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Bis(-1 5-cyclooctadiene)cobaltlithium.

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shows that the strength of the arsenic-chlorine bond increases
[2.04+2.59 mdyne/A] in the transition AsCl3+AsOCI3,
exactly as in the system PCI3+POCl3 [2.34-+2.98 mdyne/A].
The compounds are therefore also related in the details of
their bonding.
AsOCI3 slowly decomposes at -25"C, and much more
rapidly at ca. O'C, with formation of As2O3Cl4.
3 AsOC1,
+ C12 + As20,C14
+ AsC1,
This compound is stable up to 150°C. Its vibrational spectrum reveals disappearance of the As=O double bond, thus
ruling out the structure P2O3CI,[Cl2P(O)-O-(0)PCl2].
It is also not volatile, but decomposes above 200°C with loss
of AsCI3+Cl2 to give "AszOS"-a process which can be
readily monitored in the mass spectrum.
As203CI4 is obviously a polymer. I t can be isolated in
analytically pure form, but is X-ray amorphous. No crystallization takes place even after 50 hours' annealing at 120°C.
In this compounds arsenic is doubtless pentacoordinated, or
hexacoordinated by way of chlorine bridges.
Recrystallization of (3) from ether gives
(COD)2CoLi(THF)2( 3 a )
and on addition of dimethoxyethane (DME), yellow crystals
of
(COD)2CoLi(DME)3( 3 h )
are obtained. The new cobalt complexes ( 3 ) were characterized
by metal analyses and by their reaction with CO, in which
four C O per LiCo were consumed with displacement of COD.
The IR spectrum (THF) shows all four double bonds are
complexed both in (3) and in the isoelectronic compound ( I ) .
The 'H-NMR spectrum ([D,]THF, RT) of (36) displays
two broad signals at ~ = 7 . 5 7(--CH2) and ~ = 7 . 9(CH=CH),
intensity ratio 2 : 1, for the cyclooctadiene.
Received: September 14, 1976 [Z 559 IE]
German version: Angew. Chem. 88, 806 (1976)
CAS Registry numbers:
AsOCIJ. 60646-36-8: ASCIS,7784-34-1 : 0 s . 10028- 15-6: A s ~ O ~ C I60646-37-9
J.
[ I ] W Dr/iiiicke and J . Weidlriri. Z. Anorg. Allg. Chem. 342. 225 (1966).
[2] K . Seppelt. Angew. Chem. X8. 410 (1976): Angew. Chem. Int. Ed. Engl.
15. 377 ( I 976).
[3] Calculation according to the method ofJ. Becher and R . Motre.+,Spectrochim. Acta, Part A, 23, 2449 (1967).
Bis(q-l,5cyclooctadiene)cobaltlithium
By Klaus Jonas, Richard Mynott, Carl Kriiger, Janine C . Sekutowski, and Yi-Hung Tsay[*l
Nickel(o)-olefin complexes which d o not contain
pronounced acceptors as ligands form defined dilithium-nickel-olefin complexes with lithiom[']. We now wish to report
a further example of this class of compounds.
Reaction ofmetallocene complexes (C5H&M with an alkali
metal leads to release of the two C5H5 rings and formation
of alkali metal-CsHS and elemental transition metal[21. In
the case of cobaltocene and nickelocene we have now found
that the deposition of transition metal is suppressed on addition of cyclooctadiene (COD). The new cobalt complex (3)
and the known nickel complexes (1)[31 and (2)"' can then
be isolated in high yield [ e . g . (3): 85 %]['I.
(CsH5)zCo
LI. COD
C ~ H ~ C O C O+D L I C ~ H ,
THF. 0°C
THF. 0°C
1
2 LI. COD
(COD)ZCoLi(THE'), 1 3 )
2 LI.2 COD
(C,H5)2Ni
THF. 0°C
(C0D)zNi
+
+
L1C5H5
2 LiC5H,
(1)
THF.0-C
1
2 LI
(COD)2K~Li2(THF)4
(2)
[*I
Dr. K. Jonas ['I, Dr. R. Mynott [**I, Dr. C. Kruger [***I, Dr. J. C.
Sekutowski [***I [****I,and Dr. Y.-H. Tsay [***I
Max-Planck-Institut fur Kohlenforschung
Lembkestrasse 5. D-4330 Mulheim (Germany)
['I
T o whom correspondence should be addressed.
[**] '-'C-NMR spectra.
[***I X-Ray structure analysis.
