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Bis(3-allylnickel) 2 4 6-Heptanetrithionediate.

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Bis(q3-allylnickel) 2,4,6-Heptanetrithionediate
By Borislav BogdanooiC, Carl Kruger, and Oleg Kuzrnin'']
We report here the synthesis, characterization, and X-ray
crystal structure analysis of bis(q3-allylnickel) 2,4,6-heptanetrithiodiate (3), the first organometallic derivative of a 1,3,5trithiotriketone['l. Compound (3) was synthesized by reaction of 2,5-dimethyl-1,6,6ah4-trithiapentalene
with
bis(q3-allyl)nickel (2) or q'-allylnickel chloride. We have already prepared oxygen analogs of (3) via a different
route''].
(1) reacts with (2) in the molar ratio 1:2.0-2.2 in ether, tetrahydrofuran (THF) or toluene at 0 ° C within 8-12 h to
give intensely dark blue (in ether) or dark violet (in THF) solutions of (3). Compound (3) crystallizes from the ethereal
solutions at 0 or - 78 "C as violet crystals having a metallic
luster and can be isolated analytically pure in ca. 70% yield.
In the synthesis of (3) in toluene, stoichiometric amounts of
1,5-hexadiene (4) could by isolated from the reaction products in addition to (3).
Reaction of (1) with $-allyhickel chloride (molar ratio
1 :2) in THF at 0 "C affords (3) and nickel chloride; filtration
of the THF solution and subsequent crystallization from ether furnishes (3) in ca. 48% yield. A green compound, apparently analogous to (3),is formed on reaction of 2,5-diphenyl1,6,6ah4-trithiapentalene121
with bis(q3-allyl)nickel in T H F at
0 "C.
P
nated; very slight and insignificant deviations arise due to
steric hindrance of the neighboring opposingly oriented q'ally1 groups. This hindrance causes distortion of the planar
ligandI5lwith maximum deviations %fthe plane through all
atoms of t0.17 (C2) and -0.24 A (C6). S1 lies 0.898(8) A
above and S3 0.752(8) A below a plane determined by Nil,
S2, Ni2. The S ~-S- distances (3.361(1) and 3.342(1) A, respectively) enlarge as a result of complexation; as a consequence
there is no longer S--S bonding in the complex. Th,e large
distance between the neighboring Ni atoms (3.914(1) A) likewise indicates an absence of metal-metal bonding. Apart
from substantial broadening of the angles within the ring
system at C2, C3, C5, and C6 ( + 12 to 13" w.r.t. the free ligand), the bond geometry of the sulfur ligand is maintained.
Due to steric repulsion (CIO, Cll), or to a trans-effect of the
different types of sulfur atoms SI-S2 and S2---S3, the q3-allyl groups are bound asymmetrically to the nickel atoms.
Their inclinations to the S-Ni -S planes[61are 121.6 and
128.9 "C, respectively.
Consistent with X-ray structure analyses, the 100-MHz
'H-NMR
of (3) in CbD6at + 10 " C shows the signals of two equivalent, asymmetric q3-aliyi groups: a signal
for H,,,, at ~ = 5 . 1 5(m) and two signals each for H,, and
Hun,;at ~ = 6 . 9 8(d) and 7.17 (d) (Jmeso,yn=7
Hz) and 7.82 (d)
and 7.96 (d) (Jme.~o.on,r
= 14 Hz), respectively. The signals of
the methine protons and of the methyl groups of the trithiapentalene ligands appear as singlets at T = 3.02 and 7.59, respectively. An analogous spectrum with insignificant change
in position of the signals is obtained at - 50 "C in THF. On
increasing the temperature to 20 "C the signals of the synand of the anti-protons coalesce. In the 60-MHz spectrum of
(3) in C6D6 at 20 "C, the characteristic signals of symmetric
q3-allyl groups appear as a result of dynamic equilibration['],
the H,,, as a septet at ~ = 5 . 0 7and H,,, and H,,,, as sharp
doublets at T = 7.0 and 7.86, respectively.
(3) reacts with carbon monoxide (1 bar) in toluene at 0 to
20 "C with uptake of ca. 3 in01 CO/mol (3).OAdistillation of
the reaction mixture in uucuo, 37% of the nickel employed in
the reaction is recovered as Ni(CO),; (1) can be recovered in
46% yield from the distillation residue by crystallization from
THF at - 78 "C.
The synthesis of (3) from (1)and (2) with formation of 1,5hexadiene (4) and the reaction of (3) with CO to give
Ni(C0)4 and (I) respectively constitute C C coupling reactions and formal redox processes with participation of two
transition metal atoms.
A
Received: October 7, 1975 [Z 276b IE]
German version: Angew. Chem. Y I , 744 (1979)
Publication delayed at authors' request
CAS Registry numbers:
(3a), 71277-50-4; (Sb), 71277-51-5; (Sc), 71277-52-6; (Sd), 71277-53-7; (46).
