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Ri co E. Del Sesto,
Atta M. Ari f,
Juan J. Novoa,
Bri an C. Dunn,
CN
at 2242 cm
-1
. The 1580 cm
-1
peak i s assi gned to the
ri ng CdN stretchi ng mode that i s bl ue shi fted wi th
respect to that observed for TCTdue to the ani oni c charge
resi di ng wi thi n the ri ng.
Reacti on of CoCp*
2
and TDAE wi th TCT l eads to
compounds of [CoCp*
2
][TCT] and [TDAE][TCT]
2
compo-
si ti on, respecti vel y. Al l three reducti on products of TCT
di spl ay characteri sti c peaks i n the I R spectrum at 1580,
1320, and 910 cm
-1
, and, hence, al so possess [TCT]
2
2-
.
The el ectrochemi cal behavi or of al l three sal ts of
[TCT]
2
2-
i s the same wi th an i rreversi bl e oxi dati on
occurri ng at +0.70 V, Fi gure 1d, i n addi ti on to the
reversi bl e reducti ons of the cati ons. The i rreversi bl e
oxi dati on i s al so seen i n the CV of TCT, Fi gure 1a. Thi s
anodi c peak i s therefore attri buted to the oxi dati on of
[TCT]
2
2-
to [TCT]
2
-
, whi ch i s unstabl e and breaks apart
i nto [TCT]
-
and TCT
0
, Scheme 1. The i rreversi bl e
reducti on of TCT
0
can then be expl ai ned through the
process of di meri zati on, and suggests that the radi cal
ani on [TCT]
-
i s not stabl e i n the sol vents used (MeCN,
CH
2
Cl
2
, THF) and i mmedi atel y di meri zes to [TCT]
2
2-
,
Scheme 1.
Reaction of TCB with CoCp*
2
. Gi ven the structural
si mi l ari ty of TCB wi th TCT and that the reducti on of
TCB was postul ated to form 2
2-
wi th a framework si mi l ar
to [TCT]
2
2-
,
8
we tri ed to i sol ate the TCB reducti on
product. The reducti on potenti al of TCB i s 0.96 V more
negati ve than that of TCT and shoul d onl y occur upon
reacti on wi th CoCp*
2
of the reductants avai l abl e to us.
Thi s reacti on l ed to the i sol ati on of a compound of
[CoCp*
2
][TCB] composi ti on, whose structure was deter-
mined to be {[CoCp*
2
]
+
}
2
[TCB]
2
2-
, Figure 6b. The [TCB]
2
2-
di ani on resul ts from di meri zati on at the nonsubsti tuted
ri ng carbon, whi ch i s at vari ance wi th the proposed
structure of 2
2-
. [TCB]
2
2-
has a central C-C bond of 1.560
(5) , and the bond l engths wi thi n the benzene ri ngs are
C50-C51, 1.509(4) ; C51-C52, 1.362(4) ; C52-C53,
1.424(4) ; C53-C54, 1.405(4) ; C54-C55, 1.364(3) ;
and C55-C50, 1.523(3) . There i s a shi ft of the ri ng
TABLE 1. Net Atomic Charges Obtained after a
Mulliken Population Analysis of the Density Functional
B3LYP/6-31++G(2d,2p) Wavefunction on Atoms of
Neutral and Radical Anionic [TCT]
n
and [TCBT]
n
(n ) 0, 1-)
mol ecul e atom
charge (e
-
)
n ) 0
charge (e
-
)
n ) 1-
spi n (e
-
)
n ) 1-
[TCT]
n
C1 0.921 0.914 -0.04
C2, C3 0.921 0.924 0.26
C4 -0.591 -0.634 0.00
C5, C6 -0.591 -0.648 -0.04
N1, N3 -0.112 -0.285 0.23
N2 -0.112 -0.134 -0.10
N4 -0.218 -0.337 -0.02
N5, N6 -0.218 -0.395 0.13
[TCBT]
n
C1 -0.203 -0.212 0.314
C2, C3 0.613 0.615 0.029
N1, N3 -0.194 -0.244 0.121
N2 -0.223 -0.301 0.033
C4, C5 0.159 0.100 0.001
N4, N5 -0.366 -0.466 0.003
[DCTO]
-
N1 -1.040
N2, N3 -1.052
N4, N5 -0.508
C1, C2 0.960
C3 1.415
C4, C5 0.312
O -0.797
FIGURE 6. Structure of (a) [TCT]2
2-
as observed i n the [Cr-
(mes)2]2[TCT]2 s-dimer and (b) [TCB]2
2-
as observed in [CoCp*2]2-
[TCB]2, wi th central di mer bonds of 1.570 (4) and 1.560 (5)
, respecti vel y. Li ghter spheres are carbon, darker spheres
ni trogen, and whi te spheres hydrogen.
