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Dimenzation of 1 6-Ditiniacycioaeca-3 8-diyne in the Presence of Cobalt Complexes. A Simple Synthesis of a [2

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J. Am. Chem. Soc. 108 (1986) 8267). is not “unequivocal” as no attempt
was made to dissect electronic from strain effects. “Homoconjugation”
may be a bet!er term to describe stabilizdtlons of such small magnitude,
if present.
[2] We thank Michael Waeber. Herbert Gareis. and Roland Hacker, Erlangen, for preliminary experimental investigations, and E. M. Engler for
early STO-3G calculations. Further work is described in the Diplomarbeit of M. B.. Universitat Erlangen-Nurnberg 1986.
[3] See a review on stable carbodications: G. K. Surya Prakash, T. N. Rowdah, G. A Olah, Angew. Chem. 95 (1983) 356; Angew. Chem. In!. E d .
C i y l . 22 (1983) 390. Also see: G. K. Surya Prakash, M. Formia, S.
Keyonian, G. A. Olah, H. J. Kuhn, K. Schaffner, J . Am. Chem. SOC.109
(1987)911
141 a ) R. C. Bingham, M. J. S . Dewar, D. H. Lo, J . Am. Chem. Soc. 97(1975)
1285; b) for reviews, see T. Clark: A Handbook ofComputationa1 Chemi.7rr-i.. Wiley, New York 1986; c) D. F. V. Lewis, Chem. Revs. 86 (1986)
IIII
IS] a) R. E. Pincock, J. Schmidt, W. B. Scott, E. J. Torupka, Can. J . Chem.
50 (1972) 3958; b) C. S . Gibbons, J . Trotter, ibid. 51 (1973) 87; c) R. E.
Pincock, F.-N. Fung, Tetrahedron Left. 21 (1980) 19; d) W. B. Scott, R.
E. Pincock, J Am. Chem. Soc. 95 (1973) 2040; e) R. E. Pincock, E. J.
Torupka, ihid. 91 (1969) 4593.
161 G. A. Olah. G. K. Surya Prakash, J. G. Shih, V. V. Krishnamurthy, G. D.
Mateescu, G. Liang, G. Sipos, V. Buss, T. M. Gund, P. von R. Schleyer.
J Am. Chem SOC.107 (1985) 2764. The pagodane dication is of interest
in this context: G. K. S . Prakash, V. V. Krishnamurthy, R. Herges, R.
Bau, H. Yuan, G. A. Olah, W.-D. Fessner, H. Prinzbach, J . Am. Chem
Soc. 108 (1986) 836.
171 G. P. Sollott, E. E. Gilbert, 1.Org. Chem. 45 (1980) 5405, and reference\
cited therein. A modified procedure using CSI and AII’, prepared in
situ. was employed here.
[S] a) S. Masamune, M. Sahai, A. V. K. Jones, T. Nakashima, Can. J. Chem.
52 (1974) 8 5 5 ; b) G. A. Olah, G. K. Surya Prakash, D. Whittaker, J. C.
Rees, J. Am. Chem. SOC. 101 (1979) 3935; c) G. K. Surya Prakash, M.
Arvanaghi, G. A. Olah, ibid. 107 (1985) 6017; d ) also compare the pentacyclononyl cation reported by R. M. Coates, E . R. Fretz, J . Am. Chem.
Soc. 97 (1975) 2538.
191 R. C. Fort, P. von R. Schleyer, J . Org. Chem. 30 (1965) 789.
[lo] P. von R. Schleyer, D. Lenoir, P. Mison, G. Liang, G. K. Surya Prakash,
G. A. Olah, J. Am. Chem. SOC.102 (1980) 683.
[ I I] M. Schindler, J. Am. Chem. SOC.109 (1987) 1020.
1121 Reviews on pyramidal carbocations: H. Schwartz, Angew. Chem. 93
(1981) 1046; Angew. Chem. I n t . Ed. Engl. 20(1981)991; P. Vogel: Carbocatlon Chemistry. Elsevier, Amsterdam 1985.
1131 S . Masamune, M. Sahai, H. Ona, A. J. Jones, J. Am. Chem. Soc. 94
(1972) 8956; A. V. Kemp-Jones, N. Nakamura, S . Masamune, J . Chem.
Soc. Chem. Commun. 1974. 109, and references cited therein.
[I41 H. Hogeveen, P. W. Kwant, Acc. Chem. Res. 8 (1975) 413.
