STOICHIOMETRIC INTERCONVERSION OF S-BRIDGED RHIII2AGI3 PENTANUCLEAR AND RHIII4AGI5 NONANUCLEAR STRUCTURES - SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF [AG-3(RH(AET)(3))(2)](3+) AND [AGS(RH(AET)(3))(4)](5+) (AET EQUALS 2-AMINOETHANETHIOLATE)

摘要

The reaction of fac(S)-[Rh(aet)(3)] (aet = 2-aminoethanethiolate) with 1.5 molar equiv of AgBF4 in water gave an S-bridged pentanuclear complex, [Ag-3{Rh(aet)(3)}(2)](BF4)(3) (1(BF4)(3)), while the reaction with 1.2 molar equiv of AgBF4 produced an S-bridged nonanuclear complex, [Ag-5{Rh(aet)(3)}(4)](BF4)(5) (2(BF4)(5)). The crystal structures of 1(BF4)(3) and 2(BF4)(5) were determined by X-ray crystallography: 1(BF4)(3) . H2O crystallizes in the orthorhombic space group Pnma with a = 16.609(3) Angstrom, b = 13.352(4) Angstrom, c= 15.665 Angstrom, V = 3497(1) Angstrom(3), Z = 4, and R = 0.056. 2(BF4)(5) . 4H(2)O crystallizes in the monoclinic space group P2(1)/c with a = 15.665(5) Angstrom, b = 14.003(2) Angstrom, c = 31.900(9) Angstrom, beta = 94.19(1)degrees, V = 6979(3) Angstrom(3), Z = 4, and R = 0.068. In 1 each of three Ag-I atoms is linearly coordinated by two thiolato sulfur atoms from two octahedral fac(S)-[Rh(aet)(3)] units. In 2 each of four Ag-I atoms is trigonally coordinated by three thiolato sulfur atoms from three fac(S)-[Rh(aet)(3)] units, while the remaining Ag-I atom is linearly coordinated by two thiolato sulfur atoms from two fac(S)-[Rh(aet)(3)] units. 2 was readily converted to 1 by reaction with Ag+, while the conversion of 1 to 2 was achieved by the reaction with fac(S)[Rh(aet)(3)]. [References: 29]