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Mononuclear Transition Metal Complexes with CS2-Analogous Coordination of a Thioketene.

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111
f3)
The molecule (3)(Fig. 1) exhibits only C, symmetry, and
not the possible (C2, symmetry. The two (CH3)2N-groups
are stereochemically non-equivalent. One (containing N6)
four. N5 adds nucleophilically via the lone electron pair
S3. The molecular geometry can be explained in terms of a
frozen-in intramolecular rearrangement of an (CH3)zNgroup from S1 to S3. Two sharp signals are observed in the
'H-NMR spectrum recorded at room temperature (6= 2.53
for the exo- and 6=2.35 for the endodimethylamino
group). At - 70 "C the exchange of the exo-methyl group is
frozen-in, and two broad signals appear instead of the singlet. The signal of the endodimethylamino group remains
sharp and in exactly the same position.
Procedure
A suspension of (])I9] (2.55 g, 10 mmol) in CH3CN (80
mL) is cooled, with stirring, to - 35 to - 40 C and treated
dropwise within 2.5 h with a solution of (2) (2.57 g, 22
mmol) in CH3CN (70 mL). The resulting solution is then
warmed within 2 h to room temperature. A deep-red clear
solution is obtained. After removal of solvent in a vacuum
a red oil remains. This is extracted portionwise with 100 mL
n-hexane, and the n-hexane solution is evaporated down to
60 mL. On cooling (in a deep-freeze) (3) (decomp. pt. 7072 "C) is obtained as pale-yellow crystals in 40% yield. Further amounts of (3) can be obtained by concentration of
the mother liquor. The residue insoluble in n-hexane contains S4N4 as identifiable product.
O
Received: July 7, 1980 [Z 793 b IE]
German version: Angew. Chem. 93, 624 (1981)
CAS Registry numbers:
(1). 71699-97-3; (2). 2083-91-2; (3), 78167-47-2
[A]
Fig. 1. Molecular structure of S,N4[N(CH~J2]2
(3) with bond lengths
and
angles I"] determined uia the molecular mirror symmetry. Further bond an111.8, CI-N5-C2
112.9, Nl-SI-N4
106.5,
gles are: CI-NS-Sl
N2-S3-N3
100.4, Nl-S2--S4
92.4, N2-S2-S4
92.0". Standard deviations of the determined values: bond lengths: S-S 0.002, S-N 0.0050.008, C-N 0.007-4.013 A; angles 0.2-0.7".-(3) crystallizes in the triclinic
space group Pi with a=7.559(5), b=8.496(5), c=9.480(6) A, a= 104.19(5),
8=93.4(5), y= 103.13(5)0, Z = 2 ; diffractometer data: Cu,, radiation, 1274
observed reflections (J> Zu,),corrected for absorption, measured at -60°C.
8 ,.,,=57.5", R=0.079.
occupies an exo-position on the S,N4 ring with trigonalplanar, the other (containing N5) an endo-position with
pyramidal ligand arrangement. The bond lengths in the
two SN3 groups are markedly different. The group containing S3 contains one shorter exocyclic and two longer
endocyclic S-N bonds, the group with S1 one longer exocyclic and two shorter endocyclic S-N bonds. The C2,
symmetry is also destroyed with respect to the usual S-N
bond lengths. The bonds from S2 (and S4) to N1 and N2
(and N4 and N3, respectively) are different in length. The
average S-N bond length in the S4N4ring (1.62 A), however, has almost the same size as in the S4N4 eight-membered ring of S4N>la1, S4N;[Ih1, S4N:[2a1, S4N50-IZb1,
S4N4.2C7H813],SSNP1, S5N6(CH2)4151,
S,N6(CH3)2[6a1and
SSN7Si(CH3)5[6a1,
but distinctly greater than in the Lewis
acid adducts of S4N4 with BF3[6h1,
SO,[7a1, FSOzNC0[7h1
and AsF,[*](1.588-1.599 A).
The conformation of the S4N4 ring in (3) corresponds to
that of S,N4; however, one transannular S-So bond is
opened, while the other is shortened by ca. 0.14 A to 2.447
The opened S-S bond becomes unsymmetrically
bridged by a (CH3)zN-group:N5 in the substituent forms
an S-N single bond to S1 and at the same time strong
transannular interaction with S3 (N5-S3: 2.760 A); as a
consequence the coordination number of S3 increases to
A.
a
Angew. Chem. Int. Ed. Engl. 20 (1981) No. 6 / 7
[11 a) B. D. Sharma, J . Donohue, Acta Chryst. allogr. 16, 891 (1963)); M . L.
De Lucia, P. Coppens, Inorg. Chem. 17, 2336 (1978); b) W. Flues, 0. J .
Scherer, J . Weiss, G. Wofmershauser.Angew. Chem. 88, 41 I (1976); Angew. Chem. Int. Ed. Engl. IS, 379 (1976).