[I51 E. D. Jemmis. P. von R. Schleyer, J . Am. Chem. Soc. I04 (1982) 4781,
and earlier papers in the same series. E. D. Jemmis, ibid. 104 (1982)
7017: J. Chandrasekhar, E. D. Jemmis, P. von R. Schleyer, in preparation.
1161 Natural population analysis (A. E. Reed, R. B. Weinstock, F. Weinhold,
J . Chem. Phys. 83 (1985) 735) based on natural localized molecular
orbitals (A. E. Reed, F. Weinhold, ibid. 83 (1985) 1736) and the
ST0-3G//STOO-3Gand the 3-21G//3-21C wave functions (W. J. Hehre,
L. Radom, P. von R. Schleyer, J. A. Pople: Ab Initio Molecular Orbital
77wory. Wiley, New York 1986) were employed.
1171 Spectroscopic data of 6 , 7,and 8. (The multiplicities of the NMR signals are taken from ‘H-decoupled ”C-NMR spectra; ‘Jle.,,l coupling
constants from “gated” spectra): 6 , m.p. =72-73”C; ‘H-NMR (400
MHz, CDC13): 6=2.10, 2.19 (2mc, 6 H , CF-CHZ-CF), 2.50 ( s , 6 H ,
CF-CHI-CI); “C-NMR (100 MHz, CDCI,): 6=25.5 (4, ‘ J l c F ) = 14
Hz. CI), 45.7 (t, ’ J l c e,=20 Hz, CF-CHZ-CF, ’ J l c . ~ ) 134
= Hz), 53.6 (d,
‘J(<> , = 2 0 Hz, CF-CHI-CI,
‘ J , c H ) = 136 Hz), 90.2 (dt, ‘J,C,F,= 195 Hz,
‘Jl<,,= 15 Hz. CF); IR (KBr): 3=2920, 2810, 1440, 1430, 1310, 1295,
1230, 1205, 1130, 1025. 1005,970,940, 885,860,780, 700cm-’.-7, ‘HNMR (400 MHz, [D,ltetrahydrofuran): 6 = 1.36 (d, 4 H , ’ J I H
10 Hz,
CF-CHI-C),
1.64 (d, 2 H , ‘ J , e ~ ) = 8 Hz, C-CHZ-C), 2.01 (d, 4 H .
is)=
10 HZ, CF-CHI-C), 2.22 (t. 2 H , ‘ J 1 t ~ 1 = Hz,
4 CF-CHI-CF);
“C-NMR (100 MHz, [D&etrahydrofuran): 6= 18.9 (t, ‘J,cFl=9 Hz.
CH:-C-CH?), 37.2 (t, ‘Jlc 6 1-4 Hz, C-CHz-C, ‘Jlc..HI= 159 Hz), 45.3
(dd, ‘J(c
15 Hz, “ J , c , , = 3 Hz, CF-CHZ-C, ‘ J , c H l = 136 Hz), 46.0(t,
‘J,<g , = I8 Hz, CF-CHz-CF, ‘ J , C , ~
132
~=
Hz), 98.4 (dd, ‘J1c,,,=226
Hz, ‘Jtc, , = 5 Hz, CF).-S, m.p.=132-134”C; ‘ H - N M R (400 MHz,
CDCli): 6=2.18 (t. ZH, ‘ J l b * , , = 5 Hz, CF-CHZ-CF), 2.52 (d, 4 H ,
‘JCtC
to= I I
Hz, CF-Ctf-CI),
2.62 (d. 4 H , ‘J(H.H)= 11 Hz,
“C-NMR (100 MHz,
CF-CHZ-CI), 2.91 (s, 2 H , CI-CH?-CI);
CDCI,): 6=28.8 (t. ‘J<c.11=12 Hz, CI), 45.3 (t, ‘Jlc.+)=20 Hz,
136 Hz), 53.1 (dd, ‘ J l c . F I = 18 Hz, ‘JiC-F,=3 Hz,
CF-CHI-CF, ’J,<..,~I=
CF-CH?-CI, ‘ J , < . H I =135 Hz), 60.2 ( s , CI-CHI-CI, ‘ J ( c H 1 = 136 Hz),
89.7 (dd, ‘ J t c t i = 198 Hz, ‘Ji<.,,=
14 Hz, CF); IR (KBr): C=2910, 2820,
1430, 1310. 1290, 1250, 1215, 1205, 1095, 1015, 995, 960, 945, 930, 870,
815, 725, 675 cm ~ I .
