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Di(4-pyridinio)- Di(2-benzothiazolio)- Di(2-[1 3-dithiolylio])- and Diformyltetraaza[14]annulenes and Tetraaza[14]annulenylene-Homologous Tetrathiafulvalenes.

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[12] a) H. Kast. DOS 2427606 (January 2, 1976) BASFAG: Chem. Absrr. 84
(1976) 137226g: h) R. Miiller, D. Wohrle, Makromoi. Chem. 179 (1978)
2161; c) A. R. Cutler. C. S. Alleyne, D. Dolphin, inorg. Chem. 24 (1985)
2276. 2281 : d) E. Lorch, E. Breitmaier, Chem.-Ztg. 99 (1975) 87.
W. A. Little, Phys. Rev. A 134 (1964) 1416; h) H. J. Keller (Ed.): Chemistry
and Physics cflOne-dimensional Metals, Plenum Press, New York 1977; c)
W A. Little in [13b], p. 257; d) D. Davies, H. Gutfreund, W. A. Little,
Phys. Rev. B 13 (1976) 4766; e) H. Gutfreund, W. A. Little in [13 h] p. 279;
f) cf. Nuchr. Chem. Tech. Lab. 24 (1976) 591.
A. Harriman, G. Porter, J. Chem. Soc. Faraday Trans. 2 7.5 (1979) 1532; b)
A. Harriman, G. Porter, M. C. Richoux, ibid. 2 77 (19x1) 1175; c ) J. R.
Darwent, P. Douglas, A. Harriman, G. Porter, M. C. Richoux, Coord.
Chem. Rev. 44 (1982) 83.
D. Lloyd, K. S. Tucker. D. R. Marshall, J. Chem. Soc. Perkin Trans. 1
I Y N I . 726.
Z. Janousek, H. G. Viehe in H. Bohme, H. G. Viehe (Eds.): imintum Salts
(91 Organic Chemistry. Parr 1 (Advances in Organic Chemi~stry:Melhods
and Resulrs, E. C. Taylor (Ed.), Vol. 9 ) . Wiley-Interscience, New York,
1976, p. 378.
R. Gompper, E. Kujath, H.-U. Wagner, Angew. Chem. 94 (1982) 559;
Anxvw. Chem. i n l . Ed. Engl. 21 (1982) 543; Angew. Chem. Suppi. 1982,
1302.
V. Kral, V. V. Semenov. M. I. Kanishchev, Z. Arnold. S. A. Shevelev.
A. A. Fainzilherg, Collecr. Czech. Chem. Commun. 53 (1988) 1519.
L. Michdehs, E. S. Hill, J Gen. Physiol. 16 (1933) 859.
S. Hiinig. W. Schenk, Liebigs Ann. Chem. 1979, 1523.
a) J. Davila, A. Harriman, M.-C. Richoux, L. R. Milgrom, J. Chem. Soc.
Chcjm. Commun. 1987, 525; h) W. Schuhmann, H.-P. Josei, H. Parlar,
Angcw. Chem. 99 (1987) 264; Angew. Chem. int. Ed. Engi. 26 (1987) 241.
a ) L. R. Milgrom, J. Chem. Soc. Perkin Trans. 1 1983, 2535; b) J.-R.
Fuhrhop, U.Wanja, M. Biinzel, Liehigs Ann. Chem. 1984.426.
K. Sakata, M. Hashimoto, N . Tagami. Y. Murakdmi, Bull. Chem. Soc. Jpn.
53 (1980) 2262.
a ) E:G. Jiger. Z . Chem. 4 (1964) 437; 8 (1968) 30; Z . Anorg. A&. Chem.
364 (1969) 177; b) F. A., L‘Eplattenier, A. Pugin. Helv. Chim. Acta 58
(1975) 917.
K. Sdkata, T. Naganawa, M. Hashimoto, H. I. Ogawa, Y Kato, inorg.
Chim. Actu 143 (1988) 251.
