MOLECULAR STRUCTURES AND SOME PROPERTIES OF TRIS(2-AMINOETHYL) AMINE COBALT(III) COMPLEXES WITH THIOCARBOXYLATO-O,S SUCH AS 3-MERCAPTOPROPIONATO, 2-MERCAPTOACETATO AND THEIR DERIVATIVES

摘要

Cobalt(III) complexes with a thiolate or thioether ligand, t-[Co(mp)(tren)](+) (1), t-[Co(ma)(tren)](+) (2), t-[Co(mtp)(tren)](2+) (1Me) and t-[Co(mta)(tren)](2+) (2Me), (mp=3-mercaptopropionate, ma=2-mercaptoacetate, mtp=3-(methylthio)propionate and mta=2-(methylthio) acetate) have been prepared in aqueous solutions. The crystal structures of 1, 2, 1Me and 2Me were determined by X-ray diffraction methods. The crystal data are as follows, t-[Co(mp)(tren)]ClO4(1ClO(4)):monoclinic, P2(1), a=10.877(8), b=11.570(4), c=12.173(7) Angstrom, beta=92.20(5)degrees, V=1531(1) Angstrom(3), Z=4 and R=0.060; t-[Co(ma)(tren)]Cl . 3H(2)O (2C1 . 3H(2)O): monoclinic, P2(1), a=7.7688(8), b=27.128(2), c=7.858(1) Angstrom, beta=100.63(1)degrees, V=1627.7(3) Angstrom(3), Z=4 and R=0.066; (+)(465)(CD)-t-[Co(mtp)(tren)](ClO4)(2) ((+)(465)(CD)-1Me(ClO4)(2)): orthorhombic, P2(1)2(1)2(1), a=10.6610(7), b=11.746(1), c=15.555(1) Angstrom, V=1947.9(3) Angstrom 3, Z=4 and R=0.068, (+)(465)(CD)-t-[Co(mta)(tren)](ClO4)(2)((+)(465)(CD)-2Me(ClO4)(2)):orthorh ombic, P2(1)2(1)2(1), a=10.564(1), b=11.375(1), c=15.434(2) Angstrom, V=1854.7(4) Angstrom(3), Z=4 and R=0.047. All central Co(III) atoms have approximately octahedral geometry, coordinated by four N, one O, and one S atoms. All of the complexes are only isomer, of which the sulfur atom in the didentate-O,S ligands are located at the trans position to the tertiary amine nitrogen atom of tren. 1 and 1Me contain six-membered chelate ring, and 2 and 2Me do five-membered chelate ring in the didentate ligand. The chirality of the asymmetric sulfur donor atom in (+)(465)(CD)-1Me is the S configuration and that in (+)(465)(CD)-2Me is the R one, The H-1 NMR, C-13 NMR and electronic absorption spectral behaviors and electrochemical properties of the present complexes are discussed in relation to their stereochemistries. [References: 77]