71277-54-8; (4c), 71294-38-7; (4d), 71277-55-9; (5a). 25033-12-9; (Sb), 71264-954; (Sb), monothallium salt, 72277-56-0. (ScJ, 53182-88-0 (ScJ, monothallium salt,
.
71277-57-1; (Sd), 717-10-2: (6a), 71277-58-2; (6bJ, 71277-59-3; ( 6 ~ ) 71277-60-6;
(6d), 71277-61-7; (76). 71277-62-R; (7c). 71277-63-9; (7d), 11277-64-0; (Yo),
71264-96-5; (Yb), 71264-97-6; (Yc), 71264-98-7; (9d). 71264-99-8; bisiq5-allyl)nickel, 12077-85-9; $-allylnickel bromide, 12012-90-7
W
Fig. 1. Bond lengths [A] and angles in bis(q'-allylnickel) 2,4,6-heptanetrithionediate (3).
The structure of (3) (Fig. 1) was confirmed by X-ray structure analysi~[~I.
Both nickel atoms are square planar coordiProf. Dr. B. Bogdanovic, Priv.-Doz. Dr. C. Kruger, Dr. 0. Kuzmin [''I
Max-Planck-Institut fur Kohlenforschung
Kaiser-Wilhelm-Platz 1, D-4330 Miilheim-Ruhr 1 (Germany)
[**I DFG Fellow. Present address: Institute for Petrochemical Synthesis of the
Academy of Science of the USSR, Moscow (USSR)
['I
Angew. Chem. Inr. Ed. Engl. 18 (1979) No. Y
H. Vahrenkamp, Angew. Chem. 87, 363 (1975); Angew. Chem. Int. Ed. Engl. 14. 322 (1975); review of metal pentanedithionates: S. W Schneller. lnt. J. Sulfur Chem. B7.
295 (1972).
121 N. Loroc'h, Adv. Heterocycl. Chem. 13, 161 (1971).
131 B. BogdanouiC. M. Yus, Angew. Chem. 91.742 (1979); Angew. Chem. Int. Ed.
Engl. 18. 681 (1979).
141 (3) violet plates from benzene/pentane. Crystal data: o = 12.063(1).
b=15.728(2), c=8.704(1)
p=107.04(1)", space group P2,/c. 2 = 4 ,
pC.tL= 1.63 g cm-'. Refinement of the structural model derived by direct
methods converged with data corrected for absorption ( 1 887 reflections, hkl,
fikl, 100 reflections unobserved) lo R=0.039; several hydrogen atoms could
[I]Review of sulfur atoms as ligands in metal complexes:
0 Verlog Chemie, GmbH, 6940 Weinheim, 1979
A,
0S70-0833/79/0909-0683
$ 02.50/0
683
be located and refined by a difference Fourier synthesis; for the methodology
of measurement and calculation see: D. J. Brauer, C. Kruger, P. J. Roberts,
Y . - H . Tsuy, Chem. Ber. 107. 3706 (1974). Lists of atomic parameters and
structure amplitudes are available from the author (C. K.) on request.
151 I? Leung, S. C. Nyburg, Chem. Commun. 1969, 137; L. K. Hansen, A. Horduik, Acta Chem. Scand. 27, 411 (1973).
[6] B. L. Burnerr, C. Kriiger, J . Organomet. Chem. 77, 407 (1974).
[7] We thank Professor E. C. Hoffmann and G. Schroth for recording and interpreting the 'H-NMR data.
[XI C. Wrlke. B. Bogdanovic, P. Hardt, P. Heimbach, W. Keim, M . Kroner, W.
Oberkirch, K. Tanuka, E. SteintCcke, D. Walter, H. Zimmermunn, Angew.
Chem. 78, 157 (1966): Angew. Chem. Int. Ed. Engl. 5, 151 (1966).
An ortho-Palladated Complex
l,6,6aX4-trithiapentalene
of
bond distances to the palladium correspond to those already
reported in the literatureC61.
By virtue of the structure of (2), (1) is presumably a dimer
with bridging chlorine atoms. The formation of (1) from (3)
and PdClz represents an example of the so-called ortho-metalation reaction[" and can be compared with the ortho-palladation and -platination of diarylthioketones described by
AIperf'I.
C'-1
2,J-DiphenylL
Ill
J2
By Borislau Bogdanouit, Carl Kriiger, and Paolo Locatelli[']
The previously reported reaction of 2,5-dimethyl-I ,6,6aX4trithiapentalene with bis(q 3-allyl)nickel leading to bis(q3-allylnickel) 2,4,6-heptanetrithionediate1']prompted us to investigate the reactivity of 1,6,6ah4-trithiapentalene towards
other metallic and organometallic compounds.
