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X-Ray Structure Analysis of the Li2-Compound of Bis(trimethylsilyl)metnyl Phenyl Sulfone; Structural Units of an -Sulfonyl- and a Complex-Stabilized ortho-Sulfonyl-УCarbanionФ.

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Thermal as well as photochemical decomposition of 6 in
I ,2-dichloroethylene, styrene or fumarates (as solvent)
leads exclusively to the dimers 19 and 20, and even with
N-phenylmaleimide the dimerization can only be suppressed with excess of the reagent. Since the ratio of trapping products to dimers is not changed in the sensitized
photolysis of 6, the trapping products most likely are
formed from the singlet-species present in equilibrium
with the triplet species. If one assumes that dimerization
and trapping reaction are diffusion controlled, the singlet
state must lie at least 4-5 kcal mol-’ above that of the triplet state; if the trapping reaction were slower the energy
difference would be even greater.
1.1 d U L l
Za: R = H
l a . R = R’: H
lb: R = H, R‘= D
1 C : R: D, R ’ =
Id: R = R’z D
Zb: R = D
Li--- - - -0
Received: August 7, 1987 [Z 2393 IE]
German version: Angew. Chem. 99 (1987) 1330
[ I ] P. Du, W. T. Borden, J. Am. Chem. SOC.109 (1987) 930.
[2] P. Dowd, W. Chang, Y. H. Paik, J . Am. Chem. SOC.108 (1986) 7416.
I31 IR(CC1,): v(CH2)=898 cm-’; ‘H-NMR(400 MHz,CDCI,): S=5.40 (s,
A 1,o-dilithio compound of this kind was first characterized chemically and NMR spectroscopically by Gais et al.
2H),5.30(s,2H),5.15(~,2H),0.95(s,3H),0.85(~,3H);UV/VIS(penin 1985.@’
tane): 1,,,=224 nm (&=3500), 354 (80).
The remarkable formation of the crystalline 1,o-dianion
141 IR (CCI,): v(C=C=C)= 1960 c m - ’ ; ’H-NMR (80 MHz, CDCI,): 6 =
5.3-5.1 (dd, 2H), 4.8 (s, 2H), 4.7 (8, 2H), 1.2 (s, 6H).
[3.(OEt2),], upon reaction of l a with 1.1 molar equiva151 G. Zweifel, J . Org. Chem. 47 (1982) 3364.
lents of nBuLi in etherr8’is not fully understood at the mo[6] T. Flood, P. E. Peterson, J . Urg. Chem. 45 (1980) 5006.
ment.[6’71It can be shown that the sulfones l a and l b are
[7] I R (CCI,): ~ = 3 0 3 0 ,2980, 2920, 1610, 1500, 1460, 1340, 1285, 1090,780
first completely deprotonated to the dissolved monoanion
c m - ’ ; ‘H-NMR (60 MHz, C,D,): 6=5.6 (s, 2H), 2.8 (s, 4H), 1.3 (s,
6 H).
2aJ9]but just how Za transforms into 3 and [3.(OEtZ),], is
[81 J. P. Collman, R. G. Finke, J. N. Cawse, J. 1. Brauman, I Am. Chem.
unclear. The dianion character of 13.(OEt2)J2 was
Sor 100 (1978) 4766.
confirmed by deuteriation to Id; its structure is repro[91 E. Negishi, A. 0. King, W. L. Klima, J . Org. Chem. 45 (1980) 2526.
duced in Figure 1.
[lo] ‘H-NMR (400 MHz, CDCI3): 6=4.86 (s, 2H), 4.56 (s, ZH), 2.45 (s, 2H),
1.10(s,3H),0.98 (s,3H).
[ I I] Radiation source: Osram HBO (200W) Hg high-pressure lamp with
monochromator (halfwidth 10 nm) (Bausch and Lomb); cooling equipment: Displex Closed Cycle Refrigeration System 202 (Air Products).
[I21 JR: out-of-plane CH vibration of 2,3-dimethylene-I,4-~yclohexanediyl:
770 cm - ’ [ 151.
