вход по аккаунту


CS2- and CS3-Bridged Transition Metal ComplexesЧDirected Synthesis of Metallodithiocarboxylato-Metal Complexes.

код для вставкиСкачать
to the metal by H,. 3 ml of this stock solution was added to
100 ml of the reaction mixture; this corresponds to 1.4 mg
Ru/100 ml or
mol/l.-The production of colloidal Pt
and Pd is described in ref. Is].
Received: March 30. 1979:
revised: June I . 1979 [Z 264 I E ]
German version: Angew. Chem. 91. 659 (1979)
CAS Registry numbers:
Ce. 7440-45-1: Pd. 7440-05-3: Pt. 7440-06-4: Ru. 7440-18-8; H, 12385-13-6: 0.
17778-X0-2. Ru(bpy)i ’ . 1515X-62-0: EDTA. 60-00-4 methylviologen, 1910-42-5:
poly(viny1 alcohol). 9002-XY-5
[ I ] a ) J . Kiwi, M. Grarzel, Angew. Chem. YO, 900 (1978): Angew. Chem. Int. Ed.
Engl. 17. 860 (1978): b) Chimia, in press; J Am Chem. Soc.. in press.
121 A . h c r i n i , L. Mormo, Z. Anorg Chem. 32. 55 (1902); B. V. Kurwkin. 7 S.
Dzhabieo. A . E. Shilui,, Dokl. Akad. Nauk SSSR 238, 620 (1977); J. M Lehn.
J. P S a u i q e . Nouveau J. Chim. 1.449 (1977)
131 a ) K. Kalyanusundaram, J. Kiwi. M. Grarzel, Helv. Chim. Acta 61, 2720
(197X): A. Murudpour. E. Amoui,al, P Keller. H. Kugon. Nouveau J . Chim. 2.
547 (1978)
141 KMX-6 Chrornatix instrument: see Chromatix Application Note LSH (lY78).
560 Oakmead Parkway. Sunnyvale. Calif. 94086 (USA).
[S] Quantitative oxygen analysis was performed with an “end-0-mess” model D
m t r u m e n t (Friedrichsfeld GmbH, Mannheim. Germany). The method of
detection is selective. being based on the response of. the potential of a Zr/
ZrO, (solid electrolyte) electrode to 02.
[h] G Mie. Ann Phys. (Leipzig) 25. 377 (1YOR).
171 M. Puiirbui.rt Atlas d’Equilibres Electrochimiques. Gauthier-Villars, Paris
[XI M. H Miles, E. A . Klaus. B. P. Gunn. J R. Locker. W. E. Serafin. Electrochim. Acta 23, 521 (1978).
[Y] L. D. Rampino. F. E Nurd. J. A m Chem Soc. 63. 2745 (1941).
reacts with (4a) in tetrahydrofuran (THF) to give the CS2bridged dinuclear complex (5). A platinum complex (6) having two of the same “ferriodithiocarboxylatochelateligands”
can be obtained as red crystals on reaction of (3) with PtCI,
in the molar ratio 2 :1 .
In 1975 the preparation and X-ray characterizationl’l of a
dinuclear CS2-bridged platinum complex was reported combining the structural features of a dithiocarbenemetal ( I ) and
a metal S,S’-dithiolate (2). Attempts to prepare other compounds having the same interesting kind of linkage proved
Studies on the basic metal/heteroallene/acid or Lewis acid
metal system[21have now enabled us to prepare a series of
such stable dinuclear and trinuclear “metallodithiocarboxylato-metal complexes”. The a d d ~ c t ‘obtained
from carbon
disulfide and sodium dicarbonyl(cyclopentadieny1)ferrate
Prof. Dr. W. P. Fehlhammer. Dr. A. Mayr. DipLChem. H. Stolzenberg
lnstitut fur Anorganische Chemie der Universitat Erlangen-Nurnberg
Egerlandstrasse I , D-8520 Erlangen (Germany)
[ * * I Isocyanide- and Heteroallene-Bridged Metal Complexes. Part 2. This work
was supported by the Deutsche Forschungsgemeinschaft and the Fonds der
Chemischen 1ndustrie.-Part I : [Zb].
0 V e r l q Chemie, GmbH. 6940 Weinheim. 1979
f8a). M = Pt; ( 8 b ) , M = P d
By Worf Peter Fehlhammer, Andreas Mayr, and Heribert
IR spectra [(KBr) (5): 2042, 1998 vs [v(CO)], 870 s
[ v(CS,)];(6): 2028, 1973 vs [ u(CO)], 870 s [ v(CS,)] cm - $1, elemental analysis, molecular weight determination, and synthesis support the proposed str~ctures[~l.
