Chemistry of polynuclear compounds. Part XVII. Some carboxylate complexes of ruthenium and osmium carbonyls

Abstract

Dodecacarbonyltriruthenium reacts with certain carboxylic acids, RCO,H ( R = H, Me, Et, or n-CgH19). to give orange, polymeric compounds [Ru(CO),(RCO,)]~.The acetate complex reacts with carbon monoxide under mild conditions to produce a dimeric complex Ru,(CO)~(M~CO,),.In the corresponding reactions with OS,(CO)~, analogous dimeric complexes are isolated in all cases and no evidence for the formation of polymeric dicarbonyl compounds has been found. In certain of these reactions the tetranuclear hydrides, H,M4(CO),,, are produced as secondary products. The polymers and dimers react with ligands such as tertiary phosphines, triphenylarsine or pyridine to produce dimeric complexes of the type M,(CO),(RCO,),L,.The n.m.r., i.r., and mass spectral data of these complexes are reported and discussed PREVIOUSLY we have reported the reactions of dodecacarbonyl-triruthenium and -triosmium with alcohols,2 thiols,l13 arenes? and alkane^.^ In all cases hydridocarbonyl derivatives were isolated either as the major or as a subsidiary product. The formation of these hydrides is of interest and we are examining the reactivity of Ru,(CO),, and Os,(CO),, with a series of organic compounds containing ' active ' hydrogen. We now report the first of these studies, the reactions of Ru,(CO),, and Qs,(CO),~ with carboxylic acids. The reactions of metal carbonyls with carboxylic acids have not been investigated in any detail. Wilkinson and his co-workers have reported the preparation of a series of yellow diamagnetic compounds, Mo2( RCO,),, from the reaction of Mo(CO), with the appropriate carboxylic acid. An X-ray analysis on Mo,(MeCO,), showed that the structure closely resembles those of

Sawhorse-type diruthenium tetracarbonyl complexes containing porphyrin-derived ligands as highly selective photosensitizers for female reproductive cancer cells

“…All compounds exhibit in the m (CO) region of the IR spectrum the characteristic three-band pattern of the Ru 2 (CO) 4 sawhorse unit, observed in all complexes of this type [21,28]. Similarly, for the two carboxylato bridges only one m (OCO) absorption is observed, in accordance with the spectra of other [Ru 2 (CO) 4 [21,28].…”

“…In this study, we have chosen the diruthenium tetracarbonyl structure as the organometallic agent and backbone of the complexes. These sawhorse-type diruthenium complexes have been known since 1969, when J. Lewis and co-workers [21] reported the formation of [Ru 2 (CO) 4 (l 2 -g 2 -O 2 CR) 2 ] n polymers by refluxing [Ru 3 (CO) 12 ] in the corresponding carboxylic acid (HO 2 CR), and the depolymerization of these materials in coordinating solvents to give dinuclear complexes of the type [Ru 2 (CO) 4 …”

New Dinuclear Ru2(CO)4 Sawhorse‐Type Complexes Containing Bridging Carboxylato Ligands

“…All compounds exhibit in the ν (CO) region of the infrared spectrum the characteristic pattern of the Ru 2 (CO) 4 sawhorse unit: three bands around 2000 cm Ϫ1 for the CO terminal ligands and two bands for symmetric and asymmetric vibrations of the carboxylato bridges, around 1500Ϫ1600 cm Ϫ1 [1].…”

“…Sawhorse-type diruthenium complexes are well-known since 1969, when J. Lewis and co-workers reported their formation by refluxing Ru 3 (CO) 12 in the corresponding carboxylic acid and the depolymerisation of the materials obtained in coordinating solvents to give dinuclear complexes of the type Ru 2 (CO) 4 (O 2 CR) 2 L 2 (R ϭ H, CH 3 , C 2 H 5 , C 9 H 19 ; L ϭ C 5 H 5 N, AsPh 3 , PPh 3 ), L being a two-electron donor ligand [1]. Later, by a single-crystal X-ray structure analysis of Ru 2 (CO) 4 (O 2 CR) 2 L 2 (R ϭ C 4 H 9 ; L ϭ PBu t 3 ), these complexes have been shown to have a Ru 2 (CO) 4 backbone in a sawhorse-type arrangement with two μ 2 -η 2 -carboxylato bridges and two axial ligands [2].…”

Structure of Ru4(CO)8(O2CCH2CH=CH2)4(NMe3)2

“…Subsequent reactions of these polymeric derivatives with various Lewis bases result in the formation of dimeric carboxylate complexes of the type Ru2(CO)a(RCOz)2L2 (Crooks, Johnson, Lewis, Williams & Gamlen, 1969). The X-ray structure of (CH3CO2)2Ru2(CO)4(C5HsN)2, as well as that of an analogous osmium complex, (CH3 CO2)2Os2 (CO)6, have been Table 2.2B) Data collection: P3VAX (Siemens, 1990).…”