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Lithium 7bH-Indeno [1 2 3-jk] fluorenide an Organolithium Compound Having a УSandwichФ Structure.

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< 5 % of its cis isomer (NMR spectrum) as a yellow oil which
gradually solidified. The hexafluorophosphate (yield 86 %)
forms colorless crystals (from acetone/ether) which decompose
between 79 and 80°C.
Received: May II,1977 [Z 727h IE]
German version: Angew. Chem. 89,489 11977)
CAS Registry numbers:
(1 u ) , 62882-16-0: ( I b ) , 62882-18-2; (2), 661-36-9: ( 3 ~ ) 62882-20-6:
.
(3h).
62882-22-8; ( 3 h ) , hexafluorophosphate, 62882-23-9; ( 4 1 , 62882-25-1 ; (51,
62882-27-3: (6a), 81 1-51-8; ( 6 b ) , 930-69-8; ( 6 c ) , 26628-22-8; t r u n s - ( 7 u ) .
56554-09-7; cis-( 7 u ) ,56554-01-9; trans-( 7 b ) . 62882-29-5;cic-( 7 h 62882-3 1-9:
trans-( 7b), 2,4,6-trinitrohenzenesulfonate,62882-32-0; cis-( 7 b ) . 2.4.6-trinitrobenzenesulfonate, 62882-33-1 : iruiis-( 7c), 62882-35-3; cis-( 7 c ) , 62882-37-5:
trails-( 7 c). hexafluorophosphate. 62882-38-6; cis-( 7 c ) . hexafluorophosphate,
62882-39-7
H . Braun. A . Amanri, M . R i c h t w , Angew. Chem. 89. 488 (1977); Angew.
Chem. Int. Ed. Engl. 16, 471 (1977).
F . E . Herkes, H . E . Simniorrs, J . Org. Chem. 38, 2845 (1973).
H . Bruun, A. am an^, unpublished.
a) H . Braun, A . Amann, Angew. Chem. 87. 773 (1975); Angew. Chem.
Int. Ed. Engl. 14, 755 (1975): h) H . Brnirrt, A . Amiinn, Angew. Chem.
87, 775 (1975); Angew. Chem. Int. Ed. Engl. 14, 756 (1975).
For a summary see: a ) B. M . 77a.osr. L. S . M e h i n in A. 7: Blomquisf.
H . H . Wassrrmun: Sulfur Ylides. Academic Press, New York 1975: b)
J . P. Marino in A Senning: Topics in Sulfur Chemistry. Thieme. Stuttgart
1976.
G. L‘abbd, Angew. Chem. 87, 831 (1975): Angew. Chem. Int. Ed. Engl
14. 775 (1975) and references cited therein.
“1
121
PI
[41
151
[61
Lithium 7bH-Indeno[ 1,2,3-jk]fluorenide, an Organolithium Compound Having a “Sandwich”
StructureC**J
By Dieter Bladauski, Huns Dietrich, Hans-Jiirgen Hecht, and
Dieter Rewicki“]
Crystal structure studies have shown that alkyllithium compounds[’] exist in systems associated via electron-deficient
bonds and containing Li atoms of coordination number 2 4 .
Amine121 or ether c ~ m p l e x e sof~ ~organolithium
~
derivatives
with resonance-stabilized carbanions, on the other hand, are
composed of typical intimate ion pairs with ionic and covalent
bonding contributions, the lithium lying in a trigonal environment made up of the carbanion rc-base and the N and 0
basic centers.
We have now accomplished the first isolation of the lithium
salt of a hydrocarbon exhibiting extreme charge delocalization
in crystalline form, without any need for hetero atom bases
as crystallization-promoting or stabilizing ligands. The rubyred compound lithium 7bH-indeno[ 1,2,3-jk]fluorenide ( I )
slowly crystallizes on interdiffusion of dilute benzene solutions
of 7bH-indeno[1,2,3-jk]fluorene and butyllithium and contains one half molecule of benzene per formula unit. X-Ray
structure analy~is[~l
performed at - 160°C revealed the structure shown in Figure 1.
