close

Вход

Забыли?

вход по аккаунту

?

Nucleophilic Addition of Triphenylstannyllithium to Carbon Disulfide.

код для вставкиСкачать
H. Monteiro, M. Szwarc, ibid. 59, 1353 (1963); M. Matsuda, J. Jagur-Grodzmski, M. Szwarc, Proc. Roy. SOC.(London) A 288, 212 (1965); J. JagurGrodzinski, M. Szwarc, ibid. A 288, 224 (1965).
121 H. Hopff;H. Liissi, Makromol. Chem. 62, 31 (1963).
[3] G. Laftermann, H. Hocker, Makromol. Chem. 175, 2865 (1974). H. Hocker,
G. Laltermunn. J. Polym. Sci., Symp. 54, 361 (1976).
141 a) G Schulz, Dissertation, Universitat Maim 1979; h) H. Hocker, G. Schulz,
Dtsch. Pat.-Anm. (September 25, 1979). BASF.
[51 G. G. H. Schulz, H. Hocker, Makromol. Chem. 178. 2589 (1977).
[6] R. P. FOSS,H. W Jacobson, W H. Sharkey, Macromolecules 10, 287 (1977);
G. Beinerf, P. Lun, E. Franfa. P. Rempp, Makromol. Chem. 179, 551 (1978);
L. J. Fetters, C. W. Kamienski, R. C. Morrison, R. N. Young, Macromolecules
12, 344 (1979).
171 H. Gilman, F. K. Carfledge,Organomet. Chem. 2, 447 (1974).
(81 G. Schulz, H. Hocker, unpublished.
(AsPh&[WzNCllo], a p-Nitrido Complex Containing
Tungsten(v) and Tungsten(v1)
By Frank Weller, Wolfgang Liebelt, and Kurt Dehnicke"'
The only dinuclear F-nitrido complexes of transition metals hitherto reported in the literature were those of ruthenium(rv)[l.Z1and of osmium(~v)[',~~.
We have found during
attempts to synthesize the previously described
AsPL[WNCl4] complex[4]in acetonitrile that dark brown
single crystals of the composition ( A s P ~ ~ ) ~ [ W ~ (1)
N Care
~,~]
formed in a slow side reaction. As follows from elemental
analysis, IR spectrum and a crystal structure determination151, (1) is the first dinuclear p-nitrido complex of tungsten
containing two tungsten atoms in different oxidation states.
In the anion of (1) (Fig. 1) the WNW bridge is linear. The
centrosymmetric space group P2Jn precludes any definite
decision between a symmetric or asymmetric position of the
N atom between the W atoms since disorder of the crystal
might create the impression that the former applies. Under
this assumption the refinement affords the two WN distances
of 165.7 and 207.2 pm. Also in agreement with this is the IR
spectrum, in which two WN stretching vibrations are observed at 1015 and 944 cm-'.
A comparison with the WN bond lengths of the tetrameric
[WNC13.P0Cl3J4.2POC13f61 (Z), linked via stretched
WzN-W bridges, shows that also the long WN bond in (1)
profits from a d,p, overlapping. This multiple bonding also
manifests itself in the eclipsed position of the four equatorial
C1 atoms: The W atoms utilize the two d orbitals d,, and dyz
at right angles to each other for bond strengthening. As a result of the sterically demanding WN multiple bonds the
equatorial C1 atoms are shifted outwards a little (on average
7 pm), along the WNW axis. The W...W distance of 372.9
pm in (1) is markedly shorter than in (2) (386.0 ~ r n ) ' ~corre],
sponding to a Jahn-Teller stabilization of the tungsten(v).
An analogous W .._
W distance of 372.8 pm was found in the
complex (HNMe~)2[W408C18(OH2)4]
.2H20, in which tungsten(v) and tungsten(v1) are likewise coupled via linear
WOW bridges[''.
Received August 6, 1979 [Z 415 IE]
German version: Angew. Chem. 92, 211 (1980)
[I] W. P. Grfith, Coord. Chem. Rev. 8, 369 (1972); and references cited therein.
I21 M. Ciechanowicz. A. C. Skapski, J. Chem. Soc. A 1971, 1792; R. J. D. Gee. H.
M. Powell, ibid. A 1971, 1795.
131 K. W. Given, L. H. Pignolet, Inorg. Chem. 16, 2982 (1977).
141 K. Dehnicke, W. Kolitsch, Z . Naturforsch. B 32, 1485 (1977).
151 Crystal data: monoclinic, space group P2,/n, a=1063, b=l230, c=2013
pm, P=97", Z = 2. Single crystal diffractometer CAD 4 (Enraf-Nonius.
Delft), MOK-radiation, graphite monochromator w scan, 9 = 3-22", 1461 observed independent reflections, Patterson methods, R = 4.9%.