1131 lOOOW Hg/Xe high-pressure lamp (Hanovia: 9776-1); uranium glass filter (Schott: UG 5 ) ; monochromator (Yvon Jobin: HlO-UV).
[I41 G. L. Closs, Adu. Magn. Reson. 7 (1974) 157.
[I51 W. R. Roth, M. Biermann, G. Erker, K. Jelich, W. Gerhartz, H. Corner,
Chem. Ber. 113 (1980) 586.
X-Ray Structure Analysis of the Liz-Compound of
Bis(trimethylsi1yl)methyl Phenyl Sulfone;
Structural Units of an a-Sulfonyl- and a
Complex-Stabilized ortho-Sulfonyl-“Carbanion”**
By Werner Hollstein, Klaus Harms, Michael Marsch, and
Cernot Boche*
Dedicated to Professor Ulrich Schollkopf on the occasion
of his 60th birthday
Regio- and stereo-control by complexation in reactions
with organolithium compounds (directed lithiation) not
only led to a “new arene chemistry”[’l (ortho-lithiation),
but also to the selective preparation of other lithium compounds (complex-induced proximity effects).l2I Herein we
report on the lithiation of bis(trimethylsilyl)methyl phenyl
sulfone l a , which furnishes 1,o-dilithiobis(trimethy1si1yl)methyl phenyl sulfone 3. Compound 3 crystallizes as
the dimer [ 3 .(OEt2)2]2,which contains the structural units
of an a-sulfonyl “ ~ a r b a n i o n ” ~as~well
as those of a n ortho“carbanion” complex-stabilized by the sulfonyl g r o ~ p . [ ~ . ~
Prof. Dr. G . Boche, DipLChem. W. Hollstein,
Dr. K. Harms, M. Marsch
Fachbereich Chemie der Universitat
Hans-Meerwein-Strasse, D-3550 Marburg (FRG)
This work was supported by the Deutsche Forschungsgemeinschaft
(SFB 260) and the Fonds der Chemischen Industrie.
Angew. Chem. I n [ . Ed. Engl. 26 (1987) No. I2
Fig. I. Crystal structure of [ 3 .(OEt2)2]2.The atomic radii are arbitrary. For
clarity, all H atoms, the CH, groups of the trimethylsilyl substituents and the
C H K H Zgroups of the ether molecules are omitted. One CH, position of a
diethyl ether ligand is disordered. [3.(OEt,)J2 has an inversion center; symmetry-dependent atoms are primed. Space group P2,/c, a = 11.195(3),
b=21.374(5), c = 12.619(3) A,P= I12.66(3)’, Z = 4 (referred to the monomer).
Measurements on an Enraf-Nonius CAD4 four-circle diffractometer with
graphite monochromated CuK, radiation at 210 K. 4328 measured reflections
(264-100’); after Lp correction and averaging there remained 2061 observed
reflections with Fo> 3a(F0), which were used for the calculations. Solution
by direct methods, refinement according to the least-squares method to
R = 0.048, non-hydrogen atoms anisotropic, hydrogen atoms isotropic
[B(H)= l.3Beqa(C)] at calculated positions with a riding model. Some important bond lengths [pm] and angles [“I: CI-S 180.1(5), C7-S 163.7(5), S - 0
149.4(3), C7-Si 183.9(4), C6-Li2 215.8(9), C6-Lil’ 217.8(9), Li2-01 204.8(8),
~Li2-02’ 199.3(8), Li2-04 195.0(8), Lil-01 193.8(8), Lil-02‘ 214.2(8), Lil-03
196.4(8); 01-S-02 109.6(2), Li2-C6-Lil‘ 83.3(3); torsion angles: OI-S-CI-C6
-47.8(4), 02-S-CI-C6 65.4(4), OI-S-C7-Sil - 50.8(4), 02-S-C7-Si2 13.3(4),
CI-S-C7-Sil 66.6(4), CI-S-C7-Si2 - 103.1(3), C7-S-CI-C6 - 171.8(4), S-CIC6-Li2 37.8(5), S-CI-C6-Lil‘ -47.1(4).-Further details of the crystal structure investigation are available on request from the Fachinforrnationszentrum Energie, Physik, Mathematik GmbH, D-7514 Eggenstein-Leopoldshafen 2 (FRG), on quoting the depository number CSD-52656, the names of
the authors, and the journal citation.