I21 a) T. Chiuers. L. Fiedling. W . G. Laidlaw, M . Trsic, Inorg. Chem. 18,
3379); b) P. Luger, H. Bradaczek. R. Sreudel. Chem. Ber. 109, 3441
(1976).
131 A. Griffin,G. M . Sheidrick. Acta Crystallorg. B 31, 895 (1975), G.Ertl, J.
Weiss, 2. Anorg. Chem. 420, 155 (1976).
141 T. Chiuers, D . Proctor, J. Chem. Sac. Chem. Commsn. 197, 62; H. W.
Roesky. M . N . S . Rao, T. Nakajima, W. S. Sheldrick, Chem. Ber. 112,
3531 (1979).
I51 H . W. Roesky, C.Graf, M . N . S . Roo. B. Krebs, G. Henkel. Angew. Chem.
91, 846 (1979); Angew. Chem. Int. Ed. Engl. 18, 780 (1979).
[6] a) W. S. Shefdrick, M . N . S . Rao, H. W. Roesky, Inorg. Chem. 19, 538
(1980): b) M . G. E . Drew. D. H . Templeton, A. Zalkin, ibid. 6, 1906
(1967).
171 a) A. Gieren. E. Dederer, H. W . Roesky, N. Amin, 0. Petersen. Z . Anorg.
Allg. Chem. 440, 119 (1978); b) A. Gieren, Ch. Hahn, B. Dederer. H. W.
Roesky, N . Amin. ibid. 447. 179 (1978).
181 R. J . Gillespie, J. P. Kent, J . F. Sawyer, Acta Crystallogr. B 36, 655
(1980).
I91 L. Zboriloua. P. Gebauer. 2. Anorg. Allg. Chem. 448, 5 (1979).
Mononuclear Transition Metal Complexes
with CS,-Analogous Coordination of a Thioketene"'
By Helmut Werner, Oswald Kolb, Ulrich Schubert, and
Klaus Ackermann"'
Dedicated to Professor Siegfried Hiinig on the occasion
of his 60th birthday
Metal complexes of CS, and analogous ligands SCX
(X = 0, Se, NR etc.) are of interest as model substances for
[*] Prof. Dr. H. Werner, Dip].-Chem. 0. Kolb
Institut fur Anorganische Chemie der Universitat
Am Hubiand, D-8700 Wiirzburg (Germany)
Priv.-Doz. Dr. U. Schubert, Dipl.-Chem. K. Ackermann
Anorganisch-chemisches Institut der Technischen Universitat Munchen
Lichtenbergstr. 4, D-8046 Garching (Germany)
0 Verlag Chemie GmbH, 6940 Weinheim. 1981
0570-0833/81/0707-0593 $ 02 50/0
593
the complexation of CO2[']. We recently reported the synthesis of C5H5(PMe3)Co(qZ-CS2)[31
and C5H5(PMe3)Co(q2SCSe)['], which are formed by attack of the strong metal
base C5H5Co(PMe,)z[51
at the electrophilic carbon atom of
CS2 and SCSe, respectively. 1,1,3,3-Tetramethyl-2-thiocarbonylcyclohexane ( I ) , which in contrast to other dialkylthioketenes is remarkably stable, also reacts with this metal
base (in benzene, 25 C), rapidly and quantitatively to give
the cobalt complex (2). The corresponding rhodium complex (3) is formed from C5H,Rh(PMe3)C2H4I6]
and (I) in
benzene on warming to 60 C for a day.
multiple bonding cannot be ruled out in the case of the
Co-C bond[*].Thus, similarly to CS2, SCSe and other heteroallenes, ( I ) could also exhibit considerable n-acceptor
character. The hypothesis of comparable ligand properties
of CSz and dialkylthioketenes such as ( I ) is, moreover,
supported by
the very similar bond
angles
S-C-C=138.6"
in (2) and S-C-S=141.2"
in
C5H5(PMe3)Co(q2-CSz)'3'.
Very few mononuclear thioketene-metal complexes have
so far been mentioned in the literature. Behrens et ~ 1 . ' ~de"~
scribe a complex in which (I) is presumably bound only
via the S atom to Cr(C0)5.Iridium(r) and platinum(0) complexes with q'-coordinated bis(trifluoromethy1)thioketene
have been synthesized by Stone et u I . ' ~ ~ ' , not however from
(CF,),C=C=S as starting material, but from heterocyclic,
CF,-substituted sulfur compounds.
(Z), M = co
(31, M = R h
Received: August 21, 1980 [Z 782 IE]
Revised: October 15, 1980
German version: Angew. Chem. 93, 583 (1981)
The air-stable solids (2) and (3)are readily soluble in the
usual organic solvents. The characteristic stretching frequency at 1750 cm-' for the S=C=C group in (1) is no
Table 1. Spectroscopic data of the new thioketene-metal complexes (2) and
(3).