2,5-Diphenyl-l,6,6aX4-trithiapentalene(3)['] reacts with
PdC12 in boiling methanol/benzene (10: 1) in the presence of
LiCl with loss of HC1 to give a violet, air-stable complex ( I )
(yield 97%).
According to an X-ray crystal structure analy~is'~],
compound (2), the triphenylphosphane adduct of (1) crystallizing
from toluene, is a square-planar palladium complex ( k 0.05
A) whose coordination geometry is determined by a C1-, a P-,
a S-, and a a-bonded phenyl C-atom.
Upon treatment of (1) with PdClz in the presence of LiCl
(molar ratio 1: 1 :3) in methanol/benzene (1 :1) no reaction
was observed even after five days' boiling under reflux.
Thus, under analogous conditions as for the synthesis of (I),
palladation of the second phenyl group could not be accomplished. In contrast, reaction of (1) with MoCIS (molar ratio
1:1) in boiling toluene[91quantitatively afforded a violet
complex of the composition [(1).MoCl3Ix of presently unknown structure. Thus, the palladium compound ( I ) is suitable as starting material for the synthesis of complexes containing several different metal atoms.
Procedurer"]
LJ
CO
Fig. 1. Bond lengths [A] and angles in the complex (2).
The interaction of only one sulfur atom of the ligand with
palladium leads to removal of the non-bonding
in (3) and to rupture of a S--S bond. Whereas the S-S distances in (3) are 2.362 and 2.304['l, the S -S bond remaining
in complex (2) is shortened to 2.067. This is accompanied by
a disruption of the origin:l planarity of the ligand with formation of planar (+ 0.01 A) subunjts (A, B, C, D; deviations
from the best plane each kO.01 A) and an increase in the
double bond character of the C1-C2 bond. The metallaheterocycle B is oriented along the S1 -C6 vector (159"); the
['I
Prof. Dr. B. Bogdanovic, Priv.-Dor. Dr. C. Kriiger. Dr. P. Locatelli
Max-Planck-Institut fur Kohlenforschung
Kaiser-Wilhelm-Platz 1, D-4330 Mulheim-Ruhr 1 (Germany)
[**I
[**I Present address: Istituto di Chimica delle Macromolecole del C.N.R.
Via A. Corti 12, 1-20133 Milano (Italy)
684
0 Verlug Chemie, GmbH, 6940 Weinherm, 1979
Synthesis of (1): To a suspension of (3) (3.10 g, 9.94
mmol)['] in methanol (230 ml) and benzene (25 ml) was added 1.76 g (9.92 mmol) PdC12 and a solution of 1.33 g (31.3
mmol) LiCl in 20 ml methanol. The stirred suspension was
heated for 3 h under reflux, and, after cooling to room temperature, the product was collected on a G3 filter. The mother liquor was shown to contain 93.6% of the liberated HCl by
acidometric titration. The residue was washed with methanol
and ether and dried at l o p 3 torr; the yield of (1) (m.p.
304 "C, dec.) was 4.38 g (97%). (1) is soluble in pyridine, morpholine, and chloroform, but sparingly soluble in pentane,
benzene, ether, ethanol, and tetrahydrofuran.
Synthesis of (2): A mixture of (1) (0.36 g, 0.80 mmol) and
triphenylphosphane (0.21 g, 0.80 mmol) in ether is stirred for
18 h at room temperature; the violet precipitate which is
formed is filtered off, washed with ether, and dried at
torr. Yield of (2) (m. p. 203-205 OC): 0.50 g (87%).
Received: November 6, 1978 [Z 276c IE]
German version: Angew. Chem. 91, 745 (1979)
CAS Registry numbers:
( I ) , 71328-64-8; (21, 71264-59-0 (3), 1033-90-5; PdCL 7647-10-1
[ I ] B. Bogdunouic, C. Kruger. 0. Kurmin, Angew. Chem. 91, 744 (1979); Angew. Chem. Int. Ed. Engl. 18, 683 (1979). and references cited therein.
[Z] E. Klingsberg, J. Am. Chem. SOC.X5, 3244 (1963).
131 Crystal data: a=10.004(1), b= 13.826(3), c = 15.534(2)
a=65.35(1),
p = 81.69(1), y = 71.16(1)", V = 1848
2 = 2 , space group Pi, pLalc= f.52 g
cm - 3 ; 3426 reflections, 1757 unobserved, R = 0.059. The structural analysis
was hampered by randomly disordered solvent (toluene) in the general position and about an inversion center. The solvent was included with partial
occupation numbers in the final refinement of the structural model.
A',
0570-0833/79/0909-0684
$ 02.50/0
Angew. Chem. Int.
A,
Ed. Engl. I8 (1979) No. 9
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