The crystal lattice consists of isolated units containing two
carbanions and two lithium ions each. The essentially planar
[“I Uip1.-Chem. D. Bladauski,
Dr. H.-J. Hecht, Prof. Dr. D. Rewicki
lnstitut fur Organische Chemie der Freien Universitat
Thielallee 63-67, D-1000 Berlin 33 (Germany)
[‘I
Prof. Dr. H. Dietrich
Fritz-Haher-lnstitut der Max-Planck-Gesellschaft
Faradayweg 4--6, D-I000 Berlin 33 (Germany)
[‘I To whom correspondence should be addressed.
[‘*I Strained Alkyl-Aromatic Systems, Part 4. This work was supported
by the Fonds der Chemischen 1ndustrie.-Part 3: P. Luyer, Ch. Tuchscherer.
M . Crossr.. D. R n i i r k i . Chem. Ber. 109, 2596 (1976).
474
Fig. I . Structure of the lilhium salt ( 1 ) : Y! projection of a section of
the unit cell. The benzene molecules incorporaied in the lattice are omitted
for the sake of clarity.
c a r b a n i o n ~ [(mean
~]
deviation of the plane through the molecule: 0.04A) are mutually parallel and separated by 3.9A; the
central six-membered rings are anti orientated. The lithium
ions are coordinated in sandwich fashion with a pair of external
six-membered rings. The distance between the lithium ion
situated almost concentrically above the :ix-membered rings
and the two rings is uniformly 1.93(4)A, and the distance
to the C atoms of the six-membered ring varies between
2.343(4) and 2.453(6)A, having a mean value of 2.41(4)A.
The benzene incorporated into the lattice lies outside the
coordination sphere of the lithium.
On comparison with the known structures of organolithium
compounds, structure ( I ) is seen to have the following distinctive features: t ) This i s the first case of lithium being present
in linear coordination with two hexahapro-bonded six-membered ring ligands in the form of a bis(arene)mebal type
complex. The Li-C distances, which are only 0.25A longer
on average than in alkyllithium compounds and correspond
approximately to those in indenyllithium[21, as well as the
short Lis-ring
distance[‘’ show the “sandwich’ structure
to be a consequence of bonding interactions and not merely
a packing phenomenon.-2) In contrast to the lithium compounds with resonance-stabilized carbanions examined so
far[’] no preferred orientation of the lithium atoms on the
C center of highest charge density can be detected in the
case of (1). On the basis of charge densities at the carbanion
calculated by MO methods, the Lie should be preferentially
located over the five-membered rings. The observed position
of the lithium can be interpreted by assuming that, given
pronounced charge delocalization within the carbanions and
in the absence of hetero atom bases, the structure of the
lithium compound is largely determined by covalent interaction between the unoccupied atomic orbitals of lithium and
the occupied molecular orbitals of the carbanion and to a
lesser degree by electrostatic interactions.
Received: May 12, 1977 [Z 733 IE]
Grrman version: hngew. Chem. 89,490 (1977)
CAS Registry numbers:
( 1 ), 50888-67-0
H . Dietrich, Acta Cryslallogr. 16, 681 (1963J; E . Weiss, E . A . C . L u c k m ,
.I. Organomet. Chem. 2, 197 (1964); R . Zerger. W Rhrne, G. Srucky,
J . Am. Chem. Soc. 96, 6048 (1974).
W E . Rhine, G. D . Stuckv, J. Am. Chem. Soc. 97,737 (1975); and references
cited therein.
D . Bluduuski, D. Rewicki, Chem. Ber., in press; H . Dietrich, D . Rebvicki,
unpublished work.
Monoclinic space group
P2,:a;
rr=1114.?(7), b=1482.9(6),
c=1008.1(4)pm,
i 17.99(5)”: Z = 4 . 8818 independent data recorded
on an automatic single-crystal diffractometer (Siemens-AED) up t o
o=
Angen. Chem. l n t .
E d . Eiigl. 16 (1977) No. 7
8=40.0" with Zr-filtered M o K J radiation and corrected in the usual
way. Refinement gave R =0.089 after convergence of all parameters.
[S] Coinparison of the ring strain of the carbanion with that of 7bHindcno[l.2,3-jk]fluorene is considered elsewhere. See also H . Dietrich,
D. Bluduiiski. M . Grosar. K . Rorh, D Rewicki, Chem. Ber. 108. 1807
(1975).
[6] Having a value of 1.93A this distance is considerably smaller than
the sum of the van der Waals radius of an aromatic ring (cu. 1.7A)
and the ionic radius of LiB (0.68A). The shortening is comparable
with that in bis(i1-cyc1opentadienyl)beryllium and -magnesium [ R .