Formation of Novel 4,4,6,6-Tetracyano-2,2-bitriazine
J . Org. Chem, Vol. 68, No. 9, 2003 3371
CdC
stretch at 1430 cm
-1
i n TCB to 1497 cm
-1
i n
[TCB]
2
2-
, agai n i ndi cati ng that there i s a negati ve charge
wi thi n the ri ng, as observed for [TCT]
2
2-
. The C-H
stretch di sappears upon reducti on; however, an expected
new peak does not appear. The [TCB]
-
di meri zati on at
the unsubsti tuted carbons, as opposed to the ni tri l e-
substi tuted carbons, i s due to the spi n densi ty of the
radi cal ani on bei ng the greatest at the unsubsti tuted
carbons. Thi s most l i kel y forms a ki neti cal l y stabi l i zed
product as i t preci pi tates i mmedi atel y upon the reducti on
of TCB wi th CoCp*
2
.
20
[TCB]
2
2-
can be oxi di zed to TCB
0
wi th 2,3-di chl oro-5,6-benzoqui ni one (DDQ), i .e., vi a cl eav-
age of the central di mer C-C bond, anal ogous to the TCT
oxi dati on mechani sm shown i n Scheme 1.
Formationof C
10
N
10
, TCBT. I n addi ti on to formati on
of the charge-transfer compl ex [TMPD][TCT], the reac-
ti on of TCT wi th the weak reduci ng agent TMPD l ed
to i sol ati on of a compound of [TMPD][C
10
N
10
] com-
posi ti on i n l ow yi el d (2%). The structure of [TMPD]-
[C
10
N
10
] was determi ned by si ngl e-crystal X-ray di f-
fracti on and reveal s that C
10
N
10
i s the new cyanocar-
bon 4,4,6,6-tetracyano-2,2-bi tri azi ne, TCBT, Fi gure 7.
[TMPD][TCBT] i s val ence ambi guous, because i t can
be formul ated as ei ther [TMPD]
0
[TCBT]
0
, [TMPD]
+
-
[TCBT]
-
, or [TMPD]
2+
[TCBT]
2-
.
As the reducti on i s i rreversi bl e, i t i s possi bl e that a
smal l fracti on of TCT i s reduced and di meri zed to
[TCT]
2
2-
and then forms TCBT through the l oss of two
cyani des. Hence, onl y a smal l amount of TCBT forms,
as observed.
The I R spectrum of TCT of [TMPD][TCBT] has
CN
absorpti ons occurri ng as a three-band pattern (2269,
2254, and 2241 cm
-1
) but i s shi fted sl i ghtl y hi gher i n
energy by 10 cm
-1
wi th respect to TCT. Al so present
for TCBT are absorpti ons at 1342, 1250, and 766 cm
-1
,
whi ch are not present i n the spectrum of [TMPD][TCT].
The resul ti ng compl ex i s di amagneti c and EPR si l ent,
(20) The theory of the ki neti cal l y stabi l i zed product i s suggested on
the basi s of other reported exampl es: (a) Effenberger, F.; Mack, K.
E.; Ni ess, R.; Rei si nger, F.; Stei nbach, A.; Stohrer, W.-D.; Stezowski ,
J. J.; Rommel , I .; Mai er, A. J . Org. Chem. 1988, 53, 4379. (b) Hei nze,
J.; Wi l l mann, C.; Bauerl e, P. Angew. Chem., I nt. Ed. 2001, 40, 2861.
SCHEME 1
FIGURE 7. (a) ORTEP drawi ng (50%) of [TMPD][TCBT] and
(b) vi ew of the offset stacki ng of TMPD and TCBTri ngs, where
TMPD are the l i ghter spheres and TCBT the darker spheres.
Bond l engths for the tri azi ne ri ngs are 1.3333 (15) for C6-
N2, 1.3332 (15) for N2-C7, 1.3335 (16) for C7-N3, 1.3285
(16) for N3-C8, 1.3298 (15) for C8-N4, and 1.3402 (16)
for N4-C6. Bond angl es around the ri ng ni trogens are
113.43, 112.41, and 113.10 (10) for C6-N2-C7, C7-N3-C8,
and C8-N4-C6, respecti vel y, whi l e those around the ri ng
carbons are 126.08, 127.21, and 127.73 (10) for N4-C2-N2,
N2-C7-N3, and N3-C8-N4, respecti vel y.
Del Sesto et al .
3372 J . Org. Chem., Vol. 68, No. 9, 2003
suggesti ng but not concl usi vel y showi ng, as di meri zati on
may occur, that the product i s a charge-transfer compl ex
and not a one-el ectron-transfer sal t, [TMPD]
+
[TCBT]
-
.
The el ectrochemi cal behavi or of [TMPD][TCBT] has a
reversi bl e reducti on of TCBT (TCBT/[TCBT]
-
) at +0.03
V, whi ch i s noti ceabl y di fferent from the reducti on of
TCT, Fi gure 1d. Al so present are the TMPD redox pai rs
of TMPD
0/+
and TMPD
+/2+
at +0.10 and +0.72 V,
respecti vel y.
11
The formul ati on of [TMPD]
0
[TCBT]
0
i s pri nci pal l y
based on the structure of the TMPD mol ecul e as a
functi on of i ts charge. The TMPD ri ng bond l engths are
1.3800 (18) for C1-C1 and 1.4050 (18) for C2-C3
wi thi n the TMPD ri ng, and the C2-N1 bond l ength i s
1.3923 (16) ; these val ues are i n good agreement wi th
the 1.39 reported for TMPD
0
.