161 W.Musterle, J. Striihle, W. Liebelt, K. Dehnicke, Z . Naturforsch. B 34, 942
(1979).
[7] Y. Yeannin, J.-P. Lounnay, J. Livage, A. Nel, Inorg. Chem. 17, 377 (1978).
Nucleophilic Addition of Triphenylstannyllithium
to Carbon Disulfide
By Paul-Reiner Bolz, Udo Kunze, and Werner Winter[']
Triorganoelement anions of Group IVb elements, R3E1(R=Ph, Me; El=Si, Ge, Sn, Pb), are strong nucleophiles
and therefore should react readily with electrophilic heteroallenes such as C 0 2 , COS, CS2, R'NCO, and R'NCS according to
Fig. 1 Structure ofthe [W,NCl,o]2- ions with ellipsoids of thermal vibration (at
21 "C; 50% probability).
Bond lengths [pm]
Bond angles ["I
Wl-N
W2-N
W-CH
w-c12
w-c13
w-c14
w-c15
C12-W-CIl
C13-W-Cll
C14-W-CI1
C14-W-Cl2
C14-W-Cl3
C15-W-Cll
C15-W-CI2
C15-W-CI3
C15-W-CI4
N-W-CI1
N-W-CI2
N-W-C13
N-W-C14
N-W-CIS
165.7(71)
207.2(72)
242.616)
233.3(6)
228.0(6)
230.5(8)
232.5(6)
87.6(2)
85.8(2)
90.2(2)
177.2(3)
94.2(2)
89.5(2)
87.4(2)
173.1(3)
90.8(3)
176.7(18)
95.2(18)
9 2 317)
87.0(18)
92.5(17)
to give element-functional ligand systems which can be stabilized with Lewis acids (X@).Almost all such attempts have
hitherto failed, since formation of the stable di-element compounds, R3E1-ElR3, with reduction of the heteroallene predominates[". On the other hand, the reactions of carbonylmetalate ions[21and diorganoph~sphides[~~
with carbon disulfide (and other heteroallenes) demonstrate that the proposed
reaction route is fundamentally possible.
['I
Doz. Dr. U. Kunze [ '1, DipLChem. P.-R. Bolz
Institut fur Anorganische Chemie der Universilat
Auf der Morgenstelle 18, D-7400 Tiibingen (Germany)
Doz. Dr. W. Winter [ '1
Institut fur Organische Chemie der Universitat Tiibingen (Germany)
+
[*] Dr. W. Liebelt, Prof. Dr. K. Dehnicke, Dr. F. Weller
Fachbereich Chemie der Universitat
Hans-Meenuein-Strasse, D-3550 Marburg 1 (Germany)
220
0 Verlag Chemie, GmbH, 6940 Wernheim. 1980
[ '1 Author to whom correspondence
I' 'I X-ray structure analysis.
0570-0833/80/0303-0220
.$ 02.50/0
should be addressed.
Angew. Chem Int. Ed. Engl. 19 (1980). No. 3
We have now been able to show that a nucleophilic addition takes place on reaction of triphenylstannyllithium with
carbon disulfide. The initial product (1) can be trapped by
alkylation with methyl or ethyl iodide in tetrahydrofuran
(THE').
Crystallographically, ( 2 4 has a tetraphenyltin structure
exhibiting "ordered disorder"l6' in which the phenyl groups
with a population factor of 0.25 are replaced by methylthiothiocarbonyl ligands. An outstanding feature of this completely planar structural unit['] is that the S---C' bonds are,
within the limits of error, of equal length, thus suggesting
participation of the mesomeric resonance hybrid 11:
20 "c
After separation by column chromatography, the products
(2a) and (2b) can be crystallized from petroleum ether as airstable violet needles of m. p, 128-129 "C and 4 7 4 8 "C, re-
spectively, with the given composition.
With aryl halides such as iodobenzene or p-bromotoluene,
however, no substitution products could be detected, but
only bis(tripheny1tin) sulfide in small amounts. Attempted
nucleophilic addition of trimethylstannyllithium also failed;
apparently stabilization of the electron-rich initial product
by mesomerizable groups attached to tin is essential.
Procedure
Double the stoichiometric amount of CS2 is added dropwise to a stirred solution of Ph3SnLi[8J(16 mmol) in THF (50
ml), whereupon the solution becomes warm and turns reddish-brown in color. After cooling, Me1 or EtI is added in excess. Column chromatographic separation (silica gel, THF)
of the violet solution affords a red fraction and a dark brown