0 VCH Verlagsgesellschaft mbH. 0.6940 Weinheim. 1987
0570-0833/87/1212-I287$ 02.50/0
Coupling to the dimer takes place via two Li-0-Li-0
four-membered rings. Each Lie (e.g. Li2) is bound to an
ortho C atom (C6), to two 0 atoms of two different sulfonyl groups ( 0 1 and 02’) and to one diethyl ether 0 atom
(04). The sp2 orbital at C6 is oriented almost centrally between Li2 and Lil‘ (the torsion angles S-CLC6-Li2 and
S-C 1-C6-Li 1‘ are 37.8(5) and - 47.1(4) respectively). The
two Lie (e.g. Li2 and Lil’) which are coupled to an ortho C
atom (C6) are complexed by the neighboring sulfone 0
atoms 01 and 0 2 such that five-membered rings are
formed (e.g. C6-Li 1’-02-S-CI).r’01The ease of ortho-lithiation of arenes with an RS02 groupf4]is thus understandable. The structure computed for Li,CHS02CH3 by Streitwieser et al.L”lis very similar to that of [3.(OEt2),], in one
respect: the two Lie are bound to the two sulfone 0 atoms
and an “anionic” C (a-C).
The structural characteristics of the a-sulfonyl anion
moiety of [3-(OEt,),], are not influenced to any great extent but, nevertheless, noticably so by the dianion formation: the C7-S bond is shortened from 174.7(5) pm in the
sulfone la“*] to 163.7(5) pm, and the S - 0 bonds are
lengthened from 144.3(3) pm to 149.4(3) pm; hence, the SO bonds here are ca. 3 pm longer than in the known asulfonyl carb bani on^".^^^ This could be due to the fact that
each 0 atom in the “dianion” [ 3 .(OEt2)2]2is coordinated
to two Li5, but in the monoanions to only one Lie. The
dihedral angles OI-S-C7-Sil ( - 50.8(4)”)and 02-S-C7-Si2
(13.3(4)”) would indicate that the lone pair on C7 assumes
a gauche conformation to the sulfone 0 atoms, which is
rotated through ca. 18.5” from the ideal position; the same
situation is found in m ~ n o a n i o n s . [ ~
~ Iis almost planar
coordinated: the sum of the torsion angles Cl-S-C7-Sil
and CI-S-C7-Si2 is 169.7’. Further, the eight-membered
ring (e.g. S-O1-Lil-O2’-S’-O1 ’-Lil’-O2), which characterizes a-sulfonyl “carbanion” dimers, is also still present.
The X-ray structure analysis of [3 -(OEt2)2]2thus confirms the structural characteristics found in a-sulfonyl
“carbanions” ; further, the five-membered ring complexation of Lie by the 0 atoms of an RS02 group in an aromatic ortho anion is recognizable which contributes to its
ease of formation.
Received: August 17, 1987 [Z 2401 IE]
German version: Angew. Chem. 99 (1987) 1279
[I] D. Seebach, R. Hassig, J. Gabriel, Helu. Chrm. Acta 66 (1983) 308.
121 The significance of these selective reactions is covered in a series of new
reviews: a) P. Beak, D. B. Reitz, Chem. Reu. 78 (1978) 275; H. W.
Gschwend, H. R. Rodriguez, Org. React. 26 (1979) I ; c) P. Beak, V.
Snieckus, Acc. Chem. Res. 15 (1982) 306; d) P. Beak, A. 1. Meyers, Acc.
Chem. Res. 19 (1986) 356; e) G. W. Kiumpp, J. R. Neth. Chem. Sac. I05
(1986) 1.
131 X-ray structure data have recently become available for some a-sulfonyl
“carbanions”: a) [(PhCHSO2Ph)Li(tmeda)l2:G. Boche, M. Marsch, K.
Harms, G. M. Sheldrick, Angew. Chem. 97 (1985) 577; Angew. Chem.