21a
I n contrast, for
[TMPD]
+
as the [I
3
]
-
and [Cl O
4
]
-
sal ts, the correspondi ng
bond l engths are 1.362 ( 0.001, 1.426 ( 0.004, and 1.346
( 0.002 .
21b,c
Thus, the i nteratomi c TMPD di stances,
parti cul arl y the C2-N1 di stance, are characteri sti c of
TMPD
0
, not [TMPD]
+
.
The two tri azi ne ri ngs of TCBT i n the TMPD charge-
transfer compl ex are connected by a 1.492 (2) C-C
bond, as expected for a sp
2
-sp
2
si ngl e C-C bond and
observed i n the structure of bi pyri mi di ne, whi ch has a
central C-C bond of 1.498 .
22
Al l of the bond l engths
wi thi n the ri ngs are 1.34 ( 0.01 , and the bond angl es
are 127 and 113 for the N-C-N and C-N-C angl es,
respecti vel y, wi thi n the ri ng, as seen i n most neutral
tri azi ne ri ng systems.
4b
The TMPD and TCBT pl anes
stack al ong chai ns wi th al ternati ng TMPD and TCBT
moi eti es and devi ate from copl anari ty by 1.73, wi th each
TCBT fragment di spl aced from the next TCBT i n the
chai n by a hal f uni t. The pl anes are approxi matel y 3.1
apart, wi th the cl osest contact to the cyano-substi tuted
ri ng carbon of the tri azi ne (C8) bei ng the TMPD ni trogen
(N1) wi th a di stance of 2.903 . The short contact resul ts
i n a sl i ght devi ati on of pl anari ty of the di methyl ami no
group wi th respect to the TMPD central ri ng, as the
ni trogen i s el ectrostati cal l y attracted toward the tri azi ne
ri ng.
2,2-Bi tri azi nes are rare, wi th onl y four other exampl es
previ ousl y reported, 3a-d, i n whi ch the 4- and 6-posi -
ti ons are substi tuted wi th el ectron-donati ng groups.
23
Thi s i s the fi rst structural l y characteri zed bi tri azi ne
reported. The azi de 3d (Y ) N
3
) has been postul ated as
a product i n the decomposi ti on of 2,4,6-tri azi do-1,3,5-
tri azi ne en route to ni trogen-ri ch carbon ni tri de network
sol i ds but has not been i sol ated.
24
However, TCBTcoul d
not be i sol ated from [TMPD][TCBT] by ei ther subl i ma-
ti on or sol vent extracti on, as TMPD and TCBTcosubl i me
and have si mi l ar sol ubi l i ti es. Thi s bi tri azi ne coul d be of
i nterest i n the devel opment of mol ecul e-based magnets
or three-di mensi onal network structures i n general due
to the number of possi bl e coordi nati on si tes for metal s
as wel l as i ts reversi bl e one-el ectron reducti on to the
radi cal ani on.
Formationof [C
10
N
10
]
-
, [TCBT]
-
. Reducti on of TCT
wi th ei ther Cr(mes)
2
, CoCp*
2
, or TDAE, resul ts i n a
second deepl y col ored product i n addi ti on to formati on
of the di mer [TCT]
2
2-
. The sol i d-state EPR spectra of al l
three reducti on products from the reacti on wi th Cr(mes)
2
,
CoCp*
2
, or TDAE i ndi cate the presence of a radi cal , A
-
,
wi th g ) 2.003. Di ssol uti on of any of these products i n
ei ther MeCN or THF al l ows the resol uti on of the EPR
hyperfi ne spl i tti ng pattern due to the coupl i ng of the
radi cal wi th the S ) 1
14
N nucl eus. The observed
spectrum i s i denti cal to that reported for the i n si tu Na
or K reducti on of TCT, and 1
-
was postul ated as the
resul ti ng product.
7
Our room-temperature EPR spectrum
coul d be fi t wi th g ) 2.0035 and wi th a set of two
equi val ent ni trogens wi th
2
A14
N
) 3.347 G, a val ue
characteri sti c of aza ri ng ni trogens,
25
and a set of four
equi val ent ni trogens wi th
4
A
14
N
) 0.765 G and a l i ne
wi dth of 0.240 G, Fi gure 8. These val ues are si mi l ar to
those previ ousl y reported wi th
2
A
14
N
) 3.78 G and
4
A
14
N
) 0.82 G,
7
as evi denced by the di fference spectrum,
Fi gure 8. The 2:4 ni trogen rati o i s i nconsi stent wi th the
structure of [TCT]
-
, whi ch l ed Carri ngton et al . to
propose two possi bi l i ti es: (1) a mol ecul ar rearrangement
to 1
-
, whi ch woul d support a 2:4 rati o, or (2) a Jahn-
Tel l er di storti on of the radi cal ani on of TCT. Al though
reducti on of some al kyl tri azi nes wi th Zn/MeCO
2
H
decompose upon heati ng (through the l oss of NH
3
) to form
tri al kyl i mi dazol es, Scheme 2,
26
anal ogous formati on of
(21) (a) I kemoto, I .; Katgi ri , G.; Ni shi mura, S.; Yakushi , K.; Kuroda,
H. Acta Crystallogr., Sect. B 1979, B35, 2265. (b) de Boer, J. L.; Vos,
A.; Huml , K. Acta Crystallogr. 1968, B24, 542. (c) de Boer, J. L.; Vos,
A. Acta Crystallogr. 1972, B28, 835.
(22) Fernhol t, L.; Rommi ng, C.; Samdal , S. Acta Chem. Scand. Ser.
