Copper derivatives of tetrathiafulvalene

Abstract

Oxidation of tetrathiafulvalene with CuCI,. 2H,O in ethanol produced the mixed valence metallotetrathiaethylene (TTF),(CuCI,), containing both TTF? and TTF2+, which was converted into (TTF), CuCI, on dissolution in hot acetonitrile while the CUCI,~-and BF,salts of TTF2+ were prepared using CuC1,-2II,O and Cu (BF,), in acetonitrile ; resonance Raman spectroscopy was used to probe the oxidation state of TTF in these copper metallotetrathiafulvalenes, and e.s.r. and magnetic susceptibility data indicate the presence of threedimensional magnetic interactions in the TTF" and TTF2+ CuC1,2-salts.

Crystal and molecular structure of an unusual salt formed from the radical cation of tetrathiafulvalene (TTF) and the trichloromercurate anion (HgCl3), (TTF)(HgCl3)

“…The crystal density was measured by the neutral buoyancy method in a mixture of bromoform and carbon tetrachloride. Standard crystallographic data are as follows: a = 12.661 (3) Á, b = 15.969 (4) A, c = 7.416 (2) A, ct = 98.69 (2)°, ß = 95.73 (2)°, 7 = 120.01 (2)°, V= 1256.2 A3, mol wt = 511.30, Z = 4, Dmea8d = 2.68 (1) g cm"3, A»icd = 2.70 g cm"3, g(Mo ) = 136.0 cm"1.…”

“…Inorganic Chemistry, Vol. Hg(l) 793 (l)6 545 (1) 2678 (1) Hg( 2) 1342 (1) 4805 (1) 5164 (1) 0(11) -130 (3) 1106…”

(Tetrathiafulvalene)bis(acetylacetonato)palladium(II), (TTF)Pd(acac)2, a metallotetrathiaethylene containing neutral tetrathiafulvalene

“…The intermolecular interactions are van der Waals in nature, consisting in the main of CH3(acac)••• CH3(acac) and CH3(acac)-S(TTF) contacts. The shortest contacts within these two groups are C(7)-C (7) [-x, 1 -y, -z] = 3.424 (8) A and S(9)-C(8) [-x, -y, -z] = 3.878 (5) A.…”

“…The former bond is much stronger (2.07 Á) than the relatively weak Mo-OH bond (2.36 Á) which resembles the weak Mo-OH2 bond in the molybdenum-aquo complexes 3 and 6.9 •11 Obviously, this lenghthening of the axial Mo-06 bond is due to the strong trans influence of the multiple Mo-05 bond. In the related complex 5 the axial Mo-F bond trans to the multiple Mo-0 bond exhibits an analogous weakening.10…”