Inr. Ed. Engl. 24 (1985) 573; b) [(CH,SO,Ph)Li(tmeda)],: H.-J. Gais, H.
J. Lindner, J. Vollhardt, ibid. 97 (1985) 865 and 24 (1985) 859; c)
[(CH2=CHCHSO2Ph)Li(diglyrne)l2:H.-J. Gais, H. J. Lindner, J. Vollhardt, ibrd. 98 (1986) 916 and 25 (1986) 939; d) the structure of
[(MeiSiCHSOzPh)Li(tmeda)]2 corresponds in many respects to the structures of the compounds mentioned under (a-c): G. Boche, W. Hollstein,
M. Marsch, K. Harms, unpublished.
[4]The strong directing effect of the RSOl group (R=aryl, tert-butyl, NR;,
NLiR‘) is known: a ) W. E. Truce, M. F. Amos, J. Am. Chem. Sac. 73
(1951) 3013; b) H. Gilman, S. H. Eidt, ibid. 78 (1956) 2633; c) H. Watanabe, C. R. Hauser, J . Org. Chem. 33 (1968) 4278; d ) H. Watanabe, R. A.
Schwarz, C . R. Hauser, J . Lewis, D. W. Slocum, Can. J. Chem. 47(1969)
1543; e) F. M. Stoyanovich, R. G. Karpenko, Y. L. Gol‘dfarb, Tetrahedron 27 (1971) 433; f) J. G. Lombardino, J. Org. Chem. 36 (1971) 1843;
g) D. Hellwinkel, M. Supp, Chem. Eer. 109 (1976) 3749; h) D. W. Slocum, D. I. Sugarman, Adu. Chem. Ser. 130 (1974) 222; i) S. J. Shafer, w.
D. Closson, J. Org. Chem. 40 (1975) 889; j) D. W. Slocum, C . A. Jen-
0 VCH Verlagsgesellscha/r mbH, 0-6940 Weinheim, 1987
nings, ibid. 41 (1976) 3653; k) y-deprotonation of a,P-unsaturated sulfones: E. Block, V. Eswarakrishnan, K. Gebreyes, Tetrahedron Leu. 25
(1984) 5468.
orrho-Li compounds which are complexed intramolecularly by RO- or
R,N-groups have been investigated X-ray crystallographically: a) J. T.
B. H. Jastrzebski, G. van Koten, M. Konijn, C. H. Stam, J. Am. Chem.
Sac. 104 (1982) 5490; b) I. R. Butler, W. R. Cullen, J. Reglinski, S . J.
Rettig, J. Organomet Chem. 249 (1983) 183: c) J. T. B. H. Jastrzebski, G.
van Koten, K. Goubitz, C. Arlen, M. Pfeffer, ibid. 246 (1983) C 7 5 ; d) H.
Dietrich, D. Rewicki, ibrd. 205 (1981) 281; e) see also: W. Neugebauer,
A. J. Kos, P. von R. Schleyer, rbid. 228 (1982) 101.
a) In the reaction of ally1 phenyl sulfone with two molar equivalents of
nBuLi in T H F at low temperatures the initially formed a-sulfonyl “carbanion” reacts further to give the I,o-dianion corresponding to 3. Transprotonation to the I,l-dianion takes place at 50°C [7]; see J. Vollhardt,
H.-J. Gais, K. L. Lukas, Angew. Chem. 97 (1985) 607; Angew. Chem. Int.
Ed. Engl. 24 (1985) 608; b) the second lithiation of (trimethylsily1)methy1 phenyl sulfone proceeds exclusively to the 1,l-dianion; see J. Vollhardt, H.-J. Gais, K. L. Lukas, ibid. 97 (1985) 695 and 24 (1985) 696; c)
the a-sulfonyl “carbanions” mentioned under [3a-d] are formed from
the sulfone and one molar equivalent of nBuLi; nothing has been reported about a further reaction product. 2,o-Dilithio compounds are
also known: J. E. Mulvaney, S. Groen, L. J. Carr, Z. G. Garlung, J. Am.