We thank Bayer AG (Dr. G. Heywang) for carrying out the conductivity
measurements.
could therefore only lead to zwitterions. In the case of 5,14dihydrodibenzotetraaza[l4]annulene derivatives, whose
cationic substituents are attached to the ring via a C atom,
the deprotonation should however lead to 7,16-bis(methylene) derivatives of tetraaza[ 141annulenes, which stem
from the 7,16-dihydro isomers (C7’’6H form instead of
N5/14Hform). Ni-complexes of tetrahydro derivatives of
such compounds are already known.[’] If the methylene
groups were part of a 1,3-dithiole ring then such compounds
would be dibenzotetraaza[l4]annulenehomologues of TTF.
They should have interesting redox and complexation properties.
2
BF,O
1
Q
SYN-Me
Q
SY.N-Me
8
‘N-Me
Di(4-pyridinio)-, Di(2-benzothiazolio)-, Di(2-[1,3dithiolylio1)- and Diformyltetraaza[141annulenes
and Tetraaza[141annulenylene-Homologous
Tetrathiafulvalenes**
By Florian Adams and Rudolf Gompper *
Dedicated io Professor Christoph Riichardt on the occasion of
his 60th birthday
Tetrathiafulvalene (TTF) (cf. Refs. [I ,2]) and bis(ethy1enedithio)tetrathiafulvalene (BEDT-TTF or ET) [’, 31 still
have special importance as donors for the production of synthetic metals and organic superconductors, even though a
whole series of derivatives, vinylogues, phenylogues, and
pentalenylene homologues[41of TTF have been sythesized in
the meantime (cf., e.g., Refs. [2,3]). Metal complexes ofcyclic
n-electron systems such as porphyrin, phthalocyanine and
dihydrodibenzotetraaza[ 14]annulene, bearing cationic substituents of the cyanine dye type, should according to Little
et
have snperconducting properties. As models for
such compounds we have prepared 7,16-di(1-pyridinio)and -( 1-[4,4-bipyridindio])-5,14-dihydrodibenzotetraaza[
141
annulenes and some metal complexes thereof.16] In these
compounds, the (bi)pyridinio moieties are bound via the N
atom to the fourteen-membered ring; an NH deprotonation
[*I
[**I
Prof. Dr. R . Gompper, DipLChem. F. Adams
Institut fur Organische Chemie der Universitat
Karlstrasse 23, D-8000 Miinchen 2 (FRG)
This work was supported by the Deutsche Forschungsgemeinschdft and
the Fonds der Chemischen Industrie.
Angeu Chem. Inr. Ed. EngI. 28 (1989) No. 8
(3
a : M = H , H ;b: M=Ni,Cu,Co
In the previous communication16] we have only described
such compounds in which two carbocation or phosphonium
centers are coupled with the fourteen-membered ring (see 14
therein). A system 2a (for physical data of the new compounds see Table I), in which the benzothiazole rings carry
the positive charges, can be obtained from the benzothiazoliovinamidinium salt
1 by reaction with o-phenylenediamine. If the reaction is carried out in the presence of
metal(I1) acetates the metal complexes 2 b are formed. Deprotonation of 2a with sodium methoxide yields the desired orange 7,16-bis(methylene)-7,16-dihydrodibenzotetraaza[l4]annulene in 86% yield (the FAB mass spectrumc9]
shows the required molecular mass of 582). It can be regarded as a [14]annulenylene homologue of the electron-rich 2,2‘bi(3-methyl-2,3-dihydrodibenzothiazolylidene).
Tetraaza[l4]annulenylene-homologous tetrathiafulvalenes 6 are obtained by deprotonation of the dithiolylium salts
5, which in turn are prepared by heating the methylenemalonaldehydes 4[’01 with o-phenylenediamine in the presence of tetrafluoroboric acid-ether in methanol. A nickeland a copper-complex can be prepared from 6e.