Another electron-rich adduct which, like (3), should be
able to react with electrophilic metal compounds is q*-(carbon disulfide)bis(triphenylphosphane)platinum (7) described in 1966 by Wilkinson et all4’.Indeed, its reaction in
dichloromethane with the chlorine bridged complex cation
(4a) immediately and quantitatively leads to Angelici ’s complex (Sa) which was formed in an unexplained manner on deThe tendency of
composition of [(Ph3P)2Pt(C1)(CS)]BF4“1.
formation of the hererometallic dinuclear complex (8b), on
the other hand, is much less pronounced.
CS2- and CS3-Bridged Transition Metal ComplexesDirected Synthesis of MetallodithiocarboxylatoMetal Complexes[**]
c p ( C 0 ) ~eF- C j . /Pt, ~;C-Fe( CO),Cp
Prolonged times are also required for reactions of
(Ph3P),Pt(CS2) with neutral dichlorobis(tripheny1phosphane)nickel(rI), -palladium(n), and -platinum(II); the nickel
and palladium compounds exclusively giving respectively
the red-brown and orange neutral complexes (9), whereas
cis-(Ph,P),PtCI, also gives rise to the yellow cationic complex (10) which in solution readily eliminates triphenylphosphane to form (9) with M = P t .
A remarkably constant band pattern (ca. 930 s, 870 m [v,,,
v,(CS,)] cm-I), which seems to be characteristic of the
Pt CS,M group, is found in the IR spectra of the complexes
(8) -(1 0) .
The “P-NMR spectra prove the trans configuration at the
C-bonded platinum and the equivalence of the cis-triphenylphosphane ligands on the chelated metal in (8) and (lo),
which in turn provides evidence for the equivalent nature of
the two S ligands in lrans position.
We suspect the first step of formation of these platiniothiocarboxylato complexes to consist in coordination of the electropositive metal to the “exo-sulfur atom” of (?), which is
followed by intra- or intermolecular halogen transfer between the metals with concomitant opening of the PtCS
three-membered ring and chelatization at the entering metal.
In the absence of mobile halogen ligands in the Lewis acid
metal component the reaction with (7) ceases at the stage of
primary coordination. The complexes (11) obtained in high
0570-0~33/7Y/OX~)X-U626$ 02 5O/U
AnKeu. Chem I n [ . Ed. Engl. 18 (1979) Nu. X
(2) and CsHs(PMe3)Co(SCS)Mn(COj2CsH5(3) in which the
CS2 ligand bridges two different metal atoms[21.The carbon
disulfide moiety of (2) and (3) is rigidly fixed [as in (A)], i. e.
isomerization according to
(111, M = C r , W
yield from (7) and M(CO)5THF (M=Cr, W) apparently
contain the same kind of CS2 bridge as considered for the
known compounds
and C~(M~,P),CO(SCS)C~(CO)~['~.
A variant of the basic metal/CS2 interaction is found in
the reaction of Na2Cr(CO), with CS2 and (Ph3P),PtC12.The
compound isolated as yellow crystals (37% yield) on work-up
is not an isomer of (11) as would be expected from the method of preparation. Instead it contains more sulfur and is to be
formulated as the trithiocarbonate-bridged species (12) (1R
(KBr): 1040 m [v(CS,)] cm-I). CS, bridge formation has
also been observed on reaction of pentacarbonylmanganate( - I) and -rhenate( - I ) with CS2['].
CS2 (0.15 ml, 2.5 mmol) in T H F (50 ml), and then
(2.1 g, 1.25 mmol), are added to a 0.1
M solution of Na[CpFe(CO)2] in T H F (25 ml) [prepared
from [CpFe(CO)2]2(3.54 g) and NaK,% (1.35 ml) in T H F
(200 ml)] at -70 "C under N2. A clear light-orange solution
arises on warming to 0 "C. The solvent is evaporated at this
temperature, the residue dissolved in dichloromethane (ca.
50 ml), and the solution filtered through cellulose. After concentration of the filtrate to half the volume, the product crystallizes on addition of n-pentane. The yellow platelets of (5)
(yield 76%, dec. pt. 170°C) can be stored indefinitely at
Received March 9. 1979 [Z 265 LEI
Angew Chem 91, 661 (1979)
[ I ] J. M. L i s p . E. D. Dobrzvnski, R. J. Anpelici, J. Clurdy, J . Am. Chem. Soc. Y7.
656 (1975).
