3916 destruction of the starting material. Unchanged 11 and 12 were isolated by GLC on column B at 65 OC. NMR analysis showed a 65:35 ratio of 1 1 and 12. Similarly, recovery of 11 and 12 from a reaction with sodium in ammonia (85% destruction of starting material) afforded a 65:35 mixture of these isomers. Product Stability under Reductive Cleavage Conditions. To a solution of 0.17 g (7.4 g-atom) of sodium in 10 ml of ammonia was injected 50 ~1 ( ~ 0 . mmol) 3 of alkyl- or allylindene. After stirring for 1 h, the reaction was quenched and worked up as described above for the synthesis of alkylindenes. The products were analyzed on GLC column D at 65 OC. The product mixture from the treatment of 17a consisted of 74% I-isopropylindan (16a) and 26% 17a, whereas the product mixture from the cleavage of 17c consisted of 20% 1-n-propylindan (16b), 76% I-allylindan ( I ~ c )2% , 3-allylindene (17c), and two unidentified products each formed in 0.3% away from calculated. Polarography, of an acetonitrile solution of TTF-TCNQBr affords T T P , TTF+, TCNQBrO, TCNQBr- concentrations from which one may calculate the ratio: [TTF] [TTF-+] = 1.05 f 0.03 [TCNQBr] [TCNQBra-] Thus, in spite of its unfortunate elemental analysis, TTF. TCNQBr is essentially 1 : 1, and no reaction other than electron transfer seems to have occurred. Elemental analysis for complex 12.( 19a)4-5 falls between four and five T C N Q molecules per tetraaminoethylene. On the basis of uv absorption a t 394 and 342 nm for T C N Q and LiTCNQ, the ratio of TCNQ/TCNQ-- = 1.4. Hence, if the tetraaminoethylene donor has the expected +2 charge, 12. (19a)4_5contains 4.8 TCNQ's per tetraaminoethylene consistent with elemental analyses.
+
+
TI'XI
200
XQ
Figure 1. Single crystal resistivity vs. temperature
Tetrathionaphthacene affords an interesting series of conductive materials that is admittedly poorly characterized by elemental analysis. Of the 28 tetrathionaphthacene based complexes in this report, only seven had a carbon analysis within 0.3% of calculated, compared with 20 with carbon too low and 1 with carbon too high. In the specific case of TTN. T C N Q (6*19a), parents of both T T N and T C N Q were apparent in the mass spectrum, suggesting no structural changes accompany complexation. Preparation of TTNsTCNQ by direct reaction gave complex with nitrogen 2.5% too high, whereas preparation by metathesis gave complex with nitrogen 1.3% too low-but resistivities were essentially indistinguishable, 1.5 and 1.8 R cm, respectively. Recrystallization of T T N - T C N Q from trichlorobenzene gave further apparently random variation in analysis as did gradient sublimation of the starting materials. Uv and polarographic analysis were not possible on account of the extreme insolubility of T T N complexes. Tetrathionaphthacene complexes have given analytical problems in the past.43 Cyclic Voltametric Data. Redox potentials for most of the donor and acceptors in this report are gathered in Tables 111 and IV. While redox potentials have been measured in the past for a number of these compounds (for example, T T F and TCNQ), many have been redetermined here to obtain a selfconsistent set vs. S C E in acetonitrile. Whenever there is a choice between values, we have thus used our own for calculaton of the difference between first redox potentials of acceptor and donor, E l A - E ~ Din, Table 111. Rather surprisingly the E 1's of the TCNQ's plot very badly against op+and um values, rather poorly for up,and marginally better against (up om)/2.44,45A plot of El vs. (a, up)/245 is shown in Figure 2 and suggests that OMe is considerably more inhibiting on solution electron affinity that would be predicted from its u value.
Wheland. Gillson
+
/
+
Synthesis of Electrically Conductiue Organic Solids
3920 Table 1.
ComDaction Resistivities of ComDlexes Analyses, % Calculated Complex
Found
- ResistivN ityo
C
H
N
C
H
56.87 41.61 45.51
3.47 1.65 1.81
12.06 10.22 11.17
56.73 41.69 45.41
3.57 1.63 1.99
11.92 9.92 11.25
49.94 52.04 44.36 38.18 55.02 48.81 32.74 45.28 45.00 53.00
1.99 2.30 1.45 1.07 2.77 1.59 0.92 1.27 0.84 2.97
12.26 12.78 1 1.49 9.89 12.83 12.65 8.48 11.74 11.66 13.01
49.69 52.40 44.32 38.16 55.33 48.92 32.79 45.12 45.19 52.96
2.27 2.43 1.72 1.17 2.94 1.98 1.09 1.73 1.02 3.13
