STABLE SILVER COMPLEXES WITH C2B9H12- DERIVATIVES

The reaction of 7,8-dithio-7,8-dicarba-nido-undecaborate(1-) (L(s2c-)) and L(s2n-)) and 7-thio-8-methyl-7,8-dicarba-nido-undecaborate(1-) (L (s1-)) derivatives with Ag+ and Lewis base, PPh3 or bipy, yields white stable solids with the stoichiometries [Ag(L(s2n))(Lewis)], [Ag(L(s2c ))(Lewis)], and [Ag(L(s1))(Lewis)], respectively. The stoichiometry is independent of the length of the S,S'-connected strings in L(s2c-) co mplexes. When the S,S' connected string contains a possible coordinati ng element such as oxygen, the extra coordinating ligand, a Lewis base , is not required. Crystal structure data for [Ag(L(s2c15))]: mol wt 4 63.6; space group Pna2(1); Z = 4; a = 14.0211(7) angstrom, b = 16.658( 8) angstrom, c = 8.196(3) angstrom, beta = 90.0-degrees; R(w)(F(o)) = 0.038. Crystal structure data for [Ag(L(s2c6))(PPh3)].0,5CH2Cl2: mol w t 636.2; space group P2(1)/n; Z = 4; a = 13.069(3) angstrom, b = 17.41 4(5) angstrom, c = 13.545(4) angstrom, beta = 110.32(2)degrees; R(w)(F (o)) = 0.034. In most of the crystal structures the sulfur atoms bridg e two silver ions. However, the two S-Ag interactions are not equivale nt, with a longer and a shorter S-Ag bond. The usual distances are Ag( 1)-S(1) = 2.558(3) angstrom and Ag(1)-S(2) = 2.711(3) angstrom (L(s2c6 -), {7,8-mu-(SCH2CH2S)-7,8-C2B9H10}-; L(s2c15-); mu-(SCH2CH2OCH2CH2OCH 2CH2OCH2CH2S)-7,8-C2B9H10}-).