Chem. Sac. 91 (1969) 388; H. M. Walborsky, P. Ronman, J. Org. Chem.
43 (1978) 731.
1,l-Dilithiosulfones have been known for some time: a) E. M. Kaiser, L.
E. Solter, R. A. Schwarz, R. D. Beard, C. R. Hauser, J. Am. Chem. Sac.
93 (1971) 4237; b) J. B. Evans, G. Marr, J. Chem Sac. Perkin Trans. I
1972, 2502; c) K. Kondo, D. Tunemoto, Tetrahedron 1975, 1397; d) A.
Roggero, T. Salvatori, A. Proni, A. Mazzei, J . Organomel. Chem. I77
(1979) 313; e) S. P. J. M. van Nispen, C. Mensink, A. M. van Leusen,
Tetrahedron Lett. 21 (1980) 3723; f) M. C. Mussatto, D. Savoia, C.
Trombini, A. Umani Ronchi, J. Org. Chem. 45 (1980) 4002; g) J. J. Eisch,
S. K. Dua, M. Behrooz, ibid. 50 (1985) 3674.
Procedure for [3-(OEt2),],: A solution of la (90 mg, 0.30 mmol) in diethy1 ether (1 mL) was treated at room temperature with 0.33 mmol of
nBuLi in hexane. After 10min the solution was evaporated down to
about 0.5 mL in an oil-pump vacuum. Single crystals suitable enough for
an X-ray analysis could be isolated from the solution after I hour.
Yield: 44 mg (0.05 mmol), 30°/o.
The exclusive formation of 28 from l b additionally shows that the deprotonation of 1 does not initially lead to an ortho anion that is transprotonated in a second step to the a-anion 2. Otherwise 2b and, after
protonation, l e would have to be formed; deuterium determinations
were carried out mass spectrometrically. A corresponding experiment
was carried out for the first time by Gais et al., see [6b]. A related problem has recently been investigated by other authors: A. I. Meyers, K. B.
Kunnen, W. C . Still, J. Am. Chem. Sac. 109 (1987) 4405. For the mechanism of the second lithiation in some other compounds see: W. Bauer,
T. Clark, P. von R. Schleyer, J. Am. Chem. Sac. 109 (1987) 970; W.
Bauer, G. Miiller, R. Pi, P. von R. Schleyer, Angew. Chem. 98 (1986)
1130; Angew. Chem. I n t . Ed. Engl. 25 (1986) 1103.
I-Magnesio-2-pivaloyl-l,2,3,4-tetrahydroisoquinolineis characterized
by a structurally related five-membered ring formation by intramolecular complexation of the carbonyl 0 atom with the C-bonded Mg:
D. Seebach, J. Hansen, P. Seiler, J. M. Gromek, J. Organomet. Chem.
285 (1985) 1.
D. A. Bors, A. Streitwieser, Jr., J. Am. Chem. Sac. 108 (1986) 1397.
Structure of l a : W. Hollstein, M. Marsch, K. Harms, G. Boche, unpublished.
Coupling of Two Ethyne Molecules at a Nickel
Center to Form a Nickelacyclopentadiene Complex
By Klaus-Richard Porschke*
The nickel catalyzed cyclooligomerization reactions of
acetylene discovered by Reppe presumably proceed stepwise by a mechanism involving a nickelacyclopentadiene
Compounds of this type are already known
for other
whereas with nickel so far only substituted derivatives have been obtained.L31Continuing our investigations on ethyne complexes of nickel(^)[^^ we have
now observed for the first time a coupling of two ethyne
molecules on nickel(o) at -78°C (!), leading to formation
[*I Dr. K.-R. Porschke
Max-Planck-lnstitut fur Kohlenforschung
Postfach 10 13 53, D-4330Mulheim a. d. Ruhr 1 (FRG)
0570-0833/87/1212-1288 $ 02.50/0
Angew. Chem. Int. Ed. Engl. 26 (1987) No. I 2
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complex, stabilizer, compounds, phenyl, sulfonyl, unit, trimethylsilyl, structure, metnyl, уcarbanionф, analysis, bis, li2, sulfone, ray, ortho
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