(21 a ) W f. Fehlhummer. A. M a y , M . Ritter, Angew. Chem. HY. 660 (1977): Angew. Chem. Int. Ed. Engl. 16. 641 (1977): b) W. f. Fehlhammer, A . Maw. C.
Christiun. ibid. 90. 920 (1978) and 17. 866 (1978).
[3] In contrast, (3) and CpFe(C0)21form a CS,-bridged complex in which ferriodithiocarboxylate functions as a monohapto S ligand: J. E. Ellis, R. W.
Fennel/. E. A . Nom, Inorg. Chem. IS, 2031 (1976).
141 M. C. Burrd, C. Wilkinson. J. Chem. SOC.Chem. Commun. IY66. 514.
[ S ] M. Herherhold, M. Suss-Fink, C. C Kreiter. Angew. Chem. 89. 191 (1977);
Angew Chem. Int. Ed. Engl. 16, 193 (1977).
[6] U . Oehmichen. T. G. Southern. H. LeBozec, P. DixneuL J . Organomet. Chem.
1.76, C29 (1978).
171 H. Werner, K Leunhard, Ch. Bursrhku. J. Organomet. Chem. 160. 291
[ X I I. B. Benson. J. Hunt. S. A. R. Knox, V Oliphanr, J. Chem. SOC.Dalton
Trans. 107X. 1240.
(91 W. Beck. K. 1:. Werner, Chem. Ber. 104, 2901 (1971): C. Euborn. N . Furrell. J.
L. Murphr. A . fidrock. J. Chem. Soc. Dalton Trans. 1476. 58.
is not detectable.
We expected a non-rigid structure (i.e. a flexible CS2
bridge) for the analogous symmetrical dinuclear complex
having ML, = Co(PMe,)C5Hs. Herberhold et al.[']observed a
flexibility of this kind in C5H5(C0)2Mn(SCS)Mn(C0)2CsH5
which is completely frozen in at low temperature (210 K).
However, reaction of (1) with C5H5(PMe3)Co(kC0)2Mn(CO)C5H4Me(4), which we used as a source for the
16-electron fragment CsH5CoPMe3[41,
followed a completely
different course. Instead of the expected product
we obtained the trinuclear complex (C,H,),Co,(CS)(S) (5) as black crystals that
are only slightly air-sensitive. On reaction of (1) and (4) in a
molar ratio of 1 :2, compound (5) is isolated in ca. 80%
Crystal structure analysisl'l shows that the three cobalt
atoms form an equilateral triangle with the two bridging ligands located above and below its midpoint. An analogous
trigonal-bipyramidal arrangement of the skeletal atoms occurs in the complexes (C5Hs)3C03(C0)(0)'61 and
(CsHs),Co,(CO)(S)r'~, which are obtained in very low yield
by photolysis of C5H5Co(C0)2 and by reaction of
CsHsCo(C0)2with S(N-tBu),, respectively.
(5) behaves as a Lewis base and reacts smoothly with methyl and ethyl iodide and with Cr(C0)5THF to give the complexes (6)-(8). The sulfur atom of the CS bridge is apparently the site of maximum nucleophilicity, in accord with the
results of X-ray crystal structure analysis (relatively long
C S distancel5l).
(C5H5),Co,(CS)(S); The First Complex to Have a 11,Thiocarbonyl Bridge'']
By Helmut Werner and Konrad Leonhard[']
The complex C5HS(PMe3)Co(q2-CS,)(1) readily obtained
from CsHsCo(PMe3j2and CS2 reacts with the tetrahydrofuran (THF) adducts Cr(CO)STHFand C5HsMn(C0)2THFto
give the dinuclear complexes CSH5(PMe3)Co(SCS)Cr(CO)s
I*]Prof. Dr. H. Werner. Dr. K Leonhard
Institut fur Anorganische Chemie der Universitit
Am Hubland. D-8700 Wurzburg (Germany)
Angeu Chem I n l . Ed. t n g l . I H ( I Y 7 Y l Nu. X
(61, R
(7), R
= Et
A notable feature of the synthesis of (5) is the ease with
which the carbon disulfide coordinated very strongly in (1) is
cleaved to CS and S. Numerous carbon monosulfide (or
thiocarbonyl) complexes having terminal CS ligands are
known['], and several dinuclear compounds of manganese,
0 Verlug Chemie, GmbH, 6Y40 Wemheim, 1Y79
OS?O-OX33/ 7Y/OXOX-O627 $ 02.50/0
Без категории
Размер файла
227 Кб
metallodithiocarboxylato, synthesis, complexesчdirected, metali, bridge, cs3, cs2, transitional, complexes
Пожаловаться на содержимое документа