6 b does not react with p-tetracyanoquinodimethane. This
is understandable on the basis of the cyclovoltammogram of
6 b (irreversible oxidation at 0.75 eV). 6a, b,f react with
iodine to give black complexes whose elemental analyses
correspond approximately to the composition 6 . (13)1 and
which have only insignificant powder electrical conductivi-
VCH Verlagsge.~ellschafr~a~
mhH. 0-6940 Weinheim, 1989
0570-0833i89jORoR-tO~3$02.50/(1
1063
Table 1. Some physical data of the new compounds.
yield86%; red powder, m.p. = 242-243"C;UV/VIS(DMSO):
Amdx(1g
c) = 367 nrn (4.76), 405 (4.78)
Z b-Ni :
yield 57%; red powder, m.p. > 360°C
Zb-Cu . H,O: yield 35%; blue-violet powder
Zb-Co H,O: yield 20%; blue-violet crystals
3:
yield 86%; orange powder, m.p. 296°C; UVjVIS (DMSO):
i
,
,
=
,373 nm, 465, 510 (sh); MS (FAB [Y]): mjz 589 (lOO%,
( M Li)O
Sa:
yield 85%; red powder, m.p. = 181 'C; UVjVIS (DMF):
&,,,,(lg E ) = 275 nm (4.28). 305 (4.21), 352 (4.38), 410 (4.15, sh)
Sb:
yield 45%; red-violet powder, m.p. 271 -272 T; UVjVIS
E ) = 285 nm (4.30), 350 (4.25, sh), 385 (4.29,
(DMF): LmaX(lg
sh), 420 (4.36). 470 (4.33)
sc:
yield 91 %; dark-red powder, m.p. 305-306 'C
Sd:
yield 86%; red powder. m.p. 305-307 "C
5e:
yield 8 0 % ; red-violet powder, m.p. 284°C
5f:
yield 82 YO;
olive-green crystalline powder m.p. = 279-280 " C ;
UVjVIS (DMF): j.ma,(lg E ) = 316 nm (4.13). 391 (3.65, sh), 509
(4.31)
6a:
yield 9 6 % ; yellow powder, m.p. 237-238 "C; UVjVIS
(CH,CI,): Amax = 283 nm. 338, 410
6b:
yield 38%; bright-red powder, m.p. 237-238 "C; UVjVIS
(CH,CI,): A,.,(Ig E ) = 230 nm (4.62), 306(4.41), 344(4.38), 370
(4.30), 471 (4.65); IR (KBr): d = 3060cm-', 1606, 1579, 1550,
1471, 1458, 1439, 1355, 1262, 1191. 1108, 755, 677; MS
(DCI)"51: m / z 489 (100%, ( M H)@)
6e:
yield 82%; bright-red powder, m.p. 262°C
6d:
yield 76%; orange powder, m.p. 288-289°C
6e:
yield 74%; bright-red powder, m.p. 297°C; MS (DCI) [15]: mjz
673 (100%, ( M + H)O)
6f:
yield 45%; red powder, m.p. 257-258°C; UVjVlS (CH,CI,):
i
,
,
,
= 258 nm, 314, 366 (sh), 495; IR (KBr): d = 2920 cm-',
1606, 1581, 1550, 1472, 1460, 1440, 1354, 1262, 1193, 755. 678
8a:
yield 75%; orange powder, m.p. 290-291 "C; UVjVIS
(DMSO): %,,,ax(lgE ) = 324 nm (4.66), 354 (4.77); IR (KBr):
j = 1614cm-', 1592, 1572, 1345, 1267, 1084, 761
nb:
yield 22%; red-violet powder, m.p. > 350°C; UVjVIS
(DMSO): imax(lgE ) = 273 nm (4.47), 413 (4.72), 490 (4.90)
nc:
yield 15%; brown powder, m.p. > 350°C; UVjVIS (DMSO):
;.,ax(lg~) = 266 nm (4.48). 405 (4.61), 529 (5.00)
8d:
yield 91 "4; orange needles, m.p. 346-347°C; UVjVIS
(DMSO): &,ax(lgc) = 310 nm (4.70), 340 (4.61). 355 (4.68), 384
(4.35), 397 (4 29, sh); MS (EI) [9]: m / i 344 (loo%, ( M e ) )
8e-Ni:
yield 69 %; red powder
8e-Cu:
yield 67%; red-brown crystalline powder; UVjVIS (DMSO):
