Reactions of dinuclear carboxylate ruthenium (I) complexes with alcohols. The unexpected oxidation of primary alcohols to carboxylic ligands

16 The noble metals

“…86 Studies on potentially bridging diphosphinites (4-Ph 2 POC 6 H 4 ) 2 X (L; X CMe 2 , O or S) included the synthesis of [{RuCl 2 (Z 6 -p-Pr i C 6 H 4 Me)} 2 (m-L)], whose structures and reactivity were investigated. 87 Polynuclear organoruthenium compounds 94 The crystal structure determination of [PMePh 3 ] 2 [Ru 3 (CO) 11 ] con¢rmed the IR and 13 C NMR spectral indications that the anion contained two {Ru(CO) 3 } units bridged by CO and by {Ru(CO) 4 }. 95 Reactivity studies of the methoxynitrene complex [Ru 3 (CO) 9 (m 3 -CO)(m 3 -NOMe)] have continued with the reaction with phosphines to give [Ru 3 (CO) 7 (m 3 -CO)(m 3 -NOMe)(dppm)] and [Ru 3 (CO) 9Àn (m 3 -CO)(m 3 -NOMe)-(PPh 3 ) n ] (n 1 or 2).…”

“…12 The bridging formates in [Ru 2 (O 2 CH) 2 (CO) 4 (PPh 3 ) 2 ] can oxidise primary alcohols RCH 2 OH to give [Ru 2 (m-O 2 CR) 2 (CO) 4 (PPh 3 ) 2 ] (R Pr or Bu i ) but other ruthenium(I) dinuclear carboxylate-bridged complexes of this type reacted with R H OH to give [Ru 2 (m-OR H ) 2 (CO) 4 (PPh 3 ) 2 ] (R Ph, Bu n or Me 2 CHCH 2 CH 2 ). 13 Treating [Ru 2 (O 2 CBu t ) 4 (H 2 O) 2 ] with the nitroxide L 1 gives the polymeric chain complex [{Ru 2 (O 2 CBu t ) 4 (L 1 ) 2 }] [{Ru 2 (O 2 CBu t ) 4 (H 2 O) 2 }] 2 n , which appears to show antiferromagnetism between nitroxides and ferromagnetism between these and the metal together with a high zero ¢eld splitting. 14a The ¢rst room temperature mesomorphism in a mixed valence compound was found in the palmitoleate [Ru 2 {O 2 C(CH 2 ) 7 CHCH(CH 2 ) 5 Me} 5 ], made from [Ru 2 Cl(OAc) 5 ] by removal of chloride with Ag followed by carboxylate exchange.…”

“…In discussion the authors comment that many earlier structure determinations were in fact of chiral complexes, though this feature was not recognised by the scientists involved. 195 A spin-labelled phosphine such as L 13 197 A reinvestigation of the effects of added halide ions on the electrochemistry of [PdX 2 (PPh 3 ) 2 ] (X Cl, Br or I) shows these result in the formation of [PdX 3 (PPh 3 )] À . 198 Tetrahedral Pd II is found in [PdCl 2 (dppfO 2 )], ¢rst isolated as a product from COS and [Pd 2 (dppf) 2 (m-S) 2 ], but better prepared from [PdCl 2 (NCMe) 2 ] and dppfO 2 ; its room temperature magnetic moment of 2.48 m B is curious.…”

“…247 A review describes the structures and reactions of compounds containing the {Pt 2 S 2 } core, along with some palladium and nickel analogues. 248 Turning to nitrogen donors, a thorough survey reviews the structures and 1 H, 13 C and 195 Pt NMR spectra of [PtX 2 (Mepy) 2 ] with special reference to isomerism, the trans in£uence and other structural effects. 249 The limited co-ordination chemistry of naphthyridines has been extended to include substitution at the positions adjacent to nitrogen, thus allowing considerable variation in structure, and giving complexes containing up to three Pt atoms with bridging by the ligand N atoms; some palladium examples were also made.…”