NOVEL IONIC HALF SANDWICH RUTHENIUM COMPLEXES SUPPORTED BY N-HETEROCYCLIC CARBENE AND/OR PHOSPHINES, AS EFFICIENT TRANSFER HYDROGENATION CATALYSTS

摘要

Acridine...................................................................................................................244-[CH3C(=O)]C6H4CN........................................................................................... 254-[HC(=O)]C6H4CN...............................................................................................264-Et(C=O)NHC6H4CN............................................................................................274-MeO-C6H4CN......................................................................................................284-NH2C6H4CN........................................................................................................29Ethylmethacrylate...................................................................................................30Sulfonylbenzonitrile..................................................................................................31VIII-3. X-ray crystal structure of[Cp(IPr)Ru(pyr)2][PF6]..........................................32Figure 9. The molecular structure of complex [Cp(IPr)Ru(pyr)2][PF6]. Thecounter-anion, the THF solvate, and hydrogen atoms are omitted forclarity........................32IX.Reference...........................................................................................................32I. TitleNovel ionic half sandwich ruthenium complexes supported by N-heterocycliccarbene and/orphosphines, as efficient transfer hydrogenation catalysts.II. AbstractThe ionic half-sandwich complexes of ruthenium (II) with the formula of (I),where Cp* areselected from cyclopentadienyl or pentamethylcyclopentadienyl groups. LigandsL1, L2 and L3of the complex (1) can be the same or different from each other, the moietiesgroups of ligands L1,L2 and L3 are N-containing molecules, and/or O-containing molecules, and/or S-containingmolecules, and/or P-containing molecules, for examples, N-heterocylic carbene,phosphines,pyridines, nitriles, thiourea, and others. Anion of the compound (I) can bevaried from lowcoordinating to non-coordinating anions, for example, triflate (CF3SO3-)tetrafluoroborate ([BF4]-), hexafluorophosphate ([PF6]-), perchlorate ([ClO4]-),tetrakis-[3,5 -bis(trifluoromethyl)phenyl]borate ion, [B[3,5-(CF3)2C6H3]4]-, tetrakis-(pentafluorophenyl)-borate(B(C6F5)4-) and A1(OC(CF3)3)4-. Furthermore, the preparation and catalyticreactivity of thesecomplexes are described.L1, L2, L3 = N-containing molecules and/or O-containing molecules and/or S-containing moleculesand/or P-contaning molecules, for examples, N-heterocylic carbene, phosphines,pyridines, nitriles,thiourea,and othersAnion.THETA. = Either low-coordinating or noncoordinating anions such astriflate (CF3SO3-) tetrafluoroborate([BF4]-), hexafluorophosphate ([PF6]), perchlorate ([ClO4]-), tetrakis[3,5 -bis(trifluoromethyl)phenyl]borate ion, [B[3,5-(CF3)2C6H3]4]-,tetrakis(pentafluorophenyl)borate(B(C6F6)4-) and Al(OC(CF3)3)4-Cp*=Cyclopentadinyl or pentamethylcyclopentadienylFigure 1. Half sandwich ruthenium complexesIII. Field of the inventionThe present patent relates to new ionic half sandwich ruthenium complexes,which are usefulas efficient transfer hydrogenation catalysts.IV. A broad description of the inventionOne of the most important processes to synthesis N-containing compounds is thereduction ofnitriles. The conventional method to reduce nitrile is the stoichiometricusage of metal hydridesLiA1H4 or NaBH4, hydrosilanes, or Hantzsch ester.1-3 These methods normallyend up with manyeconomic and environmental issues such as poor atom efficiency, lowselectivity, expensive andhazardous reagents, less tolerated to functional groups, and wasteful by-products. In thisinvention, we have now surprisingly discovered the new half sandwich rutheniumcomplexes,4-11which shows the significant performance in the transfer-hydrogenation ofnitriles under mildconditions. In addition, these new compounds also display excellent bio-reactivities. The scope