A,,,(Igc) = 312 nm (4.65), 372 (4.48. sh), 389 (4.76). 420 (4.17,
sh)
8e-Co:
yield 37 %; violet crystalline powder
10a:
yield 9 7 % ; yellow powder, m.p. 300 "C (decomp.); MS (El) [Y]:
m / z 354 (100%, ( M e ) )
lob:
yield 98%; orange powder, m.p. 305-306°C; UVjVIS (DMF):
i.,,,(lg E ) = 305 nm (4.22). 366 (4.37, sh), 383 (4.53). 405 (4.59,
429 (4.561, 485 (4.09), 512 (4.02)
1oc:
yield 9 7 % ; dark-red powder, m.p. 265°C (decomp.); MS (EI)
[9]: mjz 444 (loo%, ( M e ) )
10d:
yield 76%; dark-red powder, m.p. 310-311 "C (decomp.)
lla-Ni:
yield 8 8 % ; bronze colored crystals, m.p. 360°C
lla-Cu:
yield 8 7 % ; olive-green crystals. m.p. 310°C
llb-Ni:
yield 73%; brown crystals, m.p. > 360°C
llb-Cu:
yield 63%; gold colored powder, m.p. 325°C (decomp.); UVj
VIS (DMF): I.,,,(lg&) = 313 nm (3.89), 365 (4.26), 388 (4.06),
480 (4.05, sh) 520 (4.24, sh), 545 (4.39), 585 (4.39)
Za:
4
'
+
Y
6
R R
= a.CH,-CH,,
b CH=CH , C CH=C(Ph) , d. o-C6H4 ,
e:C(SMe)=C(SMe) ; f : r\
+
sws
ties'"] (4-electron measurement, 1800 kp; 6 a . (13)1,7:
(T = 1.7 x lo-''
S/(cm-'; 6 b . (13)1,7: cr = 2.7 x lO-''S/
S/cm-').-6c,d weresyncm-'; 6 f . (13)1,7:(T = 1.3 x
thesized in the same way.
An interesting further entry to tetraaza[l4]annulenes of
the structural type 2/3 and 5/6 is opened up by the diiminium
salt 8 a , which can be obtained in 75 % yield from the vinamidinium salt 7[lZ1and o-phenylenediamine. 8 a can be condensed with 1,4-dimethylpyridinium tetrafluoroborate or
2,3-dimethylbenzothiazoliumtetrafluoroborate to give the
tetraaza[l4]annulenes 8 b and 8c, respectively. Hydrolysis of
8 a affords the dialdehyde 8d, which can be converted into
the metal complex 8e. As the syntheses of 8b, c, e indicate,
8a, d could be valuable starting materials for further interesting tetraaza[l4]annulene derivatives.
a
2
BF,O
8
7
R
8
8a: M = H, H; R = -CH=NM~,BF,O
8b:
M=H,H;
R=
VCVN
9
Attempts to prepare derivatives 5 and 6 without annelated
benzene rings by reaction of diaminomaleic dinitrile 9 with 4
have thus far only led to the open-chain compounds 10, from
1064
(0 YCH
Verla~szesellschnfi
mbH. 0-6940 Weinheim.1989
N-CN
H
M(OWz
NC-N,
H
10
R R =
a CH,-CH,
NC,N,
H
H
11: M=Ni,Cu
,b CH=CH , c C(SMe)=C(SMe), d CH=C(Ph)
0570-0X33j89jOXO8-1064 $02.50/0
Anzew. Chem. Int. Ed. Engl. 28 (1989) N o . 8
which the metal complexes 11 can be obtained. The reactions
of 9 with ethoxyacrolein to give dihydrotetraaza[l4]annuiene tetra~arbonitrile"~]
and of 9 with 1,3-diketones to
give diazepines were first reported more than a decade
ag0.1~~1
Received: February 7, 1989 [Z 3163 IE]
German version: Angeiv. Cheni. 101 (1989) 1046
Publication delayed at author's request
[I] a) D. 0. Cowan, F. M. Wlygul, Chem. Eng. News 64 (1986) No. 29, p. 28;
b) H. Perlstein. Angew. Chem. 89 (1977) 534; Angew. Chem. Inr. Ed. Engi.
