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Crystal structures and electrical properties of radical-cation salts of the chiral organic donor TMET (S.S,S,Sbis-(dimethylethylenedithio)tetrathiafulvalene) are described. Two structural types, 2:l with octahedral anions PF;, AsF;, SbF;, IT (incommensurate), and 3:2 with tetrahedral anions BF: , Cloy, ReO; are observed. Resistivity measurements between 2 and 298 K indicate that the 3:2 types are organic metals, while the other compounds are semiconductors. (TMET), (CIO,), is metallic down to about 120 K at ambient pressure and remains metallic down to 2 K at 8 kbar.

Additional work is in progress on characterization, physical properties and on varying the central metallic atom, and the size as well as the side chains of the azamacrocyclic ligand. Experimental S,S-DMBEDT-TTF

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Reaction of (η 4 -2,5-norbornadiene)dimethylplatinum(II) with (2-diphenylphosphinoethyl)dimethylamine, (3-diphenylphosphinopropyl)dimethylamine, 2-diphenylphosphino-N,N-dimethylaniline, or (o-diphenylphosphinobenzyl)dimethylamine resulted in the formation of the corresponding dimethyl platinum complexes containing the P,N-chelating ligands, while reaction with (diphenylphosphinomethyl)dimethylamine gave only the bis(phosphine) complex. Reaction of the P,N-chelated dimethyl complexes with iodotrimethylsilane stereoselectively gave the corresponding methyl iodo complexes in which only the methyl group trans to the phosphorus atom was exchanged. Reaction with 1,2-bis(dimethylsilyl)benzene yielded cyclic bis(silyl) complexes. Analogous experiments with (dppe)PtMe 2 revealed that the P,N-chelated complexes exhibit a considerably higher reactivity than the bis(phosphine) complex. The most interesting feature in the solid-state structures of [(κ 2 -Pis the very long Pt-N distances (221.0(7), 223.3(6), and 236.8(5) pm, respectively), showing that the nitrogen atom of the P,N-chelating ligand is only weakly bonded. The Pt-C and Pt-Si distances trans to nitrogen are much shorter (203.7(9), 230.4-(2) pm) than those trans to phosphorus (206.9(8), 237.2(2) pm).