Journalartikel

Jahr der Veröffentlichung: 1998

Seiten: 1943-1950

Zeitschrift: Journal of Inorganic and General Chemistry

Bandnummer: 624

Heftnummer: 12

ISSN: 0044-2313

Verlag: Wiley

Abstract: 
Black crystals of Tl-2[MoCl6] are formed in the reaction of TlCl with MoOCl3 in a sealed evacuated glass ampoule at 350 degrees C. The crystal structure analysis shows that Tl-2[MoCl6] (cubic, , a=986.35(7)pm) adopts the K-2[PtCl6] structure with a Mo-Cl bond length of 236.6 pm. TI[MoOCl4(NCCH3)] was obtained by the reaction of TlCl with MoOCl3 in acetonitrile in form of yellow, moisture sensitive crystals. The structure (orthorhombic, Cmcm, a = 746.0(1), b = 1463.8(3), c = 857.3(2) pm) is built of Tl+ cations and octahedral [MoOCl4(NCCH3)](-) anions in which the acetonitrile ligand is bound in trans position to the oxygen. The reaction of TlCl and MoOCl3 in dichloromethane yields Tl[Mo2O2Cl7] and Tl-2[Mo4O4Cl14] as green moisture sensitive crystals. The structure of TI[Mo2O2Cl7] (orthorhombic, Pmmn, a = 694.3(1), b = 951.9(2), c = 904.7(1) pm) consists of Tl+ cations and dinuclear [Mo2O2Cl7](-) anions, with two equidistant chlorine bridges of 248.2 and one longer chlorine bridge of 265.7 pm. The oxygen atoms are located in the trans positions of the longer chloro bridge. The structure of Tl-2[Mo4O4Cl14] (triclinic, , a=692.8(1), b=919.6(1), c=998.9(1)pm, alpha=104.94(1)degrees, beta=90.31(1)degrees, gamma=108.14(1)degrees) is build of Tl+ cations and [Mo4O4Cl14](2-) anions which form tetramers of distorted octahedral, edgesharing (MoOCl5) units with chlorine atoms in the bridging positions. The oxygen atoms are located in the trans positions of the longest chlorine bridges.