16 (1977) 519, c) J. B. Torrance, Ace. Chem. Res. 12 (1979) 79; d) F. Wudl,
Purr Appl. Chem. 54 (1982) 1051; Acc. Chem. Res. 17(1984) 227; e) M. R.
Bryce, L. C. Murphy, Nuture (London) 309 (1984); f) R. L. Greene, G. B.
Street, Science (Washingfon) 226 (1984) 651.
[2] J. M. Williams, M. A. Beno, H. H. Wang, P. C. W. Leung, T. J. Emge. U.
Geiser, K. D. Carlson, Acc. Chem. Rex 18 (1985) 261.
[3] E. Amberger. K. Polborn, H. Fuchs, Angew. Chem. 98 (1986) 749, 751;
Angew. Chem. I n f . Ed. Engl. 25 (1986) 727, 729.
[4] W. Frank, R. Gompper, Tetrahedron Letf. 27 (1987) 3083.
(51 a ) W A. Little, Phys. Rev. A 134 (1964) 1416; b) H. J. Keller (Ed.): Chemisirv und Phwics of One-dimensiunul Melals, Plenum Press, New York
1977: c) W. A. Little in [Sbj, p. 257; d) D. Davies, H. Gutfreund, W. A.
Little. Phys. Rev., B f 3 (1976) 4766: e) H. Gutfreund, W. A. Little in [5b],
p. 279; f) cf. Nuchr. Chem. Tech. Lab. 24 (1976) 591.
[6] F. Adams, R. Gompper. E. Kujath, Angew. Chem. 101 (1989) 1043:
A n p w . Chem. I n f . Ed. Engl. 28 (1989) 1060.
[7] W. P. Schammel, L. L. Zimmer. D. H. Busch, Inurg. Chem. 19(1980) 3159.
[S] J. R. Owen, US-Pat. Off. 890002 (September 21, 1971); Chem. Ahslr. 76
(1972) 47394r.
[Y] We thank BASF AG (Dr. W Ereitschaff, Dr. G . Glas) for recording the
m d S S Spectra.
1101 F Adams, R. Gompper, A. Hohenester, H.-U. Wagner, Tetrahedron Lett.
ZY (1988) 6921.
[ l l ] We thank Bayer AG (Dr. G. Heywang) for carrying out the conductivity
measurements.
[I21 a) 2. Arnold. A. Holy, Collect. Czech. Chem. Cummun. 25 (1960) 1318; b)
Z. Arnold, rbid. 26 (1961) 3051; 30 (1965) 2125; c) M. Keshavarz, S. D.
Cox, R. 0. Angus, Jr., F. Wudl, Synrhesis 1988, 641.
[13] I. Kohlmeyer. E. Lorch, G . Bauer, E. Breitmaier, Chem. Ber. 111 (1978)
2919.
[14] a ) R. W. Begland, D. R. Hartter, F. N. Jones, D. J. Sam, W. A. Sheppard,
0. W. Webster, F. J. Weigert, Jr., J. Org. Chem. 39 (1974) 2341; b) Y
Ohtsuka, ibid. 41 (1976) 629.
[I 51 We thank Finnigan MAT GmbH, Bremen, for measuring the mass spectra.