A 1981, 35, 707.
(23) Ki taji ma, H.; Nakatsuji , A.; Yamauchi , H. Nippon Kagaku
Kaishi 1982, 8, 1425.
(24) Gi l l i an, E. G. Chem. Mater. 2000, 12, 3906.
(25) The symbol x i n
x
A14
N represents the number of equi val ent
ni trogens.
FIGURE 8. EPR si gnal (red) and fi t (bl ue) for [TDAE]
2+
-
{[TCBT]
-
}2 i n THF at room temperature. Fi t was made wi th
2
A
14
N ) 3.347 G and
4
A
14
N ) 0.764 G. The di fference between
the cal cul ated and observed spectra i s i n green at the bottom.
Formation of Novel 4,4,6,6-Tetracyano-2,2-bitriazine
J . Org. Chem, Vol. 68, No. 9, 2003 3373
the fused i mi dazol e 1
-
i s mechani sti cal l y unreasonabl e
due to the number of bonds that need to be broken and
formed.
I t was al so suggested that a di storti on of the structure
of [TCT]
-
, due to breaki ng the degeneracy of two LUMO
orbi tal s of TCTfol l owi ng reducti on, coul d expl ai n the 2:4
ni trogen rati o.
7
Thus, the structure of [TCT]
-
was
computati onal l y i nvesti gated to ascertai n i f a di storti on
occurs and, i f so, the predi cted EPR spectrum. Densi ty
functi onal theory (DFT) cal cul ati ons at the B3LYP l evel
usi ng 6-31+G(2d,2p) basi s sets were carri ed out on the
neutral and radi cal ani on of TCT. The TCT contai ns a
set of degenerate e HOMO orbi tal s and a set of degener-
ate e LUMO orbi tal s, wi th the structural symmetry
bei ng D
3h
. Upon addi ti on of an el ectron to form [TCT]
-
,
the degeneraci es are broken as the symmetry of the
mol ecul e i s reduced to C
2v
. Thus, a Jahn-Tel l er di storti on
i s predi cted upon reducti on, and the resul ti ng SOMO and
cal cul ated spi n densi ty of [TCT]
-
, Fi gure 9b, i ndi cate
that a 2:2:1:1 rati o of i nequi val ent ni trogens usi ng the
atom l abel s i n Tabl e 1 woul d resul t wi th predi cted
hyperfi ne spl i tti ngs of 3.44 (N1,N3), 1.41 (N2), 2.73
(N5,N6), and 0.18 (N4) G, respecti vel y. Hence, al though
a di storti on i s anti ci pated for [TCT]
-
, i ts predi cted EPR
spectrum i s i nconsi stent wi th that observed.
Furthermore, the CV of [TDAE]
2+
[A
-
]
2
does not show
the i rreversi bl e oxi dati on and reducti on characteri sti c of
TCT, but a new, reversi bl e one-el ectron peak at +0.03 V
(vs SCE) appears, Fi gure 1e. Thi s peak at +0.03 V i s
i denti cal to that observed for [TMPD][TCBT]. Li kewi se,
the el emental anal ysi s of the [TDAE]
2+
[A
-
]
2
al so sug-
gests that A
-
i s [TCBT]
-
. Therefore, al though 1
-
i s not
expected on the basi s of the number of bonds that woul d
have to be broken and reformed, the experi mental EPR,
as compared wi th the predi cted spectra, the el emental
anal ysi s, and the di fference i n el ectrochemi cal behavi or
of A
-
, as compared wi th the behavi or of TCTand [TCT]
-
,
suggest that a new speci es i s formed fol l owi ng the
reducti on of TCTand i s [TCBT]
-
. Formati on of [TCBT]
-
can be expected vi a more reasonabl e mechani sti c pro-
cesses as compared to 1
-
(vi de i nfra).