[****] J . C S. thanks the Deutsche Forschungsgemeinschaft for a study
grant.
A i i g w . Climni. I i i r
Ed. Engl.
1 Vol. 15 ( 1 9 7 6 ) No.
12
Fig. 1. Crystal structure of (COD)ICoLi(THF), (30)
Figure 1 shows the result of an X-ray structure analysis
of ( 3 a ) [a=14.094(1), b= 18.799(3), c = 17.500(3)&
/?=97.74(1)", space group C2/c, 3219 reflections, 1485 unobserved, R =0.064]. The bond angles at the cobalt atoms diverge
'pairwise so markedly from an ideal tetrahedron (such as occurs
in the isoelectronic complex Ni(COD)2141)that the molecule
is better described as a trigonal bipyramid. Its equatorial
positions are occupied by Li and by one double bond each
of the two olefinic ligands [ C l - C S : 1.413(7)A; C 1 1 4 1 8 :
1.419(7)A]. Owing to bridging with the axial positions of
the Co [C4-C5: 1.391(8)A; C 1 4 4 1 5 : 1.401(8)A] the COD
ligands assume a highly distorted boat conformation. Short
L i - C distances ( L i - C I ; L i - C l 1) indicate strong ion-pair
interaction['] between the Li atom in a tetrahedral environment and C atoms of the double bonds in equatorial positions.
The L i - C o distance [2.654(8)A] is significantly longer than
the sum of the respective covalent radii.
The 13C-NMR spectrum[61of ( 3 a ) at room temperature
shows only two signals for the C O D at 69.1 and 34.7ppm
([D,]THF) or at 69.5 and 33.7 ppm ([D,]toluene). On cooling a
solution in [DJTHF the C O D signals become much broader
only below -60°C. In [D,]toluene, on the other hand, broadening begins at O'C, and at -77°C eight signals of approximately equal intensity are observed. Four of the signals lie
at 79.6, 74.3, 71.5, and 50.7 ppm (all d, average chemical shift
69.0ppm), and the other four at 38.3, 38.0, 30.2, and 29.0ppm
(all t, average chemical shift 33.9 pprn). These temperature
effects are reversible. The 13C-NMR spectrum of ( 3 a ) in
[D8]toluene at -77°C is compatible with the structure of
the crystalline complex: owing to the equatorial position of
the Li atom on the cobalt, four distinct pairs of olefinic and
aliphatic C atoms are expected. On raising the temperature
in [D8]toluene, the Li atom is found to undergo a shift in
767
the (COD)2Co group. The strongly solvating [Ds]THF accelerates this exchange.
Table I . Physical properties of complexes ( 3 )
Color
Received: September 20. 1976 [Z 560 IE]
German version: Angew. Chem. 88. 808 (1976)
CAS Registry numbers:
O,
I3C, 14762-74-4
(COD)zCoLi(THF)z,60718-95-8; ( C S H ~ ) ~ C1277-43-6;
- ..
(3h)
(31.)
[2]
131
[4]
[5]
161
[7]
K . Jorras. Angew. Chem. 87, 809 (1975): Angew. Chem. lnt. Ed. Engl.
14, 752 (1975): K . R. Porschkt., Dissertation, UniversitPt Bochum 1975.
D . S. Trfart and L . N I ~ I I O I NJ.F . Am. Chem. Soc. 79, 2746 (1957): H .
D . Frirz and L . Scltu/er. Chem. Ber. 97, 1829 (1964); C. E . Wrrr and
L . J . Baye, J. Inorg. Nucl. Chem. 26, 2099 (1964); A . B. B ~ o i n tand
H . R e i d . J . Org. Chem. 35, I191 (1970).
B. Bogdartovii. M . K r i j w r . and G. Wilkr. Justus Liebigs Ann. Chem.
699, 1 (1966); K . fischer, K . Jonas, and G . Wilke, Angew. Chem. 85,620
(1973); Angew. Chem. Int. Ed. Engl. 12, 565 (1973).
H . Dierks and H . Dietrich, 2. Kristallogr.. Kristallgeom.. Kristallphys.,
Kristallchem. 122. 1 (1965).
D . J . Brairer. C. Kriigrr. P . J . Roherrs, and Y - H . Tsa?., Angew. Chem.
XX, 52 (1976); Angew. Chem. Int. Ed. Engl. IS, 48 (1976); R. Zergrr,
W Rhirir, and C. Strick?., J . Am. Chem. Soc. Y6. 6048 (1974).
