CHIRAL RUTHENIUM(IV)-OXO COMPLEXES - STRUCTURE, REACTIVITIES OF [RU(TERPY)(N-BOOLEAN-AND-N)O](2+) (N-BOOLEAN-AND-N=N,N,N',N'-TERAMETHYL-1,2-DIAMINOCYCLOXHEXANE) AND [RU(ME(3)TACN)(CBPY)O](2+) (CBPY=(-)-3,3'-[(4S-TRANS)-1,3-DIOXOLANE-4,5-DIMETHYL]-2,2

摘要

The complexes [Ru-IV(terpy)(cxhn)O](ClO4)(2) (cxhn = N,N,N'N'-tetramethyl-1,2-diaminocyclohexane, terpy = 2,2':6',2 ''(terpyridine) and Ru-IV(Me(3)tacn)(cbpy)O](ClO4)(2) (cbpy = (-)-3,3'-[(4S-trans)-1,3-dioxolane-4,5-dimethyl]-2,2'-bipyridine and Me(3)tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane) have been prepared and crystal structures of [Ru-IV(terpy)(cxhn)O](ClO4)(2) and [Ru-II(Me(3)tacn)(3,3'-Me(2)bPY)(OH2)](ClO4)(2) have been determined [Ru-IV(terpy)(cxhn)O](ClO4)(2) H2O, C25H35Cl2N5O10Ru, M(r) = 737.68, space group P2(1), monoclinic, a = 8.215(5), b = 14.650(7), c = 24.261(10) Angstrom, beta = 94 78(4)degrees, Z = 4, [Ru-II(Me(3)tacn)(3,3'-Me(2)bpy)(OH2)](ClO4)(2), C21H35Cl2N5O9Ru, M(r) = 673.52, space group P2(1), monoclinic, a = 8.463(1), b = 10.751(1), c = 30.192(3) Angstrom, beta = 91.77(1)degrees, Z = 4. The Ru = O distance in [Ru-IV(terpy)(cxhn)O](ClO4)(2) is 1.827(14) Angstrom. All the ruthenium-oxo complexes react with alkenes to give the corresponding epoxides. Stoichiometric oxidation of styrene and 4-chlorostyrene by [Ru-IV(terpy)(1R,2R-cxhn)O](ClO4)(2) gave the corresponding epoxide with no enantiomeric excess, Using [Ru-IV(Me(3)tacn)(cbpy)O](ClO4)(2), a 9% enantiomeric excess of R-styrene oxide and R-4-chlorostyrene oxide were found in the oxidation of both styrene and 4-chlorostyrene, respectively. [References: 37]