POLYSULFONYLAMINES .29. SYNTHESIS OF ORGANOTHALLIUM(III) DIMESYLAMIDES AND X-RAY STRUCTURAL-ANALYSIS OF (ME3SICH2)2TLN(SO2ME)2 AND (ME3SICH2)2TLN(SO2ME)2.H2O

The compounds R2TlN(SO2Me)2 (R = Me3SiCH2 (2), Me (3), Ph (4)) were prepared by metathesis of R2TlCl with AgN(SO2Me)2. The reaction of PhTl(O2CCF3)2 with Me3SiN(SO2Me)2 afforded PhTl[N(SO2Me)2]2 (5). Further, the (1/1) addition compounds of 2 with H2O (2a), 3 with 18-crown-6, 4 with DMF, and 5 with pyridine were isolated and characterized. 2 crystallizes in the monoclinic space group P2(1)/n with a = 1026.4(4), b = 1118.0(3), c = 1798.3(7) pm, beta = 102.67(3)-degrees, U = 2.0133(12) nm3, Z = 4. The thallium atoms are linked by two (NSO) bridges originating from different (MeSO2)2N- ligands to form eight-membered [TlNSO]2 rings (Tl-N 260.9(3) pm, Tl-O 281.3(3) pm, C-Tl-C 175.9(2)-degrees). The MeSO2 groups exocyclic to the eight-membered rings act as (SO) bridges between nitrogen and thallium atoms of neighbouring rings (Tl-O 279.9(3) pm). Thus, layers consisting of centrosymmetric eight-membered [TlNSO]2 rings and centrosymmetric twenty-membered [TlNSOTlOSNSO]2 rings are formed. The coordination polyhedron of the thallium atoms is a moderately distorted trigonal bipyramid with the two carbon atoms as apices. This structure is compared with the known crystal structure of the corresponding indium compound. The hydrate 2a crystallizes in the triclinic space group P1BAR with a = 742.7(2), b = 1003.8(2), c = 1446.5(3) pm, alpha = 92.33(2), beta = 97.98(2), gamma = 92.40(2)-degrees, U = 1.0659(4) nm3, Z = 2. Its structure consists of polymeric strands, in which [R2Tl(OH2)] units are connected by (NSO1) bridges (Tl-N 272.3(3), Tl-O1 277.5(2), Tl-OH2 251.2(2) pm, C-Tl-C 172.3(1)-degrees). Additionally, at each thallium atom a four-membered [TlNSO2] chelate ring is formed through a weaker interaction with the oxygen atom O2 geminal to the bridging oxygen O1 (Tl...O2 288.1(3) pm). The thallium atoms in 2a display irregular (C2NO3) hexacoordination.