Radical salts of TTF derivatives with the metal–metal bonded [Re2Cl8]

84 E.W. Reinheimer et al. / Journal of Molecular Structure 890 (2008) 81–89
Table 6
Bond distances for (o-Me 2TTF) 2[Re 2Cl 8](4) inÅ
Re(1)–Re(2) 2.2249(4)
Re(1)–Cl(8) 2.3071(18)
Re(1)–Cl(5) 2.3267(17)
Re(1)–Cl(6) 2.3385(16)
Re(1)–Cl(7) 2.3411(18)
Re(2)–Cl(3) 2.3158(18)
Re(2)–Cl(2) 2.3254(16)
Re(2)–Cl(4) 2.3279(18)
Re(2)–Cl(1) 2.3378(17)
S(1A)–C(5A) 1.722(7)
S(1A)–C(3A) 1.742(7)
S(2A)–C(5A) 1.702(7)
S(2A)–C(4A) 1.728(7)
S(3A)–C(6A) 1.712(7)
S(3A)–C(7A) 1.727(8)
S(4A)–C(8A) 1.700(8)
S(4A)–C(6A) 1.724(7)
C(1A)–C(3A) 1.502(9)
C(2A)–C(4A) 1.508(9)
C(3A)–C(4A) 1.337(9)
C(5A)–C(6A) 1.401(8)
C(7A)–C(8A) 1.342(11)
S(1B)–C(5B) 1.713(7)
S(1B)–C(3B) 1.746(7)
S(2B)–C(4B) 1.727(7)
S(2B)–C(5B) 1.727(6)
S(3B)–C(7B) 1.717(9)
S(3B)–C(6B) 1.718(7)
S(4B)–C(6B) 1.718(7)
S(4B)–C(8B) 1.719(10)
C(1B)–C(3B) 1.485(10)
C(2B)–C(4B) 1.491(9)
C(3B)–C(4B) 1.356(10)
2.1.2. (TMTSF) 5[Re 2Cl 8] 2 6CH 2Cl 2(2 6CH 2Cl 2)
(TBA)2[Re2Cl8] (0.102 g, 0.090 mmol) was added to each compartment
of the electrochemical cell in 10 mL of CH 2Cl 2 and TMTSF
(0.020 g, 0.044 mmol) was added to the anodic compartment. A
low current density of 0.5 lA was applied to the cell. After a period
Fig. 5. Projection of the crystal structure of (1 2CH 3CN) in the bc plane.
Table 7
Estimated degree of ionicity for the donor molecules for (1 2CH 3CN), (2 6CH 2Cl 2), 3
and 4
Salt Molecule A a (Å) B b (Å) Q c
(TMTTF)3[Re2Cl8] 2CH3CN (1 2CH3CN) A 1.392(8) 1.728(4) +0.95
B 1.399(3) 1.717(5) +1.17
C 1.357(5) 1.750(3) +0.25
(TMTSF) 5[Re 2Cl 8] 2 6CH 2Cl 2 (2 6CH 2Cl 2) A 1.377(9) 1.859(8) +1.10
A 1.377(9) 1.859(8) +1.10
B 1.381(5) 1.877(4) +1.10
B 1.381(5) 1.877(4) +1.10
C 1.401(8) 1.872(7) +1.40
(BEDT-TTF) 2[Re 2Cl 8](3) A 1.408(6) 1.717(5) +1.29
B 1.385(7) 1.725(6) +0.89
(o-Me 2TTF) 2[Re 2Cl 8](4) A 1.401(3) 1.715(3) +1.22
B 1.373(2) 1.717(4) +0.82
a Central C@C bond distance.
b Mean central C–S bond distance.
c Q = charge estimated with the formula Q = 17.92 + 23.43 * (A/B) from Ref. [34].
of 1 week, small black needle-shaped crystals of the salt were
apparent on the electrode surface; the product was carefully removed
with a spatula, washed with CH 2Cl 2 and dried in air.
2.1.3. (BEDT-TTF) 2[Re 2Cl 8](3)
Both compartments of the electrochemical cell were treated with
150 mg (0.131 mmol) of (TBA) 2[Re 2Cl 8] in 10 mL of PhCN. BEDT-
TTF (0.025 g, 0.061 mmol) was added to the anodic compartment
and the entire cell was attached to a potentiostat to insure a constant
oxidative current biased to a low potential of 0.5 lA. After a period of
2 months, small black block-shaped crystals of the title formed on
the electrode surface. The crystals were carefully scraped from the
electrode surface, washed with PhCN and dried in air.
2.1.4. (o-Me2TTF)2[Re2Cl8] (4)
To each compartment of the electrochemical cell was added
(TBA)2[Re2Cl8] (0.100 g, 0.088 mmol) in 10 mL of CH3CN, and o-