The "C-NMR spectra were recorded at 25.2 MHz. Chemical shifts
relative to TMS. multiplicities characterized by off-resonance procedure
as d =doublet and t=triplet.
We have also prepared isoelectronic complexes of iron by the same
method, and are investigating further compounds of this type formed
by other transition metals.
-.
I R (KBr)
[cm-'1
vC=S
~.
..
.- .
.
198-202 [a]
206-209 [b]
153-156 [c]
orange
red
rust red
(3N)
~~
[I]
M.p. (dec.)
["CI
..
~~~~~
-~
~
-
~~
~~
I IM) vs. br
1087 vs. br
1092 vs. br
~
.
. .
~~~~~
~~
~
[a] Dissolved in dibromomethane and precipitated with ether
[b] From benzene.
[c] From dibromomethaneiacetone.
Proof of the structure was afforded by an X-ray structure
analysis of (3b), which on the basis of 2121 significant reflections was solved by usual methods and refined to an R value
0.072. (36) crystallizes in the triclinic space group P i
witha=1073.9, b=1124.5, c=1448.3pm; rw=90.58, p=91.12,
y = 1 16.94"; Z = 2. The nickel atom forms an inversion center
and is bonded in a planar array to two trans P and S atoms
(see Fig. 1).
Bis(diorganylphosphinodithioformato-S,P)nickel(lI)
Complexes-Novel Four-Membered Ring Chelates[**]
By Jiirgen KopJ RudolfLenck, Sigurjon N . Olafsson, and Reinhard Kramo/owsky[*]
Substituted dithioformate ions of type (1) react with many
elements to give well known['] four-membered ring chelates
in which they coordinate via the two S atoms. A chelate
formation with the donor atom of the residue Y and an
S atom has been discussed but not proven['].
S
/IY-C<?
S
(1)
Fig. I . Molecular structure of the bis(chelateJ ( 3 h ) with important bond
lengths (righthand side) and important bond angles (lefthand side); standard
deviations in parentheses.
Y = N R z , O K , SR
As novel ligands of type ( I ) , we prepared the phosphinodithioformates (2) by reaction of secondaryphosphanes and carbon disulfide in the presence of aqueous potassium hydroxide13.41,
The exocyclic C-S bond is significantly longer than in thioformaldehyde (rcZs = 161.I pm)I7l, and the endocyclic C - S
distance is shorter than the value ( 1 . ~ - ~ = 1 7 to
6 178 pm)[']
calculated for C ( s p z ) - Ssingle bonds. Together, these findings
are consistent with a marked contribution of the resonance
structure (3'). The Ni-S and Ni-P bond lengths are notably
(31
The salts (2) react with nickel(l1) salts to give apolar, diamagnetic bis(che1ates) (3) having the composition
[Ni(S,CPR,),][4~51. We have now found that the anions of (2)
occur as P,S-bonded chelates in these complexes, for, in contrast to (2), they do not react in organic solvents at room
temperature with sulfur[61.The high-frequency position of a
band attributable to an approximate C=S stretching vibration
in the IR spectra (cf. Table 1) also provides evidence for this
structure.
[*] Dr. J. Kopf, Dr. R Lenck. Dr. S . N. 0lafsson.and Dr. R. Kramolowsky [ '1
Institut fur Anorgdnische und Angewandte Chemie der Universitiit
Martin-Luther-King-Platz 6. D-2000 Hamburg I3 (Germany)
['I Author to whom correspondence should be addressed.
[**I We thank Professor Weiss and the Deutsche Forschungsgemeinschaft
for supplying the diffrdctometer.
768
/3')'
shorter than in all previously investigated four-membered ring
chelates containing a NiS4 skeleton ( r ~= 21
i 8~ to 224 pm)['bl
or planar nickel(l1)complexes with trans-NiP,X2 coordination
(rNi--p=225 to 238 pm; X = CI, Br)I9I.
Exper-imental
Potassium diorganylphosphinodithioformates (2): All
operations must be carried out under nitrogen. A solution
of the secondary phosphane (30 mmol) and carbon disulfide
(30mmol) in tetrahydrofuran (25 ml) is treated with a saturated
aqueous solution of potassium hydroxide and the mixture
stirred vigorously for 15 h at room temperature. After concentration of the THF solution and addition of ether [or of
n-hexane in the case of (2c)] (2) separates out as fine, brightpink to red crystals. Yield 80 to 85 %.
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