DFT cal cul ati ons of TCBT and [TCBT]
-
were carri ed
out at the B3LYP l evel , and the MO di agram as wel l as
the spi n and charge densi ti es were cal cul ated, Fi gure 10
and Tabl e 1. TCBT contai ns two cl osel y spaced, but not
degenerate, HOMO and HOMO-1 orbi tal s. Upon addi ti on
of an el ectron to form the radi cal ani on, [TCBT]
-
, al l of
the orbi tal s i ncrease i n energy, wi th the two hi ghest fi l l ed
sti l l l yi ng fai rl y cl ose i n energy to one another. The
LUMO orbi tal and spi n densi ty of [TCBT]
-
are predi cted
to be l ocal i zed predomi nantl y wi thi n the ri ngs, wi th a
mi ni mal spi n resi di ng on the ni tri l e ni trogen atoms,
Tabl e 1 and Fi gure 10b. The resul ti ng D
2h
symmetry of
the spi n densi ty woul d propose a set of 2 and a set of 4
equi val ent ni trogens wi thi n the ri ngs and another set of
4 equi val ent ni trogens due to the ni tri l es. Whi l e strong
coupl i ng of the spi n to the two sets of ni trogens wi thi n
the ri ngs are expected, weaker coupl i ng to the ni tri l es i s
al so expected, as there i s very l i ttl e spi n densi ty on the
ni tri l es (<0.003 e
-
). Thi s i s consi stent wi th the observed
EPR spl i tti ngs, wi th a set of 2 and a set of 4 equi val ent
ni trogens wi th strong coupl i ng to the ri ng ni trogens. The
broad peaks (0.24 G l i ne wi dth) i n the spectra obtai ned
coul d be due to the concomi tant weak spl i tti ng of the
peaks from the ni tri l e groups, but the sensi ti vi ty of the
i nstrument does not al l ow thi s very weak coupl i ng (<0.1
G) to be resol ved. I n contrast to the spi n densi ty, the
charge resi des on the ni tri l e and i mi de Ns, Fi gure 10c
and Tabl e 1.
Al l three compounds possessi ng [TCBT]
-
have the
same I R wi th absorpti ons at 1530, 1275, 1180, 950, 915,
and 775 cm
-1
, as wel l as a weak
CN
absorpti on at 2242
cm
-1
. Furthermore, the sol uti on (MeCN) UV/vi si bl e
spectra of the three [TCBT]
-
-contai ni ng compounds have
several i denti cal absorpti ons centered at 18 000 cm
-1
(556 nm), Fi gure 11, i n addi ti on to those attri buted to
the cati on. Thi s l ower-energy absorpti on i s assi gned to
the b
2g
2
b
3u
1
f b
2g
1
b
3u
2
(HOMO-SOMO) transi ti on of the
radi cal ani on, as seen i n the MO di agram for [TCBT]
-
,
Fi gure 10a. Thi s absorpti on i s spl i t i nto fi ve di sti ngui sh-
abl e peaks separated by approxi matel y 1430 cm
-1
, whi ch (26) Cook, A. H.; Jones, D. G. J . Chem. Soc. 1941, 278.
FIGURE 9. (a) Cal cul ated mol ecul ar orbi tal di agram for TCT
o
and [TCT]
-
speci es wi th 90%of the charge pl otted at a contour
of 0.01 e
-
, (b) the spi n densi ty of [TCT]
-
showi ng 95% of the
spi n at a contour of 0.005 e
-
, showi ng sets of equi val ent
ni trogens of 2:2:1:1, and (c) the predi cted charge densi ty for
[TCT]
-
speci es, where red and bl ue represent negati ve (-) and
posi ti ve (+) potenti al s, respecti vel y.
SCHEME 2
Del Sesto et al .
3374 J . Org. Chem., Vol. 68, No. 9, 2003
are attri buted to vi brati onal overtones due to phonon
coupl i ng wi th the exci ted state of the radi cal ani on,
si mi l ar to that noted for [TCNE]
-
.
27
The 1430 cm
-1
spl i tti ngs observed wi thi n the 18 000
cm
-1
(556 nm) absorpti on correspond very cl osel y to the
energy of the ground-state
CdN
absorpti on of 1530 cm
-1
.
The 100 cm
-1
decrease i n frequency i s due a decrease
i n the ri ng CN bond l engths i n the exci ted state, as the
p* orbi tal i s a bondi ng orbi tal for some CdN bonds and
anti bondi ng for the other CdN bonds wi thi n the ri ng,
and the popul ati on of the p* woul d both i ncrease and
decrease CdN bonds, resul ti ng i n a symmetri c (D
2h
)
di storti on of the [TCBT]
-
, wi th l i ttl e change i n the ni tri l e
bonds, as seen i n the change bond l engths cal cul ated i n
Tabl e 2.
The radi cal ani on has a hi gher-energy absorpti on at
29 000 cm
-1
(345 nm), whi ch i s attri buted to the b
3u
1
b
1g
o
f b
3u
o
b
1g
1
transi ti on, whi ch i s consi stent wi th the cal cu-
l ati ons, Fi gure 10a. The b
3u
1
b
ag
o
f b
3u
o
a
g
1
transi ti on i s
i nappropri ate for use i n maki ng thi s assi gnment, because
the ani ons a
g
SOMO + 1 orbi tal i s a vi rtual di ffuse
Rydberg orbi tal that i s more appropri ate to the di ani on
than to the ani on.