Schiierder. E. 0.Fischer, Naturwissenschaften 50, 349 (1963): Ch. W i n g ,
7.Lre, K. Chuo. S. Lee. Acta Crystallogr. B 2 8 , 1662 (1972)J.
5-Methox ysemibullvalene
By Reinhard W. Hqffmaiin, Norbert Hauel, and Fritz Frickelrl
Dedicated to Professor Burckhardt Hererich on the occasion
of his 90th birthday
The equilibrium between the valence isomers of semibullvalene is influenced by substituents in the 1,S-positions['! In
all the derivatives (alkyl, aryl, cyano) so far obtained, the
1-isomer predominates. However, a n-donor substituent is
predicted to favor the 5-position[21. We describe the synthesis
of 5-methoxysemibullvalene ( 6 1 , the first donor-substituted
semibullvalene.
planar to the halogen thwarted attempted E,-eliminations
(KOtBu, DMSO, S O T ) . Reaction of ( 2 a ) with an excess
of sodium methanethiolate (DMF, 24 h, 25°C) gave 80 of
crude ( 3 ) , which has been alkylated by an excess of methyl
iodide to ( 4 ) (neat, 24h, 25"C, 71 %) (cf. Table 1).
Elimination of the axially positioned sulfonium group in
( 4 ) (KOtBu/DMSO, 1 h, 25°C) proceeded smoothly to give
> 70 % of a methoxysemibullvalene[s~(b.p. 19°C/0.01 torr)[61.
The structure (6) rather than ( 5 ) is deduced from the 'HNMR-spectrum (CC14): t=4.5 (d, J=4.6Hz, 4-H, 6-H); 5.0
(dd, J 1 = 4 . 6 H z , J z = l . S H ~ ,3-H, 7-H); 6.7 (d, J = 5 H z , 2-H,
8-H); 6.9 (s, OCH3); 7.1 (t, J = 5 H z , I-H). "C-NMR
(CDCI~/TMS):6=51.43,d;51.60,d;52.41,q;
100.26,s; 120.26,
d ; 124.43, d. The I3C-NMR spectrum (CF2C12)exhibited a
broadening and a shift of the C-2, C-8 and the C-4, C-6
signals between -30 and - 130°C. This can be interpreted
by assuming the presence of less than 10% of ( 5 ) in the
equilibrium. Hence the prediction['] of (6) being favored in
the equilibrium ( 5 ) * ( 6 ) is substantiated.
x,
Received: May 2. 1977:
supplemented: May 16, 1977 [Z 735 IE]
German version: Angew. Chem. 89. 491 (19771
CAS Registry numbers:
( I ) . 14224-84-1: ( 2 0 ) , 62962-12-3: ( 2 b ) , 62962-13-4; (Zc), 62962-14-5:
(3), 62962-15-6: ( 4 ) , 62962-16-7: ( 5 ) , 62962-17-8: (6), 62962-18-9
Cf. D. R. Jumes, G . H . Birizberg, L. A . Puyuerte. J. Am. Chem. Soc.
96, 7465 (1974): L. A . Puyuerre, M! E. Volz, ibid. 98, 2910 (1976).
M. J . S. Dewar, W W Schoeller, J. Am. Chem. SOC. 93. 1481 (1971):
R . Hoffmuiin, W D. Stohrer, J. Am. Chem. Soc. 93, 6941 (1971): M .
J . S . Dewor, D. H . Lo, J. Am. Chem. Soc. 93, 7201 (1971).
Ct'. R . Bicker, H K r s s k r , A . Sfc,iyel, Chem. Ber. 107, 3053 (1974): and
references quoted therein.
This reaction has been independently discovered by M . A . Rorrisrr.
University of Florida, personal communication, July 1975.
The substance yielded a correct CH-analysis.
Reaction of ( 2 0 ) with CbHsSeNa and m-chloroperbenzoic acid-induced
oxidative elimination also led to the formation of ( 6 ) .
