Stoichiometric Interconversion of S-Bridged Rh(III)(2)Ag(I)(3) Pentanuclear and Rh(III)(4)Ag(I)(5) Nonanuclear Structures: Synthesis and Structural Characterization of [Ag(3){Rh(aet)(3)}(2)](3+) and [Ag(5){Rh(aet)(3)}(4)](5+) (aet = 2-Aminoethanethiolate).
The reaction of fac(S)-[Rh(aet)(3)] (aet = 2-aminoethanethiolate) with 1.5 molar equiv of AgBF(4) in water gave an S-bridged pentanuclear complex, [Ag(3){Rh(aet)(3)}(2)](BF(4))(3) (1(BF(4))(3)), while the reaction with 1.2 molar equiv of AgBF(4) produced an S-bridged nonanuclear complex, [Ag(5){Rh(aet)(3)}(4)](BF(4))(5) (2(BF(4))(5)). The crystal structures of 1(BF(4))(3) and 2(BF(4))(5) were determined by X-ray crystallography: 1(BF(4))(3).H(2)O crystallizes in the orthorhombic space group Pnma with a = 16.609(3) Å, b = 13.352(4) Å, c = 15.771(3) Å, V = 3497(1) Å(3), Z = 4, and R = 0.056. 2(BF(4))(5).4H(2)O crystallizes in the monoclinic space group P2(1)/c with a = 15.665(5) Å, b = 14.003(2) Å, c = 31.900(9) Å, beta = 94.19(1) degrees, V = 6979(3) Å(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)].
Konno
Takumi
T
Department of Chemistry, University of Tsukuba, Tsukuba, Ibaraki 305, Japan.
Okamoto Ki
Ken-ichi