The magneti c suscepti bi l i ty, , of the sal ts of the
[TCBT]
-
was determi ned between 2 and 300 K. The
room-temperature-effecti ve magneti c moments,
eff
[) (8T)
1/2
] are 1.72, 2.34, and 2.43
B
for [CoCp*
2
]-
[TCBT]
-
, [Cr(mes)
2
]
+
[TCBT]
-
, and [TDAE]
2+
[[TCBT]
-
]
2
,
respecti vel y. The val ues are consi stent wi th one spi n for
the former compound and two spi ns for the l atter two
compounds as expected. The 2.34
B
moment i s reduced
from the expected 2.45
B
due to the presence of an
i mpuri ty, most l i kel y di amagneti c [TCT]
2
2-
. The (T) can
be model ed as typi cal Curi e-Wei ss behavi or, [T -
]
-1
, and [TDAE]
2+
{]TCBT]
-
}
2
and [Cr(mes)
2
]
+
[TCBT]
-
show weak anti ferromagneti c coupl i ng, wi th ) -3.6
and -0.2 K, respecti vel y. I n contrast, [CoCp*
2
][TCBT]
-
exhi bi ts weak ferromagneti c coupl i ng, wi th ) +3.8 K.
(27) (a) Di xon, D. A.; Mi l l er, J. S. J . Am. Chem. Soc. 1987, 109, 3656.
(b) Mi l l er, J. S.; Krusi c, P. J.; Di xon, D. A.; Rei ff, W. M.; Zhang, J. H.;
Anderson, E. C.; Epstei n, E. J. J . Am. Chem. Soc. 1986, 108, 4459. (c)
Hal l er, I .; Kaufman, F. B. J . Am. Chem. Soc. 1976, 98, 1464.
FIGURE 10. (a) Cal cul ated mol ecul ar orbi tal di agram for
TCBT
o
and [TCBT]
-
speci es wi th 90% of the charge pl otted
at a contour of 0.017 e
-
, (b) the spi n densi ty of [TCBT]
-
showi ng 90%of the spi n at a contour of 0.002 e
-
, showi ng sets
of equi val ent ni trogens of 2:4:4, and (c) the predi cted charge
densi ty for [TCBT]
-
speci es, where red and bl ue represent
negati ve (-) and posi ti ve (+) potenti al s, respecti vel y.
FIGURE 11. Mol ar exti ncti ons of (a) [Cr(mes)2]
+
[TCBT]
-
(dashed l i ne), (b) [CoCp*2]
+
[TCBT]
-
(sol i d l i ne), (c) [TDAE]
2+
-
{[TCBT]
-
}2 (dotted line), and (d) {[Cr(mes)2]
+
}2[TCT]2
2-
(dashed
sol i d l i ne) as sol uti ons i n MeCN. I nset shows the vi brati onal
coupl i ng of [TCBT]
-
.
TABLE 2. Optimized Geometries of Neutral and
Radical Anion of [TCBT]
n
(n ) 0, 1-) fromCalculations
at the Density Functional B3LYP/6-31++G(2d,2p) Level
a
bond
bond l ength ()
n ) 0
bond l ength ()
n ) 1- % change
a 1.506 1.406 -6.6%
b 1.315 1.363 +3.7%
c 1.314 1.295 -1.4%
d 1.316 1.335 +1.4%
e 1.455 1.462 +0.5%
f 1.133 1.136 +0.3%
a
Resul ti ng geometri es for both speci es have D2h symmetry.
Formation of Novel 4,4,6,6-Tetracyano-2,2-bitriazine
J . Org. Chem, Vol. 68, No. 9, 2003 3375
The I R spectrum of [TDAE]
2+
{[TCBT]
-
}
2
i s i denti cal
to the thermol ysi s product i sol ated from TGA/MS experi -
ments of the [TDAE]
2+
[TCT]
2
2-
, i n whi ch the sampl e was
heated unti l the l oss of [CN
and CN
-
occurs, whi ch resul ts i n the formati on of
[TCBT]
-
, most likely through the intermediate [C
11
N
11
]
2-
,
Scheme 3. The fi nal product of thermol ysi s woul d there-
fore be the two sal ts [TDAE]
2+
{[TCBT]
-
}
2
and [TDAE]
2+
-
[CN
-
]
2
. [TCBT]
-
i s responsi bl e for the 2N:4N EPR si gnal
that i s observed i n both the di rect reducti on of TCTwi th
TDAE, Na, or K and i n the recrystal l i zed thermol ysi s
product of [TCT]
2
2-
. As the decomposi ti on product of
[TCT]
2
2-
i nvol ves the l oss of mass, i t i s l i kel y that [TCT]
-
i s nei ther present nor the speci es responsi bl e for the
observed EPR spectra.
