CHALCOGENOHALOGENOGALLATES(III) AND INDAT ES(III) - A NEW CLASS OF COMPOUNDS FOR ELEMENTS OF THE 3RD MAIN-GROUP - PREPARATION AND STRUCTUREOF [PH4P]2[IN2SX6], [ET4N]3[IN3E3CL6]CENTER-DOT-MECN AND [ET4N]3[GA3S3CL6]CENTER-DOT-THF (X=CL, BR, E=S, SE)

[In2SCl6]2-, [In2SBr6]2-, [In3S3Cl6]3-, [In3Se3Cl6]3-, and [Ga3S3Cl6]3 - were synthesised as the first known chalcogenohalogeno anions of mai n group 3 elements. [Ph4P]2[In2SCl6] (1) (P1BAR; a = 10.876(4) angstro m, b = 12.711(6) angstrom, c = 19.634(7) angstrom, alpha = 107.21(3)de grees, beta = 96.80(3)degrees, gamma = 109.78(3)degrees; Z = 2) and [P h4P]2[In2SBr6] (2) (C2/c; a = 48.290(9) angstrom, b = 11.974(4) angstr om, c = 17.188(5) angstrom, beta = 93.57(3)degrees, Z = 8) were prepar ed by reaction of InX3, (CH3)3SiSSi(CH3)3 and Ph4PX (X = Cl, Br) in ac etonitrile. The reaction of MCl3 (M = Ga, In) with Et4NSH/Et4NScH in a cetonitrile gave [E4tN]3[In3S3Cl6] . MeCN (3) (P2(1)/c; a = 17.328(4) angstrom, b = 12.694(3) angstrom, c = 21.409(4) angstrom, 8 = 112.18(1 )degrees, Z = 4), [Et4N]3[In3Se3Cl6] . MeCN (4) (P2(1)/c; a = 17.460(4 ) angstrom, b = 12.816(2) angstrom, c = 21.513(4) angstrom, beta = 112 .16(2)degrees, Z = 4), and [Et4N]3[Ga3S3Cl6] . THF (5) (P2(1)/n; a = 1 1.967(3) angstrom, b = 23.404(9) angstrom, c = 16.260(3) angstrom, bet a = 90.75(2)degrees, Z = 4). The [In2SX6]2- anions (X = Cl, Br) in 1 a nd 2 consist of two InSX3 tetrahedra sharing a common sulfur atom. The frameworks of 3, 4 and 5 each contain a six-membered ring of alternat ing metal and chalcogen atoms. Two terminal chlorine atoms complete a distorted tetrahedral coordination sphere around each metal atom.