159668-59-4Relevant academic research and scientific papers
Nitrous oxide mediated synthesis of monomeric hydroxoruthenium complexes. Reactivity of (DMPE)2Ru(H)(OH) and the synthesis of a silica-bound ruthenium complex
Kaplan, Anne W.,Bergman, Robert G.
, p. 5072 - 5085 (2008/10/08)
Treatment of (DMPE)2Ru(H)2 with 1 equiv of N2O affords the hydroxoruthenium complex (DMPE)2Ru(H)(OH) (1) in 41% yield. Further treatment with an excess of N2O affords the dihydroxo complex (DMPE)2Ru(OH)2 (5) in 30% yield. Addition of phenols, thiols, and silanols to 1 yields the corresponding aryloxo-, thiolato-, and siloxoruthenium complexes 6-10 in 25-75% yield. The hydroxo ligand of 1 may also be exchanged with the surface silanols of silica to form the silica-bound complex (DMPE)2Ru(H)(OSilica) (14). Subsequent treatment of 14 with thiocresol removes the ruthenium complex as (DMPE)2Ru(H)(SC6H4Me) (10). The treatment of 1 with acetone affords the C-bound enolate complex (DMPE)2Ru(H)(CH2C(O)CH3) (15) in 34% yield. Terminal alkynes react with 1 to give the ruthenium acetylide complexes trans-(DMPE)2Ru(H)(CCPh) 16 (74% yield) and trans-(DMPE)2Ru(H)(CCH) 17 (32% yield). Reactivity may also be affected at both ends of 1,7-octadiyne to give the bimetallic complex (DMPE)2RuC≡C(CH2)4C≡CRu(DMPE) 2 (19, 33% yield). The addition of Ph3SnH, which does not contain an acidic hydrogen, to 1 affords (DMPE)2Ru(H)(SnPh3) (20) in 32% yield. When 1 is treated with 1 equiv of p-tolualdehyde, the hydroxo oxygen is retained, the aldehydic C-H bond is broken, and the ruthenium carboxylate complex (DMPE)2Ru(H)(OC(O)C6H4CH3) (21) is obtained in 28% yield. The structural assignment of 21 was confirmed by X-ray crystallography. Similar reactivity is observed when 1 is treated with hexafluoroacetone, in which case the C-C bond is cleaved to produce (DMPE)2Ru(H)(OC(O)CF3) (22, 55% yield). Much of the observed reactivity of 1 is rationalized using the assumption that the first step involves reversible formation of a metal cation/OH- ion pair (23). Attempts to trap the cation with ethylene resulted in formation of the ruthenium ethylene complex (DMPE)2Ru(C2H4) (2); there is strong evidence that 2 forms via a cationic hydridoruthenium ethylene complex. Treatment of 1 with CO forms the cationic hydrido carbonyl complex [(DMPE)2Ru(H)(CO)][OH] (25).
Reactions of (PMe3)4Ru(C2H4) and (DMPE)2Ru(C2H4) with weak proton-donating electrophiles HX (X = OAr, SAr, NHPh, PHPh). Synthesis of complexes with metal-heteroatom single bonds
Burn, Melinda J.,Fickes, Michael G.,Hollander, Frederick J.,Bergman, Robert G.
, p. 137 - 150 (2008/10/08)
Reactions of the ruthenium ethylene complexes (PMe3)4Ru(C2H4) and (DMPE)2Ru(C2H4) with a variety of HX compounds (X = SAr, OAr, PPhH, NHPh and Ph) have been explored. In all cases, the tetrakis(trimethylphosphine) complex reacted to form ethylene and the hydrido species, (PMe3)4Ru(H)(X). However, parallel studies with the related material (DMPE)2Ru(C2H4) suggest that these complexes react as strained metallacycles toward HX. Thus, the bis(DMPE) analog gave the ethyl species (DMPE)2Ru(X)(CH2CH3) in its reactions with HSAr and PH2Ph, and thermolysis of these ethyl complexes led to the formation of the hydrides and free ethylene. The reaction of the DMPE ethylene complex with p-cresol allowed isolation of an intermediate cationic ethylene hydride species, but this was converted rapidly to the corresponding aryloxy hydride complex, even at room temperature. With NH2Ph the bis(DMPE) complex formed only the corresponding hydride species. In an attempt to generate an acetylene complex that similarly might react as a strained metallacyclopropene, (PMe3)4Ru(CH=CH2)2 was generated from the reaction of CH=CH2MgBr with (PMe3)4RuCl2. However, thermolysis of the divinyl species led only to the formation of the butadiene complex, (PMe3)3Ru(C4H6).