Ti me-resol ved, stopped-fl ow I R studi es were performed
on the reacti on mi xture, wi th the fi rst spectra begi nni ng
at 50 ms fol l owi ng mi xi ng, and recorded approxi matel y
every 15 s over the course of 11 mi n, Fi gure 13a. The
fi rst scan shows the presence of a l arge peak at 1670
cm
-1
, characteri sti c of the [TDAE]
2+
,
28
i ndi cati ng that the
el ectron transfer from TDAE to TCT occurs i n l ess than
20 ms, the detecti on l i mi t of the system. Addi ti onal l y,
peaks characteri sti c of both [TCT]
2
2-
and [TCBT]
-
are
al so present i mmedi atel y, suggesti ng that di meri zati on
and the i ni ti ati on of decomposi ti on to [TCBT]
-
al so
requi re <20 ms. Thi s suggests that the i ntermedi ate i n
the transformati on has characteri sti cs of both [TCT]
2
2-
and [TCBT]
-
, whi ch coul d possi bl y be [C
11
N
11
]
2-
. Thi s
i s al so consi stent wi th the el ectrochemi cal behavi or of
TCT bei ng i rreversi bl e at even the greatest scan rates
studi ed (2000 mV/s). Moni tori ng of the peaks character-
i sti c of [TCT]
2
2-
, at 1590 and 1330 cm
-1
, as a functi on of
ti me shows the gradual decrease i n i ntensi ty, al ong wi th
the si mul taneous i ncrease of i ntensi ty of the character-
i sti c peaks of [TCBT]
-
at 1530 and 950 cm
-1
, Fi gure 13b.
Hence, the decomposi ti on of [TCT]
2
2-
to [TCBT]
-
occurs
i n a mul ti step process, as seen i n the change i n sl opes i n
Fi gure 13b duri ng the experi ment. However, the ki neti cs
i s not wel l understood and sti l l under i nvesti gati on.
Nonethel ess, i t i s apparent that the reducti on of TCT
resul ts i n a very rapi d di meri zati on fol l owed by a sl ower
decomposi ti on to form the new radi cal ani on [TCBT]
-
.
[Cr(mes)
2
]
+
[TCBT]
-
and [CoCp*
2
]
+
[TCBT]
-
di spl ay
the same EPR spl i tti ngs, as wel l as an I R si mi l ar pattern
to that of [TDAE]
2+
{[TCBT]
-
}
2
. However, pure sampl es
of [Cr(mes)
2
]
+
[TCBT]
-
coul d not be obtai ned, as i t
cocrystal l i zes from sol uti on wi th the respecti ve sal t of
[TCT]
2
2-
. Thermol ysi s experi ments, si mi l ar to that of the
[TDAE]
2+
sal t decomposes [TCT]
2
2-
formi ng sal ts of
[TCBT]
-
, coul d not be carri ed out on the [Cr(mes)
2
]
+
-
[TCBT]
-
and [CoCp*
2
]
+
[TCBT]
-
due to the decomposi -
ti on of the cati ons upon heati ng to temperatures suf-
fi ci ent to effect the l oss of [CN]
x
from [TCT]
2
2-
.
Mechanistic Considerations. Several feasi bl e mech-
ani sms for the formati on of TCBTand [TCBT]
-
from the
reducti on of TCT are shown i n Scheme 3. The most
feasi bl e of these i s Scheme 3a, whi ch goes through the
di mer di ani on i ntermedi ate [TCT]
2
2-
, whi ch has been
i sol ated from the di rect reducti on of TCT and, as di s-
cussed, decomposes to form [TCBT]
-
on the basi s of
thermol ysi s and spectroscopi c data. When heated or
al l owed to stand for extended peri ods of ti me (1 day or
l onger), [TCT]
2
2-
can l ose CN
2MeCN: CCDC-163649.
Reduction of TCT with CoCp*2 and TDAE in MeCN.
A sol uti on of the reduci ng agent (0.30 mmol ) i n 10 mL of MeCN
was added to TCT (47 mg, 0.30 mmol ) i n 5 mL of MeCN
resul ti ng i n a purpl e sol uti on. The sol vent was al l owed to
sl owl y evaporate to hal f the ori gi nal vol ume and then cool ed
to 0 C, al l owi ng a purpl e preci pi tate to form that was
subsequentl y fi l tered and col l ected. Crystal s sui tabl e for si ngl e-
crystal X-ray di ffracti on studi es coul d not be i sol ated.
[CoCp*
2]
+
[TCBT]
-
. Yi el d: 6 mg (4%). I R, , cm
-1
:
([TCBT]
-
) 2243 vw, 1530 vs, 1275 s, 1179 m, 951 vs, 910 m,
775 m; ([CoCp*2]
+
) 1460 m, 1375 s, 1017 s. EPR: g[TCBT]
)
2.0032,
2
A14N ) 3.347 G,
4
A14N ) 0.764 G (THF, MeCN). Anal .
(29) Dunn, B. C.; Marda, J. R.; Eyri ng, E. M. Appl. Spectrosc. 2002,
55, 751.
(30) Brandon, E. J.; Ri ttenberg, D. K.; Ari f, A. M.; Mi l l er, J. S. I norg.
Chem. 1998, 37, 3376.
(31) Al tschul er, S. A.; Kozyrev, B. M. I n Electron Paramagnetic
Resonance; Pool e, C. P., Jr., Ed.; Academi c Press: New York, 1964; p
298.