58.51 52.39 43.36 43.26
4.09 1.32 1.21 0.97
11.37 18.33 16.85 6.73
58.68 52.41 43.31 43.40
5.20, TTF-TNAP 57. 62 (5)2.23,(TTF)y 27.19 PtC4&(CN)4 30.20 (5h.27, (TTF)2* PdC4S4(CN)4 6*19p,TTNeTCNQI2 44.89 6.19c, TTN-TCNQ(OMe)2 62.32 63.46 6*19b,TTN.TCNQ(OMe) 6.19111,TTNeTCNQIMe 53.45 6.1 9 ~TTN , *TCNQEt2 66.64 6.19r, TTN.TCNQMe2 65.73 6.1 91, TTNeTCNQ Br Me 57.32 6.19q, TTN.TCNQ(OMe)- 61.47 (OCH20C H 2) 6*19d,TTNeTCNQ(0Me)- 62.84 (OW 6.19a, TTN-TCNQ 64.73 6*19a, TTN-TCNQ 64.73
2.20 0.91
12.22 6.34
1.01
5 * 1 9 ~TTF.TCNQEt2 , 5*19m,TTFeTCNQIMe 5.191, TTF-TCNQBrMe 5*19a,TTF-TCNQ 5*19k,TTF.TCNQCIMe 5-19b, TTFaTCNQ(0Me) 5*19j,TTF.TCNQBr 5.190, TTF.TCNQBr2 5.19r, TTFmTCNQMe2 5*19i,TTF-TCNQCI 5*19p,TTFeTCNQIz 5-19n, TTFsTCNQC12 5*19~,TTF-TCNQF4 (5)2360 "C. Anal. Calcd for C I ~ H ~ F ~C,N45.00; ~ S ~H :, 0.84; N , 1 1 .66. Found: C, 45.19; H , 1.02; N, 11.91. Tetrathiofulvalene-2,2',3,3',5,5',6,6'-Octafluoro-7,7,7',7'-tetracyanodiphenoquinodimethanComplex [(5)2.21]. A solution of 0.09 g of (n-Bu4N+)2TCNDQFa2- (22)in 10 ml of acetonitrile was added dropwise with swirling to 0.10 g of TTFx(BF4)s (3)in SO ml of acetonitrile. Pressure filtration under nitrogen gave 0.01 to 0.02 g (-15%) of purple solid, mp >360 OC. Anal. Calcd for C3oH8N4F&: C, 43.26; H, 0.97; N, 6.73. Found: C , 4 3 . 1 6 ; H , 1.49;N,?.lO;C,43.63;H, 1.56;N,7.23. Tetrathionaph thacene-2,5-Dimethoxy-7,7,8,8-tetracyanoquinodimethan Complex (6.19~).A solution of tetrathionaphthacene was prepared by heating 0.10 g of tetrathionaphthacene with SO ml of trichlorobenzene and the cooling back to about 40 "C. A solution of 0.080 g of TCNQ(OMe)2 in 45 ml of hot trichlorobenzene was added over several minutes. Slow cooling to room temperature, followed by pressure filtration under N2, washing with trichlorobenzene and then benzene gave 0.14 g (-80%) of dark red-purple solid, mp >360 OC. Anal. Calcd for C32H16N402S4: C, 62.32; H, 2.62; N , 9.08. Found: C , 62.02; H , 2.65; N , 8.84. Tetrathionaphthacene-Azotetracyanocyclopentadiene Complex [(6)y33].A solution of 0. I O g of TTN.+CI- (7)in 400 ml of refluxing methanol was gravity filtered into 0.10 g of 34 in room-temperature methanol. Pressure filtration under nitrogen, washing with methanol, and blowing dry gave 0.1 1 g (70%) of strikingly reflective dark brown solid, visible decomposition -240 "C, mp >360 "C. Anal. Calcd for C54H16SsNl&H30H: C , 60.42; H , 1.84; N , 12.81. Found: C, 60.26; H, 1.84; N , 13.29; C, 60.32; H, 1.84;N , 13.35. 1,1',3,3'-Diethylene-2,2'-bibenzimidazolidene-Tetracyanoquinodimethan Complexes [13*(19a)y2H20, 13*(19a)2, and 13*(19a)4-5]. A solution of 0.094 g of LiTCNQ in 25 ml of water was filtered into 0.10 g of dibromide 14 in 25 ml of water. The flocculent blue precipitate was pressure filtered off under N2, washed with water, and blown dry mp 123-125 " C under h?,giving 0.14 g ( 8 5 % ) of 13-(19a)2.2H20, with decomposition. Anal. Calcd for C42H24N12.2H~O:C, 68.84; H, 3.85; N , 22.94. Found: C, 68.89; H, 3.39; N , 23.13; C, 68.94; H, 3.47; N , 22.87. 13*(19a)2-2Hz0 (0.45g), dissolved in 100 ml of refluxing acetonitrile, was refluxed down to 50 ml and rapidly filtered and cooled. Blowing the filtrate down further with nitrogen gave a small quantity of brilliant dark blue crystals 13-(19a)2,decomposition starting a t -200 OC. Anal. Calcd for C42H24N12: C, 72.40; H, 3.47; N , 24.12. Found: C , 72.23; H , 3.37; N , 24.35. 13.(19a)2.2H20 (0.48 g) and 0.42 g of T C N Q were refluxed under N2 for 1 h in 100 ml of acetonitrile. Cooling and pressure filtration under nitrogen gave 0.42 g of 13(19a)4_5 as a black powder, mp >360 "C. Found:C,71.38;H,3.19;N,24.45;C,71.60;H,3.18;~,24.22. 12J'-Bis( 1,3-diphenylimidazolidene)-Tetracyanoquinodimethan Complexes [12*(19a)* and 12.(19a)4-5].A solution of 3.06 g of 1 C N Q in 250 ml of refluxing acetonitrile under nitrogen was treated with 3.33 g of freshly prepared l2.?'-bis(1,3-diphenylimidazolidene)(12).After 1 h of refluxing the reaction mixture was allowed to cool slowly to room temperature. Pressure filtration under nitrogen gave 1.58 g of solid that could be mechanically separated into complex 12(19a)2, mp 182-185 "C with decomposition, dark blue micaceous flakes, and complex 12f19aj4-5,mp 215-225 OC with decomposition, coarse dark blue needles. 12
