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Novel 3 -Sulfur Double-Ylide Chromium Complexes by endo-Hydride Addition to Cationic (6-Thiabenzene 1-Oxide)chromium Complexes.

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Novel q3,a-Sulfur Double-Ylide Chromium
Complexes by endo-Hydride Addition to Cationic
(I6-Thiabenzene 1-0xide)chromium Complexes**
By Lothar Weber* and Roland Boese
The unsaturated hydrocarbon ligands of cationic transition-metal complexes have electrophilic character and add
nucleophiles via kinetically controlled exo-addition1”.
In the reaction of the cations la-d with LiBHEt3 we
observed the rare case of endo-addition of hydride to a 71bonded organic ligandI3I. As a result compounds 2, having
a novel double-ylidic ligand, are formed from the cationic
(h6-thiabenzene 1-oxide)chromium complexes [(1-0x0-h6thiin)chromium) complexes] lI7 ].
r
-0
P
B
H3c/swR2
LiBHEt,
H3C/‘&’
PF6@
I
-
R‘
\/
H
Cr(C0)2N0
C r(C 0 ) z N O -
la-d
a
b
C
d
R’
R2
Ph
Ph
Me
Ph
Me
Me
t Bu
Ph
The exo-position of the 3-tert-butyl group in 2d, determined by X-ray structure analysis (Fig. l), establishes
endo-addition of the hydride. In addition, the doubleylidic heterocycle is coordinated as a 4--6q,20 ligand to
the Cr(CO),(NO) fragment.
Q
In contrast to phosphorus ylides, double-ylide ligands
with sulfonium centers are rare. Compound 2d is the first
complex having such a ligand which has been characterized by X-ray structure analysis191.
Received: February 7, 1983;
revised: March 28, 1983 [Z 270 IE]
German version: Angew. Chem. 95 (1983) 510
The complete manuscript of this communication appears in:
Angew. Chem. Suppl. 1983, 620-630
CAS Registry numbers:
la, 76831-13-5, lb, 85762-74-9, lc, 85762-76-1, Id, 85762-78-3, Za, 8576279-4, Zb, 85762-80-7, 2c, 85762-81-8, 2d, 85781-10-8, syn-tricarbonyl(l,3-dimethyl-5-phenyl-h6-thiabenzeneI-oxide)chromium(O), 85762-82-9, syn-tricarbonyl(l,3,5-trimethyl-h6-thiabenzene I-oxide)chromium(O), 85762-83-0,
syn-(3-tert-butyl-l-methyl-5-phenyl-h6-thiabenzene1-oxide)tricarbonylchromium(O), 85762-84-1.
2a-d
1, 2
B
A
=13
c7
[I] S. G. Davies, M. L. H. Green, D. M. P. Mingos, Tetrahedron 34 (1978)
3047; P. L. Pauson, J. Organomet. Chem. 200 (1980) 207.
[3] endo-Addition of hydride has been reported in only one other case: A. J.
Birch, I. D. Jenkins in H. Alper: Transition Metal Organometallics in Organic Synthesis. Vol. 1. p. 69, Academic Press, New York 1976.
[4] Zd: Space group Pbcn; a=903.0(1), b = 1763.3(2), c=2406.6(4) pm,
V=3.832(1)x lo9 pm’; Z = 8 , R=0.048. Further details can be obtained
from the Fachinformationszentrum Energie Physik Mathematik, D-7514
Eggenstein-Leopoldshafen 2, by quoting the depository number CSD
50427, the names of the authors, and the journal citation.
[7] The term double-ylides signifies not only sp5cies which contain two carbanion functions on one onium center (C-E-C), but $so thyse having
the combination of two onium carbanion moieties (6-E-C-E).
This applies, by analogy, also for triple-ylides.
[9] The sulfur double-ylide Iigands [(CH2)2S(0)CH3]- and [(CH2)2SCH3]have been described: 0. I. Kolodyazhnyi, Zh. Obshch. Khim. 45 (1973)
704; H. Schmidbaur, W. Richter, Z . Anorg. Allg. Chem. 429 (1977) 222;
H. Schmidbaur, W. Kapp, Chem. Ber. I05 (1972) 1203; P. Bravo, G. Fronza, G. Ticozzi, J. Organomet. Chem. 118 (1976) C78; F. 9. McCormick, J.
A. Gladysz, ibid. 218 (1981) C57.
Addition of Alkanethiols to Diketenea Correction
Fig. 1. Structure of the complex 2d in the crystal 141. Selected distances [pm]
and angles I”]: Cr-S 283.9(1), Cr-C2 221.9(4), Cr-C4 224.7(4), Cr-C5 219.3(4),
Cr-C6 217.1(4), S-04 145.6(3), S-C2 171.0(4), S-C6 169.8(4), S-C7 177.9(4),
C2-C3 152.2(5), C3-C4 150.3(5), C4-C5 138.2(5), C5-C6 145.6(5); C2-S-C6
95.0(2), S-CZ-C3 114.9(3), C2-C3-C4 103.2(3), C3-C4-C5 123.8(3), C4-C5-C6
121.8(3), C5-C6-S 117.8(3).
The q3-allyl moiety is considerably distorted, and hence
the bond relationships can be reproduced best by the resonance structures A and B.
[*I Priv.-Doz. Dr. L. Weber, Dr. R. Boese
[**I
498
Institut far Anorganische Chemie der Universitat
Universitatsstrasse 5-7, D-4300 Essen 1 (Germany)
Transition-Metal Sulfur Mide Complexes, Part 19. This work was supported by the Deutsche Forschungsgemeinschaft and the Fonds der
Chemischen 1ndustrie.-Part 18: L. Weber, Chem. Ber. 116 (1983)
2022.
0 Verlag Chemie GmbH, 6940 Weinheim, 1983
By John G. Dingwall* and Brian Tuck
Hertenstein“’ has recently reported that the acid catalyzed addition of alkanethiols to diketene gives B-lactones
1, in contrast to the previously reported formation of the
crotonic acid derivative 2a from the acid catalyzed addition of thiophenol to diketeneI2’.The thermal stability and
spectral data reported by Hertenstein are inconsistent with
the literature value^'^.^^ for 4-(alkylthiomethyl)oxetan-2ones 1 and with our own observations. The IR and the
NMR data (Table 1) led us to believe that the products isolated were the thermally stable isomeric y-lactones 3, one
of which, 3a, was previously observed[31as a product of the
thermal decomposition of B-lactone l a .
[‘I Dr. J. G. Dingwall, Dr.
9. Tuck
Central Research Laboratories Ciba-Geigy (UK) Limited,
Tenax Road, Trafford Park, Manchester MI7 IWT (England)
0570-0833/83/0606-0498 $02.50/0
Angew. Chem. Int. Ed. Engl. 22 (1983) No. 6
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thiabenzene, oxide, sulfur, additional, hydride, double, endo, novem, complexes, ylide, cationic, chromium
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