A Novel Approach to Ferroelectric Liquid Crystals:
the First Organotransition Metal Compound
Displaying This Behavior**
By Pablo Espinet, Jesus Etxebarria, Mercedes Marcos,
Joayuina Perez, Angel Remdn, and Jose Luis Serrano
Ferroelectric liquid crystals (FLC) are nowadays a major
area of interest in mesogenic materials, both in basic and
applied research. They are based on rodlike organic molecules with chirdl centers in one of the terminal chains." - 3 1
Recently, some fully organic mesogens having a "pseudo"-
[*] Pro!'. Dr. P. Espinet, Dr. J. Perez
Quimica Inorginica, Facultad de Ciencias
Universidad de Valladolid, E-47005-VaIladol1d(Spain)
["'I
Dr. J. Etxebarria. Dr. A. Remon
Fisica de la Materia Condensada, Facultad de Ciencias
Universidad del Pais Vasco, apartado 644. E-48080 Bilbao (Span)
Prof. Dr. J. L. Serrano, Dr. M. Marcos
Quimica Organica-ICMA, Facultad de Ciencias,
Universidad de Zaragoza-CSIC, E-50009-Zaragoza (Spain)
This work was supported by the E.E.C. (Project St2J-0387-C), C.I.C.YT.
(Spain) (Project PB86-028) and C.A.I.C.Y.T. (Spain) (Project 3282-83c02-02).
Angcw. Chem. In?. Ed. Engl. 28
i f 989) Nu. 8
discotic core and helical structure have been reportedL4]as a
novel molecular type which could be used to obtain chirdl
mesogens. We have described some ortho-palladated dimers
[Pd,(C,N),(p-X),]
derived from the alkylidenamines
R - C,H, - N = CH - C,H, - R';151 when X = acetate the
molecules have a rigid roof-shaped chiral structure; however, only one of the derivatives displayed liquid crystal behavior (monotropic). We report here that similar compounds
containing ortho-palladated azines display S, mesophases
and advantageously enable the introduction of chirality centers by means of chiral carboxylates (Scheme I), which can
9
kN
t P d l O P c I , 5 0HOAr
'/.
I
R
1
Scheme 1. Synthesis of 5 and its phase diagram. K = crystalline; S,* = chiral
smectic C phase; S, = smectic A phase; I = isotropic liquid: R = H,,C,,O.
give rise to FLC behavior. Three novel aspects may be noted: i) the unprecedented molecular shape; ii) the new way of
introducing chirality; and iii) the presence of metal atoms in
the molecule.
On refluxing with Pd(OAc), in acetic acid,16] the azine 1
was ortho-metalated only in one ring to give 2.[71Treatment
of 2 in acetone with HCI (Pd/HCI = l / l ) gave 3. Removal of
the C1 bridges in 3 with AgClO,, and addition of the optically active propionate 4 furnished the complex 5 in which two
asymmetric carbon atoms have been introduced.
As shown by 'H NMR spectroscopy, compound 5 consists of a mixture of trans-AR,R (34%), trans-AR,R (34%)
and cis-R,R (32%) isomers181(Fig. 1). A roof-shaped trans
complex is chiral; since the formation of 5 is not enantioselective, trans-5 must be a 1 :1 mixture of A and A enantiomers. When, in addition, the two carboxylate bridges are
non-racemic, the enantiomers are converted into two nonracemic diastereomers: trans-AR,R and trans-AR, R. A roofshaped cis complex is not chiral on its own; the chirality
introduced by the (R)-2-~hloropropionateligands leads to
cis-R,R as the third diastereomer present in the mixture.
The hydrogens attached to the asymmetric carbon atoms
of the propionato ligands give rise to distinct 'H NMR signals in the three diastereomers (see Fig. 1). The two trans
diastereomers, each containing two homotopic propionato
VCH Verlagsgesellschafi mhH, 0-6940 Weinheim. 1989
0570-0833j89iC)808-1065$02.50/0
1065
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annulenes, dithiolylio, homologous, tetrathiafulvalenes, tetraaza, annulenylene, diformyltetraaza, benzothiazolio, pyridinium
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