Angen, Chem. I n ! . Ed. Engl. 26 11987) No. 8
Dimerization of 1,6-Dithiacyclodeca-3,8-diyne
in the Presence of Cobalt Complexes. A Simple
Synthesis of a [2.2](2,5)Thiophenophane Derivative**
By Rolf Gleiter,* Michael Karcher. Bernhard Nuber. and
Manfred L. Ziegler
Dedicated to Professor Hermann Schildknecht
on the occasion of his 65th birthday
Recently, we showed that cyclodeca- 1,6-diyne 1 undergoes dimerization in the presence of [CpCo(CO),] o r
[CpCo(C8HI2)1(Cp =q5-C5H5)to give a superphane of cyclobutadiene, 3, doubly capped by CpCo units.“’
CP
co
CO
CP
3
2 (x=s)
4
To test the scope and limitations of this new reaction, we
have investigated the reaction of 1,6-dithiacyclodeca-3,8diyne 2IZ1with [CpCo(CO),] and [CpCo(C8H ,?)I. Heating 2
(1.0 g, 5.95 mmol) with [ C ~ C O ( C O )(1.07
~ ] g, 5.95 mmol) in
n-octane yielded a colorless product (120 mg) which contained no CpCo unit. The analytical data of the product
(see Table 1) showed a molecular weight of 336, and the
IR, UV,“’ and NMR data indicated the presence of thiophene units and two nonequivalent C H 2 bridges. When 2
was heated with less than the equimoiar amount (10%) of
the Co complexes, we obtained the same product. Three
structural possibilities, the anti and syn isomers 4 and 5 ,
respectively, and the cage compound 6, are compatible
with the spectroscopic data.
5
6
7
From the observation that the most intense peak in the
mass spectrum of the product is at m / z 168 ( M 0 / 2 ) , we
favored 4 and 5 over 6.
[*] Prof. Dr. R. Gleiter, Dipl.-Chem. M. Karcher
[**I
Institut fur Organische Chemie der Universitat
Im Neuenheimer Feld 270, D-6900 Heidelberg (FRG)
Prof. Dr. M. L. Ziegler, Dr. B. Nuber
lnstitut fur Anorganische Chemie der Universitat
I m Neuenheimer Feld 234, D-6900 Heidelberg (FRG)
This work was supported by the Deutsche Forschungsgemeinschaft, the
Fonds der Chemischen Industrie, BASF AG, and Degussa AG.
0 V C H Verlagsgesellschaji m b H . 0-6940 Wernheim, 1987
0044-8249/87/0808-0763 $ 02.50/0
763
Table I . Most relevant physical data of 4.
IR (KBr): 1=2950 (w). 2940 (m). 2920 (m), 2840 (w), 1440 (m), 1430 (m). 1365
(m), 1315 (m), I170 (m), 1045 (w) c m - '
U V (CH>CII): A.,,.,,(lg&)=253 (3.91), 288 nm (3.83)
' H - N M R (CDCI,, 300 MHz, TMS): 6=2.73-2.84, 2.97-3.07 (AA'BB'), 3.94,
3.78 (AB, J A B = 12.8 Hz)
'>C-NMR(CDCI,, 75.46 MHz): S= 146.2 (s), 138.8 (s), 30.3 (t), 27.8 (1)
MS (70 eV): m/z=336 (2.9%. Ma),168 (1004/0, M0/2)
tained from CHZC12); w scan (3"<26<60"), MoK,, radiation
(A=0.7106(9)A); 1492 reflections, of which 1453 were judged to be observed ( I > 2.50(1)). All crystallographic calculations employed the
SHELXTL program package 5. I (December 1985). Empirical absorption
correction (5 refletions, 2 8 range 9-36", w scan). Relative range of transmission factors: 0.89- 1.00 l.p= 5.9 cm-'). Least-squares refinement with
ZwIfi,I-xF,I)' ( w = I/o'((R).The structure was solved by direct methods
(SOLVE, SHELXTL). The hydrogen atoms were located from a difference Fourier map and subjected to isotropic refinernen!; R = 0.046,
R,, =0.041. A final difference Fourier map revealed no peaks greater than
0.55 e/A3. Further details of the crystal structure investigation are available on request from the Fachinformationszentrum Energie, Physik, Mathematik GmbH, D-75 14 Eggenstein-Leopoldshafen 2 (FRG), on quoting
the depository number CSD-52317, the names of the authors, and the
journal citation.
