US EPA

1197446 

Journal Article 

2 ALTERNATIVES OF HETEROALLENE INSERTION IN METAL-LIGAND BONDS OF 5-COORDINATE RUTHENIUM(II) AND OSMIUM(II) COMPLEXES [MXY(CO)(PIPR(3))(2)] 

Werner, H; Tena, MA; Mahr, N; Peters, K; Vonschnering, HG 

1995 

1 

Chemische Berichte
ISSN: 0009-2940 

128 

1 

41-47 

10.1002/cber.19951280107 

WOS:A1995QA36700007 

The five-coordinate chloro(hydrido)- and hydrido(iodo)ruthenium(II) and -osmium(II) compounds [MHX(CO)(PiPr3)2] (1, 2, 6, 7) react with CS2 to give the octahedral dithioformato complexes [MCl(CO)(PiPr3)2(eta2-S2CH)] (3, 4, 8, 9) in excellent yields. In the initial step, an addition of the heteroallene to the metal center occurs which is followed by insertion of CS2 into the M-H bond. On treatment of the dichlororuthenium(II) derivative [RuCl2(CO)(PiPr3)2] (10), which is prepared from RuCl3 . aq and PiPr3 in methanol, with carbon disulfide insertion into one of the Ru-PiPr3 bonds takes place to give the six-coordinate ruthenium(II) complex 12 with the zwitterion -S2CPiPr3+ as a chelating ligand. While the reaction of [OsH(SPh)(CO)(PiPr3)2] (13) with MeSCN leads to addition of the thionitrile to the metal center, the starting material reacts with MeNCS by insertion of the heteroallene into the Os-SPh bond to give two stereoisomers 15a, b, in which the nitrogen atom of the chelate ring is either cis or trans to the hydrido ligand. The octahedral methoxydithiocarbonato- and formatoosmium(II) compounds 16 and 17 are prepared from 2 and CS2 or CO2 in the presence of NaOMe. The crystal and molecular structures of 4 (M = Os), 12 and 15a have been determined. 

RUTHENIUM COMPLEXES; OSMIUM COMPLEXES; INSERTION REACTIONS; CARBON DISULFIDE; CARBON DIOXIDE; METHYL ISOTHIOCYANATE; ZWITTERIONIC LIGANDS