(32) (a) Shel dri ck, G. M. SHELX97-2: Programfor Crystal Structure
Analysis(Release97-2); Uni versi tat of Gotti ngen: Gotti ngen, Germany,
1998. (b) Farrugi a, L. J. J . Appl. Crystallogr. 1997, 30, 565.
(33) Hi l l , M.; Mahon, M. F.; Mol l oy, K. C. J . Chem. Soc., Dalton
Trans. 1996, 1857.
(34) Beck, G.; U.S. Patent 5,086,172, 1992.
Del Sesto et al .
3378 J . Org. Chem., Vol. 68, No. 9, 2003
Cal cd for C30H30N10Co: C, 61.12; H, 5.13; N, 23.76. Found: C,
60.96; H, 5.01; N, 23.79. Crystal s sui tabl e for si ngl e-crystal
X-ray di ffracti on studi es coul d not be i sol ated.
[TDAE]
2+
{[TCBT]
-
]2. Yi el d: 670 mg (37%). I R, , cm
-1
:
([TCBT]
-
) 2242 vw, 1528 vs, 1275 s, 1179 m, 950 vs, 908 m,
772 m; ([TDAE]
2+
) 1670 s, 1659 s, 1420 s, 1042 w, 865 w, 680
w.
26
EPR: g[TCBT]
) 2.0039,
2
A14N ) 3.347 G,
4
A14N ) 0.765 G
(THF, MeCN). Anal . Cal cd for C30H24N24: C, 50.01; H, 3.33;
N, 46.70. Found: C, 49.89; H, 3.55; N, 46.58.
Reducti on of the vol ume of the fi l trate fol l owed by l ayeri ng
of the fi l trate wi th hexanes resul ted i n a bei ge-col ored pre-
ci pi tate, determi ned to be sal ts of [TCT]2
2-
.
{[CoCp*2]
+
}2[TCT]2
2-
. Yi el d: 10 mg (7%). I R, , cm
-1
:
([TCT]2
2-
) 2237 vw, 1587 s, 1326 vs, 914 w; ([CoCp*2]
+
) 1471
m, 1382 m, 1024 m. Anal . Cal cd for Co2C52H60N12: C, 64.30;
H, 6.23; N, 17.32. Found: C, 64.14; H, 6.28; N, 17.04.
[TDAE]
2+
[TCT]2
2-
. Yi el d: 210 mg (21%). I R, , cm
-1
:
([TCT]2
2-
) 2237 vw, 1592 s, 1328 vs, 906 w; ([TDAE]
2+
) 1668
s, 1655 s, 1402 m, 1047 w, 863 w. Anal . Cal cd for C22H24N16:
C, 51.55; H, 4.72; N, 43.73. Found: C, 51.38; H, 4.67; N, 43.84.
[TMPD][TCBT]. Si mi l ar reacti on condi ti ons were used for
the reducti on of TCT wi th CoCp*2 and TDAE i n MeCN i n a
1:1 stoi chi ometri c rati o. The resul ti ng sol uti on was l eft for 2
weeks and the sol vent al l owed to sl owl y evaporate, resul ti ng
i n deep bl ue-col ored pri smati c crystal s. Yi el d: 4 mg; 2.1%. I R,
, cm
-1
: 2957 m, 2891 m, 2851 m, 2806 m, 2269 vw, 2254 w,
2241 m, 1520 s, 1498 s, 1446 m, 1406 m, 1343 s, 1322 s, 1248
m, 1219 m, 1176 m, 1121 w, 1055 m, 977 w, 949 m, 929 m,
824 m, 805 s, 765 m, 681 w, 658 m, 538 w, 515 w. Crystal
data for [TMPD][TCBT]: C
10H8N6, M ) 212.22, monocl i ni c,
space group P21/a, a ) 7.3864(3) , b ) 15.0865(3) , c )
9.4932(4) , ) 95.2112(14), V ) 1053.50(6)
3
, Z ) 4, Fcal cd
) 1.338 Mg/m
3
, absorpti on coeffi ci ent ) 0.090 mm
-1
, F (000)
) 440, refl ecti ons col l ected ) 4380, i ndependent refl ecti ons )
2381 [R(i nt) ) 0.0237], GOF ) 1.050, R ) 0.0406, wR2 )
0.0990. CCDC-178429.
Acknowledgment. The authors grateful l y acknowl -
edge the support from the NSF (Grant CHE9320478)
and the DOE (Grant DE FG 03-93ER45504). R.E.D.S
and J.S.M appreci ate the el ectrochemi cal assi stance
from Kyl e Grant, John Watki ns, and Henry Whi te.
R.E.D.S. al so thanks the Uni versi ty of Utah Graduate
School for a research fel l owshi p. J.J.N. thanks Mi ni s-
teri o de Ci enci a y Tecnol ogi a and CI RI T(Project PB98-
1166-C02-02 and 2001-SGR-00044). We thank Mi chael
A. Stecker, MD, for permi ssi on to use hi s photograph
for the front cover i l l ustrati on.
Supporting Information Available: X-ray CI F fi l es
for [TTF][TCT], [HTMPD]
+
[DCTO]
-
, {[Cr(mes)2]
+
}2[TCT]2
2-