[ S ] N. B. Pahor, M. Calligaris, L. Randaccio, J. Chem. SOC.Perkin Trans. 2
1978. 42.
[6] H. Yamazaki, N. Hagihara, J. Orgunornet. Chem. 7 (1967) 22; R. B. King,
I. Haiduc, J. A m . Chem. SOC.94 (1972) 4044.
Bis(qs-cyclopentadienyl)-1,3-diphosphabicycldl .l.O]butane-2,4-diylzirconium :
A Simple Synthesis of an Unusual Molecule**
By Paul Binger.* Bruno Biedenbach. Carl Kruger. and
Manfred Regitz
Recently, both we['] and an English groupiz1succeeded
independently in preparing q4-1,3-diphosphacyclobutadiene metal complexes 1 (M = Co, Rh; R = tert-butyl)
starting from h3-phosphaalkynes. The 2-metalla-l,4-diphosphacyclopentadienes 2, which are analogues of the
intermediates involved in the numerous reported syntheses
of q4-cyclobutadiene metal complexes,I3] can be postulated
as being involved in this cyclodimerization. However,
I
2.644
1
Fig. I . Crystal structure of 4 with important distances [A] and angles.
a) View from above; b) side-on view.
To solve this structural problem and to obtain further
details of the molecular structure, we carried out an X-ray
investigati~n.[~I
The results show that 4 is present in the
crystal (Fig. 1). The thiophene rings are envelope shaped;
the plane C2-S-C5 forms an angle of 9.2" with the plane of
the sp2 carbon-atoms. The planes of the latter are separated by 2.644 A. Similar geometric parameters were found
for the parent system [2.2](2,5)thi0phenophane.'~]
Concerning the mechanism of the reaction, we assume
as intermediate a cobaltacyclopentadiene16' in which one
sulfur center is associated with the metal. Such a complex
may yield the exomethylene derivative 7,which dimerizes
to give 4.
compounds of the type 2 have never been detected or isolated. We therefore attempted to synthesize analogous
compounds of zirconium by reaction of h'-phosphaalkynes with [Cp2Zr](Cp=q5-CsH5)generated in situ. These
coordinatively unsaturated Zr" species react with a variety
of alkynes to give zirconacyclopentadiene d e r i ~ a t i v e s . ' ~ - ~ ]
Reaction of [Cp,ZrCI,] with magnesium and 2Jdimethylpropylidynephosphane 3 in the presence of HgC12[41
afforded orange-red crystals having the stoichiometry
[Cp2Zr{P,C2(C(CH,),),)I (53% yield, correct elemental
analysis, molecular weight (MS) =420), to which structure
4 has been assigned. Complex 4 can also be obtained from
[Cp,ZrCI,], butyllithium, and 3"' (yield 26%) o r from
[Cp,Zr(butadiene)] and 318](58%).
t
Received: March 2, 1987
[Z 2121 1El
Publication delayed at the authors' request
German version: Angew. Chem. 99 (1987) 805
3
+
4
[ I ] R. Gleiter, M. Karcher, M. L. Ziegler, B. Nuber, Terruhedron Letr. 28
(1987) 195.
121 G . Eglington, 1. A. Cardy, R. A. Raphael, G A. Sim, J. Chem. SOC.1964.
1 154.
131 H. E. Winberg, F. S. Fawcett, W. E. Mochel, C. W. Theobald, J . A m .
Chem. SOC.82 ( 1960) 1428.
[41 4 : a=7.528(2), b=8.646(3), c= 11.7420) A, 8=98.44(2)", Y=756.0 A',
Z = 2. Space group P 2 , / c (No. 14). Data were collected on a Siemens Stoe
diffractometer using a crystal of dimension 0. I I x 0.22 x 0.42 mm' (ob-
764
0 VCH Verlugsgesellschafrm6H. 0-6940 Weinherm. 1987
[*] Priv.-Doz. Dr. P. Binger, DipLChem. B Biedenbach,
[**I
Prof. Dr. C. Kruger
Max-Planck-lnstitut fur Kohlenforschung
Kaiser-Wilhelrn-Platz I , D-4330 Miilheim a. d. Ruhr (FRG)
Prof. Dr. M. Regitz
Fachbereich Chemie der Universitat
Erwin-Schrodinger-Strasse,D-6750 Kaiserslautern (FRG)
This work was supported by the Stiftung Volkswagenwerk.
0044-8249/87/0808-0764 $ 02.S0/0
Angew. Chem. Int. Ed. Engl. 26 (1987) No. 8
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