75182-14-8Relevant academic research and scientific papers
SYNTHESIS OF MONOHYDRIDOHEXAMETHYLBENZENERUTHENIUM(II) COMPLEXES CONTAINING GROUP V DONOR LIGANDS. ISOMERISM ARISING FROM CYCLOMETALLATION OF A TERTIARY PHOSPHINE AT ALIPHATIC AND AROMATIC CARBON ATOMS
Bennett, Martin A.,Huang, Tai-Nang,Latten, Jozef L.
, p. 189 - 206 (2007/10/02)
The η-hexamethylbenzenehydridoruthenium(II) complexes RuHCl(η-C6Me6)L (L = PPh3 (11), AsPh3 (12), P(C6H4-p-F)3 (14), P(C6H4-p-Me)3 (15), P(C6H4-p-OMe)3 (16), P-t-BuPh2 (17), P-i-PrPh2 (18), P-i-Pr3 (19), PCy3 (20) and P-t-BuMe2 (21)) have been made by heating 2, the ligand and sodium carbonate in propan-2-ol.The triarylphosphine complexes 11, 14 and 15 react with methyllithium to give aryl artho-metallated hydridoruthenium(II) complexes such as (22) and 19 similarly gives the isopropyl cyclometallated complex (29) as a mixture of diastereomers.Reaction of 17 with methyllithium gives initially the t-butyl cyclometallated complex (25) which isomerizes by a first order process (k ca. 0.2 h-1 in C6D6 or THF-d8 at 50 deg C) to the aryl ortho-metallated complex (26).The similarly generated isopropyl cyclometallated complex (27) has not been isolated in a pure state owing to rapid isomerization to (28); both 27 and 28 exist as a pair of diastereomers.The formation of the cyclometallated complexes and the isomerizations are thought to involve intermediate 16-electron ruthenium(0) complexes Ru(η-C6Me6)L.
Synthesis and spectroscopic characterization of dinuclear mono(μ-hydrido) arene complexes of divalent ruthenium
Bennett, Martin A.,Ennett, James P.
, p. 1365 - 1374 (2008/10/08)
Dinuclear mono(μ-hydrido) arene complexes {RuX(η-arene)}2(μ-H)(μ-X) (X = Cl, Br, arene = C6Me6, 1,2,4,5-C6H2Me4, 1,3,5-C6H3Me3; X = Cl, arene = C6H4-1-Me-4-CHMe2, C6H6) containing one bridging and two terminal halide groups are formed from the reaction of [RuX2(η-arene)]2 with hydrogen (4 atm) at room temperature in the presence of triethylamine. The tendency for one chloride ion to dissociate in nitromethane is enhanced by increasing the degree of alkyl substitution on the arene, the hexamethylbenzene chloro complex being a 1:1 electrolyte in this solvent. The cations [{Ru(η-arene)}2(μ-H)(μ-X)2]+ containing two bridging halide groups can be isolated as PF6 salts. Heating of acetato complexes Ru(O2CMe)2(η-arene) with 2-propanol gives mono(μ-hydrido) bis(μ-acetato) complexes containing the cations [{Ru(η-arene)}2-(μ-H)(μ-O2CMe)2] +, which can be isolated as solid hydrogenbis(acetate) salts for arene = C6Me6 or 1,2,4,5-C6H2Me4 and as PF6 salts for all the arenes studied. The corresponding trifluoroacetato complexes could not be isolated in a pure state but were identified spectroscopically. Reaction of Ru(O2CR)X(η-arene) with hot 2-propanol gives hydrido complexes of empirical formula {Ru(η-arene)}2H(O2CR)X2 (X = Cl, Br; R = CH3, CF3) except when arene = C6H6; in this case {Ru(η-C6H6)}2HCl3 is formed. These complexes readily give PF6 salts of the cations [{Ru(η-arene)}2(μ-H)(μ-O2CR)(μ-X)] + that have three different bridging groups. In solution, the parent compounds (arene = C6Me6, 1,2,4,5-C6H2Me4) behave as the halide salts of these cations but when arene = p-cymene (C6H4-1-Me-4-CHMe2) and R = CH3, the halide salt and a neutral dimer {RuX(η-arene)}2(μ-H)(μ-O2CR) coexist. Complexes of p-cymene in which three different groups are attached to ruthenium exhibit diastereotopic aromatic protons and isopropyl methyl groups in their 1H NMR spectra; those of durene (1,2,4,5-C6H2Me4) have diastereotopic methyl groups. The hydride protons of all the carboxylato complexes become progressively more shielded with increasing alkyl substitution on the arene. The formation and structure of the hydrido(arene)ruthenium(II) complexes are compared with those of the corresponding (η-pentamethylcyclopentadienyl)rhodium(III) and -iridium(III) compounds.
SYNTHESE UND EIGENSCHAFTEN STABILER HEXAMETHYLBENZOL(PHOSPHIN)DIMETHYL- UND -DIHYDRIDO-RUTHENIUM(II)-KOMPLEXE
Werner, H.,Kletzin, H.
, p. 289 - 300 (2007/10/02)
The dimethylruthenium(II) compounds C6Me6(PR3)Ru(CH3)2 (IV-VI, R3=Me3, MePh2, Ph3) have been prepared from C6Me6(PR3)RuCl2 (I-III) and LiCH3.They react with CF3COOH under stepwise elimination of CH4 to give C6Me6(PR3)RuCH3(OCOCF3) (VII-IX) and C6Me6(PR3)R
