruthenacarboranyl ligands: 5′,6′,10′- exo - nido -[Cl(Ph 3 P) 2 Ru]-5′,6′,10′-(μ-H) 3 -10′-(1,2-C 2 B 10 H 11 Hg-9)-7′,8′-C 2 B 9 H 8 ( 4 ). The same compound was prepared by the action of Ru(PPh 3 ) 3 Cl 2 on [9,10′-Hg-(1,2-C 2 B 10 H 11 )(7′,8′-C 2 B 9 H 11 )]Cs ( 5 ). Both types of new compounds were obtained as a mixture of cis / trans isomers which were separated and characterized by elemental analysis and NMR spectra. The X-ray structure of trans -5′,6′,10′- exo - nido -[Cl(Ph 3 P) 2 Ru]-5′,6′,10′-(μ-H) 3 -10′-(1,2-C 2 B 10 H 11 Hg-9)-7′,8′-C 2 B 9 H 8 ( 4b ) was determined.

New carborane-containing amino acids and their derivatives. Crystal structures of n-protected carboranylalaninates

New alanine derivatives containing both the carboranyl and trifluoromethyl groups were synthesized by the reaction of organometallic derivatives of o-carborane with methyl trifluoropyruvate imines. When using the 1R-(−)-menthoxycarbonyl protecting group at the nitrogen atom, one of diastereomers was isolated and characterized. Trifluoromethyl-carboranylalanine methyl esters containing different protecting groups at the nitrogen atom were studied by X-ray diffraction. Both complete and partial deprotection of the amino and carboxy groups was performed.

Electrophilic substitution in eleven-vertex metallacarborane 1,2,4-CpCoC2B8H10

Bromination and mercuration of cobaltacarborane 1,2,4-CpCoC2B8H10 were investigated. Mercuration under mild conditions (Hg(OCOCF3)2 in CH2Cl2) afforded the only monomercurated complex containing the mercury atom at position 6. Bromination gave rise to 3-mono-, 6-mono-, or 6,9-disubstituted derivatives depending on the reaction conditions. The mercurated derivative was studied by the X-ray diffraction method.

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.

Reaction of exo-nido-ruthenacarborane [Cl(Ph3P)2Ru]-5,6,10-(μ-H)3-10-H-7,8-C2B9H8 with bromine

The reaction of bromine with exo-nido-ruthenacarborane [Cl(Ph3P)2Ru]-5,6,10-(μ-H)3-10-H-7,8-C2B9H8 (1) led to the replacement of the chlorine atom by the bromine atom in the octahedral environment of the ruthenium atom rather than to the substitution in the carborane cage. The structure of [Br(Ph3P)2Ru]-5,6,10-(μ-H)3-10-H-7,8-C2B9H8 was established by NMR and IR spectroscopy and X-ray diffraction analysis.

Synthesis of cobalt bis(8-methylthio-1,2-dicarbollide)- pentacarbonyltungsten complexes

A reaction of Bu4N[8,8´-(MeS)2-3,3´-Co(1,2-C2B9H10)2] with (MeCN)3W(CO)3 in dichloromethane gave a mixture of Bu4N{(CO)5W[κ-8,8´-(MeS)2-3,3´-Co(1,2-C2B9H10)2]} and Bu4N{[(CO)5W]2[κ2-8,8´-(MeS)2-3,3´-Co(1,2-C2B9H10)2]}, which were separated by column chromatography on silica gel.

CCDC 1544890: Experimental Crystal Structure Determination

Related Article: Alexander P. Molotkov, Mikhail M. Vinogradov, Alexey P. Moskovets, Olga Chusova, Sergey V. Timofeev, Vasilii A. Fastovskiy, Yulia V. Nelyubina, Alexander A. Pavlov, Denis A. Chusov, Dmitry A. Loginov|2017|Eur.J.Inorg.Chem.||4635|doi:10.1002/ejic.201700498

CCDC 1544888: Experimental Crystal Structure Determination

Related Article: Alexander P. Molotkov, Mikhail M. Vinogradov, Alexey P. Moskovets, Olga Chusova, Sergey V. Timofeev, Vasilii A. Fastovskiy, Yulia V. Nelyubina, Alexander A. Pavlov, Denis A. Chusov, Dmitry A. Loginov|2017|Eur.J.Inorg.Chem.||4635|doi:10.1002/ejic.201700498

CCDC 1544887: Experimental Crystal Structure Determination

Related Article: Alexander P. Molotkov, Mikhail M. Vinogradov, Alexey P. Moskovets, Olga Chusova, Sergey V. Timofeev, Vasilii A. Fastovskiy, Yulia V. Nelyubina, Alexander A. Pavlov, Denis A. Chusov, Dmitry A. Loginov|2017|Eur.J.Inorg.Chem.||4635|doi:10.1002/ejic.201700498