fraction. After removal of solvent and double recrystallization from petroleum ether the red fraction gives pure (Za)
(yield 60%) and (2b) (yield ca. 5%), respectively.
Table 1. Spectroscopic data of the substitution products (2a) and (2bj
Method
(24
IR (KBr) [cm- '1
(C=S), 1060 m
(C=S), 1048 s
2.74 (s, 3 H, CH,), 7.25- 1.28 (1, 3 H, CH,), 3.42 (4.
2 H, CH2), 7.24-7.72 (mc.
7.69 (mc, 15 H, C,H,)
15 H, CeH,)
427 [M-Et]+,
442 [ M + * [b]. 427 456
412
IM-CS]+',
351
[M-Me]', 398
[Ph,Sn]+
[M-CS]", 351
[Ph,Sn]+
314 (5000)
313 (5070), 532 (126)
'H-NMR (CDCI,)
S values
(26)
[w+.,
MS [a] ( '20Sn)
We1
[a] 70 eV, direct inlet.
benzene).
[b] Molecular mass, calc. 441.3, exp. 439 (osmometric in
It cannot be definitely decided from the spectroscopic data
(Table 1) whether the stannyl-substituted dithioformate (A)
or the isomeric dithiocarboxylate complex (B) is formed.
s
A
Ph3Sn- C
:
Received: July 16, 1979 [Z 418 IE]
German version: Angew. Chem. 92,227 (1980)
S
Ph&h/s)-R
B
S-R
Dithiocarboxylates of the structural type (B) are indeed
known[41(not of course, for R = Me, Et), but they differ very
little from the substitution products A in their physical properties. Therefore an X-ray structure analysis of (Za)was carried out['l, which confirmed the structural type A. ,
n
Fig. 1. Molecular structure of (2aj; Sn-C'=214+0.8,
C'-S'=164&2,
C'-S2=162+2,
C'-S2=184-r4
pm; angles around C ' : 120+1",
C'-S'-CZ=106t
1.5" (51.
Angew. Chem. Int. Ed. Engl. 19 (1980) No. 3
111 C. Tamborski, F. E. Ford, E. J. Soloski, J. Org. Chem. 28, 181 (1963); 28, 231
(1963); cf. 191.
(21 J. E. Ellis, R. W . Fennel, E. A. Flom, Inorg. Chem. IS, 2031 (1976).
131 J. KOP!R. Lenck, S. N . Olafsson, R. Kramolowsky, Angew. Chem. 88, 81 I
(1976); Angew. Chem. Int. Ed. Engl. 15, 768 (1976).
141 S. Kato, T. Kato, T. Yamauchi, Y. Shibahashi, E. Kakuda, M. Mizuta, Y Ishii,
J. Organomet. Chem. 76, 215 (1974).
151 Tetragonal, space group P42,c (Z= 2); a = 1 184, b=677 pm; 1200 reflections
with F a 3o(F), NONIUS C A D 4 (MOK.,, graphite monochromator); refinement: R = 0.0487 (isotropic, SHELX).
161 P. C. Chieh, J. Trotter, J. Chem. SOC.A 1970, 911.
171 I. S. Butler, A. E. Fenster, J. Organomet. Chem. 66, 161 (1974).
IS] H. Schumann, K. F. Thom, M. Schmidt, J. Organomet. Chem. I , 167
(1963).
(91 Note added in proof: The only reaction that has been reported is the addition
of carbon dioxide lo triorganosilyl- and germyl anions: A. G. Brook, H. G I man. J. Am. Chem. Soc. 76, 77 (1954); 77, 2322 (1955).
Photooxidation of the Ligands of
Bis(o-semiquinonediimine)nickel(n)
-platinum(Ir)'***
and
By Arnd Vogler and Horst Kunkely"]
All the photoredox reactions of transition metal complexes
examined so far involve direct participation of the metal"'.
We now report a photoreaction in which the ligands are oxidized while the oxidation state of the metal remains unchanged.
o-Hydroquinones and o-quinones['J, as well as o-phenylenediamine and o-quinonediiminer3Jform transition metal
complexes which can undergo mutual interconversion by several reversible one-electron redox reactions via stable semiquinone and semiquinonediimine species, respectively. The
complexes M[o-C6H4(NH2)]5having M = Ni, Pd, and Pt then
occur with charges z= - 2, t- 1, 0, - 1, and - 2c31.The end
members with z= + 2 and - 2 contain the ligands o-qui['I Prof. Dr. A. Vogler, Dr. H. Kunkely
Institut fur Chemie der Universitat
Postfach, D-8400 Regensburg (Germany)
[**I This work was supported by the Deutsche Forschungsgemeinschaft and the
Fonds der Chemischen Industrie.
@ Verlag Chemie, GmbH, 6940 Weinheim, 1980
0570-0833/80/0303-0221
$02.50/0
221
Документ
Категория
Без категории
Просмотров
0
Размер файла
222 Кб
Теги
triphenylstannyllithium, additional, carbon, disulfide, nucleophilic
1/--страниц
Пожаловаться на содержимое документа