14 i
(a). X
=
(5)
(6J
Synthesis and Chemistry of Alkylidenediaziridines
I; ( h ) , X = Br; (c), X = C1
(from ethanol/ether); 'H-NMR (CCL,): r=7.617.XI (m, 2 H ) : 7.40- 7.59 (m. ZH): 7.02 (s, 3 H ) : 7.00 (s, 3H): 6.59 (s, 3H):
6.15- 6.35 (m. ZH): 4.3 (dd, J 1 = 5 H z . J 2 = 3 H z . I H ) : 4.0X (dd, J , = 5 H z ,
J2-2Hz. 1 H).
By Gerrit L'abbg, Chih-Chou Yu, and Suzanne Toppet[*]
Aziridinimines have been reported by Quast['], but their
valence isomers, alkylidenediaziridines, were hitherto
unknown. We report here on their synthesis, thermal isomerization and behavior in cycloaddition reactions.
When ketenimines (1 a ) to ( 1 c) are treated with methanesulfonyl azide at room temperature, evolution of nitrogen
occurs and, as indicated by the 'H-NMR spectra (CDC13) of
the crude reaction mixtures, almost single products are
obtained. These were isolated by careful crystallization from
appropriate solvents (see Table 1) and identified as alkylidenediaziridines ( 2 u ) to (2c)''l on the basis of:
molecular weight determination (osmometric);
'H-NMR (non-equivalence of the alkylidene methyl groups
with signals at 6 = 1.7 and 1.8);
3C-NMR spectra [olefinic carbon absorptions at 8 = 98 (C-0)
and 162 (C-a), A6=64, which is characteristic for enediamine~[~]].
The IR spectra (KBr) manifested absorptions at 1630 to
1650 cni- which are unusually low for stretching vibrations
of C=C bonds attached to three-membered ringd4"1; however,
this is not without
['I
[*] Prof. Dr. G. Labbe, Chih-Chou Yu, and Dr. Suzanne Toppet
Reaction of (1
with an equimolar amount of AIX3 (ether,
0°C) led to (2) in 70 to 78 'i:
(C2Hs)2A1C1in refluxing
ether gave 90% of ( 2 c j . The enrio-position of the halogen
in (2) follows from the coupling pattern of the CHX proton
in the 'H-NMR spectra. The absence of hydrogen anti-periTable I . Physical data of the new compounds
( 2 1 1 ) [ S ] . b.p. 44-46"C/10-4
torr: 'H-NMR (CCI,): r=7.38-8.53
(m,
4 H ) ; 6.68 (s. 3 H ) : 6.59 (broad d. J = 5 Hz, I H): 5.58-5.95 (ddd, J , = I 1 Hz,
J2=7Hz, J 3 = 5 H z , IH);4.29(m.2H).
( 2 b ) [S], h.p. 28--31"C,'10~4 torr: 'H-NMR (CCI,): r=7.45 4 . 6 0 (m.
4H). 6.68 /s, 3H): 6.59 (broad d, J = 5 H z . I H ) ; 5.50-5.81 (ddd, J I = l O H z ,
J 2= 7 Hz. Ji = 5 HI. 1 H): 4.26 (m, 2 H).
f ? c ) [S], b.p X6-89"C,'11 torr: 'H-NMR (CDCI,): r=7.46- X.SX(m, 4 H ) ;
6.66 (s. 3H): 6.54 (broad d, J = S H z . IH): 5.44 -5.68 (ddd, J , = I 0 Hz,
J~=~.SH~.JJ=S.SH
I HL) .: 4 . 2 ? ( m . Z H ) .
( 3 1 . 'H-NMR ICCI,): ~ = 8 . 1 5 (m. 2 H ) : 7.X--X.O (m, I H ) with s ( 3 H ) at
7.96: 7.18 lm, I H): 6.8X (m, I H): 6.64 (5. 3H): 4.35- 4.62 (m, 2H).
( 4 ) [SJ. m.p. 136-137°C
Prof. Dr. R. W. Hoffmann. Dip1.-Chem. N. Hauel, Dr. F. Frickel
Fachbereich Chcmie der Uni\'ersitat
Lahnberge. D-3550 Marburg (Germany)
Aiiynv. C h i . lnr. Ed. E i i g l . 16 ( 1 9 7 7 )
No. 7
',
Department of Chemistry. University of Leuven
Celestijnenlaan 200 F, 8-3030 Heverlee (Belgium)
415
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structure, compounds, organolithiums, indene, fluorenide, lithium, 7bh, уsandwichф
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