Die Darstellung der kationischen Trihydridodiplatimll)‐Komplexe (IIa) erfolgt durch Behandlung des dikationischen Bis‐[pyrazoll‐PtUU‐Monomeren (I) mit KBH4.
compound K[NEt4] [Con(SC10H13)4]. The reaction of 2 equiv of LiSC10H13 with CoCl2 in ethanol or CH3CN gives a light green precipitate whose elemental analysis is consistent with a Co(SC10H13)2 formulation.14 This compound is insoluble in alcohols, CH3CN, hexane, and toluene but is soluble in DMF to give blue-green solutions.The average Co-S bond length in 1 (2.28 (1) Á) is 0.03 Á shorter than the corresponding distance in 13 The difference in the overall charge on the anions is principally responsible for the discrepancy in these parameters.2,3 Also, the differences in the Co-S-Ph conformation may contribute to the change in the bond distances. In 1 the Co-S bonds are approximately orthogonal to plane of the durene ring, while in Co(SPh)42-the Co-S bonds lie in the plane determined by the phenyl rings.13 The bond angles of the CoS3N unit show large deviations from the normal tetrahedral angle of 109.5°; these deviations result from the mixed-ligand coordination and the steric interactions among the ligands.White crystals of [N(n-Pr)4][Cu(SC10H13)2] (2) are obtained in 60% yield from the cooled filtrate of the room-temperature reaction of 1 equiv of Cu(CH3CN)4BF4 and [N(n-Pr)4]Br with 3 equiv of LiSC10H13 in ethanol. The linear digonal coordination of the copper was revealed by an X-ray crystal structure determination (Figure 2).15 The anion has crystallographic C2 symmetry with the S-Cu-S' angle equal to 178.6 (1)°. The Cu-S distance of 2.137 (2) A is substantially shorter than the average Cu-S distance in the three-coordinate copper in [Ph4P]2[Cu(SPh)3]8 and slightly less than average Cu-S distance for the two-coordinate coppers in [Cu5(SPh)7]2-and [Cu5(S-Z-Bu)6]-.9,10 The observed large change in the Cu-S distance as a function of coordination number should be a valuable consideration in the interpretation of EXAFS data of copper proteins.16A benzenethiolate complex, (PPh4)[Cu(SPh)2], which is analogous to 2, was previously reported but was not structurally characterized.8 [Cu(SPh)2]-differs from 2 in that it readily undergoes oligomerization reactions to give the cluster compounds [Cu4(SPh)6]2-and [Cu5(SPh)7]2-.8,9,11 The reaction of Cu(I) salts with C10H13S" was studied for a variety of Cu/SR ratios (5/1 to 1.5/1) and under different reaction conditions; 2 was the only isolated product, and in no case was the yellow color, which is characteristic of many Curx(SR)y cluster complexes,8-11 ever detected.The reduced tendency of 2,3,5,6-tetramethylbenzenethiolate to bridge metal centers makes it an attractive ligand for the synthesis and study of monomeric metal thiolate complexes in cases where less sterically demanding ligands give clusters or polymeric compounds.17,18
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