(2): 'H-NMR ([D6]benzene): 6=4.70 (CsH5;s), 1.96, 1.75, 1.65, 1.62 (4CH3;
s), 0.84 (PMe,; d, JpH=9.8 Hz), CH2-signals of the six-membered ring
masked by methyl resonances. MS (70 ev): m/z(I,)=382 (13; M+),366
(2; M+-CH,), 334 (3; M+-3CH4), 306 ( 1 ; M+-PMe3), 200 (100;
CsHSCoPMe;), 189 (7; Co(CsH5):), 124 (15; CoCsH:).
(3): 'H-NMR ([D6]benzene): 6=5.16 (C5H5;d x d , JPH=1.5, JRhH=0.7Hz),
1.81,1.66, 1.58, 1.57(4CH3;s), 1.05(PMe3;dxd, JpH=10.4,J ~ h H = l . 0
Hz),CH,-signalsmasked. MS (70 ev): m/z(lr)=426 (35; M+),410 (3;
M'-CH,),
244 (100; C5HSRhPMe3),168 (37; RhC5H:).
longer observed in the IR spectra of the complexes. The dihapto4q')coordination thus indicated for the thioketene is
confirmed by the crystal structure analysis of (2)17].
[ I ] Complexes with Carbon Sulfides and Selenides as Ligands, Part 5. This
work was supported by the Deutsche Forschungsgemeinschaft, the Fonds
der Chemischen Industrie, and by gifts of chemicals from BASF AG,
Ludwigshafen. We thank Dr. U . Behrens for supplying us with the the
thioketene.-Part 4: H. Werner, 0. Kolb. R . Feser. U. Schubert, J. Organomet. Chem. 191, 283 (1980).
121 P. V. Yanefl, Coord. Chem. Rev. 23, 183 (1977); I. S.Bufkr, Acc. Chem.
Res. 10, 359 (1977).
[31 H. Werner, K . Leonhard, C. Burschka. J. Organomet. Chem. 160, 291
(1978).
[4] H. Werner, 0. Kolb, Angew. Chem. 91, 930 (1979); Angew. Chem. Int.
Ed. Engl. 18, 865 (1979).
[5] H. Werner, W. Hofmann,Chem. Ber. 120, 3481 (1977).
[61 H. Werner. R. Feser, Angew. Chem. 91, 171 (1979); Angew. Chern. Int.
Ed. Engl. 18, 157 (1979).
171 CI9H32CoPS(M,=382.5), monoclinic, space group P2,/c, a=947.6(3),
b= 1400(1), c= 1541.5(5) pm, B= 100.31(3)", V=2012x lo6 pm',
pCdIc=1.26 g/cm3, Z = 4 ; 3126 reflections (2"<20C48°, M o K ,
h=71.069 pm, graphite monochrornator, Syntex P2,/XTL); heavy atom
method, R,=0.073, R2=0.071 for 2214 structure factors, &>4.20(Fo).
[8] F. Carre. G. Cerueau, E. Colomer, R . J. P. Corriu, J. C. Young, L. Ricard,
R . Weiss, J. Organomet. Chem. 179, 215 (1979).
191 a) U. Befirens, F. Edelmann, J. Organomet. Chem. 118, C41 (1976); b) M .
Green, R. B. L. Osborn, E G. A. Stone, J. Chem. Sac. A 1970, 944.
Bis(tetrapheny1phosphonium) Hexadecaphosphide,
a Salt Containing the Novel Polycyclic Anion
By Hans Georg von Schnering, Victor Manriquez, and
Wowgang Honld'l
d
Fig. 1. Molecular structure of (2). projected perpendicular to the plane of the
CsHs-ring.
The bond lengths and angles between the Co atom and
the S=C=C group of the thioketene ligand verify presence of a CoSC three-membered ring. Whereas the CoS
bond Iength corresponds to that of a single bond, partial
594
0 Verlag Chernie GrnbH, 6940 Weinheim. I981
We have recently shownf2] that the molecular compounds P7R3, PI,R3and As7R3 (R=SiMe3) are formed in
surprisingly high yields on reaction of the salts Na,P,,
Na,P,, and Rb3As7with chlorotrimethylsilane. In the mass
spectra of PIIR3 and P,R,, besides a series of fragments
which differ by P2- or P4-units there also appear small
amounts of PI6R:. We have now been able to trap the
P:, anion corresponding to this species by reaction with
salts of large cations.
(Ph&PI6: Na3P7l3](3.16 g, = 11 mmol) is suspended in
500 ml of tetrahydrofuran (THF) which has previously
been freed of oxygen by treatment with Klbenzophenone.
[*I Prof. Dr. H. G. von Schnering, DipILChem. V. Manriquez,
Dr. W. Honle
Max-Planck-Institut fur Festkorperforschung
Heisenbergstr. I, D-7000 Stuttgart 80 (Germany)
0570-0833/81/0707-0594 $ OZ.fO/O
Angew. Chem. Inr. Ed. Engl. 20 (1981) No. 6/7
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analogous, thioketenen, metali, coordination, cs2, transitional, complexes, mononuclear
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