Synthesis, characterization and reactivity studies of electrophilic ruthenium(ii) complexes: a study of H2 activation and labilization.

Dalton transactions (Cambridge, England : 2003)

PubMedID: 25077596

Naidu KS, Patil YP, Nethaji M, Jagirdar BR. Synthesis, characterization and reactivity studies of electrophilic ruthenium(ii) complexes: a study of H2 activation and labilization. Dalton Trans. 2014;.
Reaction of 2,2'-bipyridine (bpy) with dinuclear complexes [RuCl(dfppe)(µ-Cl)3Ru(dmso-S)3] (dfppe = 1,2-bis(dipentafluorophenyl phosphino)ethane (C6F5)2PCH2CH2P(C6F5)2; dmso = dimethyl sulfoxide) () or [RuCl(dfppe)(µ-Cl)3RuCl(dfppe)] () affords the mononuclear species trans-[RuCl2(bpy)(dfppe)] (). Using this precursor complex (), a series of new cationic Ru(ii) electrophilic complexes [RuCl(L)(bpy)(dfppe)][Z] (L = P(OMe)3 (), PMe3 (), CH3CN (), CO (), H2O (); Z = OTf (, , , ), BAr(F)4 () have been synthesized via abstraction of chloride by AgOTf or NaBAr(F)4 in the presence of L. Complexes and were converted into the corresponding isomeric hydride derivatives [RuH(PMe3)(bpy)(dfppe)][OTf] (, ) and [RuH(P(OMe)3)(bpy)(dfppe)][OTf] (, ) respectively, when treated with NaBH4. Protonation of the cationic monohydride complex () with HOTf at low temperatures resulted in H2 evolution accompanied by the formation of either solvent or triflate bound six coordinated species [Ru(S)(P(OMe)3)(bpy)(dfppe)][OTf]n [(S = solvent (n = 2), triflate (n = 1)] (/); these species have not been isolated and could not be established with certainty. They (/) were not isolated, instead the six-coordinated isomeric aqua complexes cis-[Ru(bpy)(dfppe)(OH2)(P(OMe)3)][OTf]2 (/) were isolated. Reaction of the aqua complexes (/) with 1 atm of H2 at room temperature in acetone-d6 solvent resulted in heterolytic cleavage of the H-H bond. Results of the studies on H2 lability and heterolytic activation using these complexes are discussed. The complexes , , , and have been structurally characterized.