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Disulfur Monoxide as Complex Ligand.

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The manner in which the new ligand is coordinated to
the metal can be determined indirectly by 'H-NMR spectroscopy. Of the four aromatic rings capable of participating
in K complex formation only the persubstituted naphthalene
moiety does not bear any hydrogen atoms. From the absence
of a characteristic high field shift for protons of a benzene
ring coordinated to (CO),Cr it follows that the reaction product has the structure (/). This is supported by the observation
that when ( I ) is warmed in solution it is completely transformed into the isomer (2), which can also be isolated as
themain product in the cyclization reaction under these conditions. The 'H-NMR spectrum of (2) shows resonances that
can be assigned to the protons forming a pseudo AA'BB'
system of the naphthalene moiety bound to the metal.
OH
oc' co
(1)
OH
co
(2)
chloride/pentane (1 : l), removal of solvent from eluant, and
recrystallization of the resulting residue from methylene chloride/pentane (1 :S), brick-red crystals of ( I ) can be obtained.
Yield 0.53 g (62 %).
Received: June I I. 1975 [ Z 267 IE]
German version: Angew. Chem. 87.671 (1975)
CAS Registry numbers:
( I ) . 55904-96-6; (2). 55904-97-7: pentacarbonyl[methoxy(phenylk.arbene]chromium(0). 27436-93-7; tolan. 501-65-5
[I] W Kirnwr: Carbene Chemistry, 2nd Ed. Academic Press. New York
1971.
[2] K . H. Diir:. Naturwissenschaften. in press.
131 E . 0. Fischur, Angew. Chem. 86. 651 (1974).
~ v , Ber. 93. 165 (1960).
[4] R. D. F i s ~ ~ hChem.
151 Cf. 5. Dorrrr and E. 0. Fischer. Chem. Ber. 107. 2683 (1974).
[6] L. I. Smirh and H. H. Hoi,hri. J. Am. Chem. SOC.63. I181 (1941): and
literature cited therein.
171 E. 0. Fiwhur. B. Herb/. K. H . Dii/:,J. Mi;//rr.and H. M w J ~J.~Organome,
tal. Chem. 16. P 29 (1969).
Disulfur Monoxide as Complex Ligand[**]
By Giinter Schmid and Giinter Ritter"]
The IR spectrum (in CS,) of ( I ) shows three bands in
the v(C0) region at 1953 vs, 1887 vs and 1869 vs cm-',
as would be expected for tricarbonylchromium(0) complexes
of condensed aromatic^'^]. The same bands of the isomer
(2) appear at 1963 vs, 1896 vs, and 1885 vs cm-'. Hence
a higher donor-acceptor ratio can be ascribed to the naphthol
ligands in ( I ) .
Two possible reaction routes come under discussion for
the unexpected formation of complex ( I ) :
1. On decomposition of the carbene complex the carbene
and a carbon monoxide ligand afford free methoxy(pheny1)ketene151. This reacts, as has been described for reactions of
diphenylketene witharylalkynes'6J,with tolan to give the naphthol derivative which finally binds to the metal.
2. Synthesis of the naphthol skeleton is effected in the coordination sphere of the metal-possibly after substitution of
a CO ligand by the alkyne.
Inconsistent with the first possibility is the finding that
2,3-diphenyl-4-methoxy-l-naphthol,
which can be obtained
by cleavage under C O pressure in ethereal solution, does
not coordinate to the metal under the conditions of the cyclization reaction, in the presence of neither hexacarbonylchromium(0) nor pentacarbonyl[methoxy(phenyl)carbene]chromium(0).
The second alternative, on the other hand, makes it quite
understandable that the isomer ( I ) is formed exclusively under
kinetically controlled conditions; for, in this compound the
metal is located almost centrally above the completely substituted naphthalene ring made up of carbene, carbonyl, and
alkyne components. Participation of the metal in the reaction
is also supported by the observation that no product corresponding to compound ( I ) or (2) could be obtained under
the same conditions from the homologous tungsten-carbene
complex and tolan.
Experimental.
A solution of (CO)5Cr[C(OCH)3)CbH5]"]
(0.58 g,
1.86mmol) and tolan (0.33g, 1.86mmol) in di-n-butyl ether
(6ml) is stirred for 3 h at 45°C. A red product separates
out, further precipitation of which is promoted by addition
of pentane (5ml). After cooling the suspension to -20°C
the precipitate is collected on a G 3 frit and purified chromatographically on silica gel (Merck, Act. 2-3) at -20°C. A
red zone is formed, from which, after elution with methylene
A n y e a . Chmi. inrrrnur. E d i t .
Vol. 14 (1975) ,INo. 9
After the complexation of sulfur monoxide, SO, and disulfur
dioxide, SZO2['],wehavenow succeeded in isolating a complex
containing disulfur monoxide, S,O. as ligand. Although free
SzO is relatively long-lived compared to SO and S 2 0 , , which
have a lifetime of only milliseconds, the monomer is stable
only in the gas phase at 2 1 tom; on condensation it decomposes with formation of SO2 and polysulfur oxidestLI. The
structure and bonding of the molecule have already been
described [31.
We have been able to synthesize the first S 2 0 complex
[~PP~=(C,H~)~P--(CH~)~[ ( d p ~ e ) ~ I r ( S ~ O ) l C 1f I )
P(C,H,),] fiiu two different routes, one based on the same
principle as for the synthesis of the structurally confirmed
S 2 0 2 complex [(dppe)21r(S202)]C1(2)['] the other on its
own chemical properties.
( 2 ) is formed on oxidation of the sulfur complex
[(dppe)21r(S2)]C1[41withIO,[''. The assumption that this reaction proceeds in two steps has now been proven by the isolation
of the S 2 0 complex:
In order to avoid further oxidation to the S 2 0 2complex,
[(dppe)21r(S,)]C1 is treated with an equimolar quantity of
NaI04, leading initially via anion exchange to the [(dppe)Jr(S2)]I04 complex, from which the cationic S 2 0 complex and
1 0 3are formed in solution by intramolecular redox reaction.
Addition of BaCI, yields Ba(I03)* and ( I ) .
The second synthetic route is based on the reactivity of
the S 2 0 2complex (2), which e.g. on treatment with excess
triphenylphosphane
undergoes
decomposition
to
[(dppe),Ir]CI
with formation of (CbH5)3P=o and
(CbH5)3P=sL11.This reaction must also proceed stepwise for
the directed partial deoxygenation to afford the S 2 0 complex
f 1).
[*] Prof. Dr. G. Schmid and Dr. G. Rittcr
Fachbereich Chemie der Universitit
355 MarburgLdhn. Lahnberge (Germany)
[**I The complex chemistry of lower sulfur oxides. Part 3.--Part
Ill.
2: Ref.
645
Indeed such a reduction of (2) leads smoothly to the same
product as the partial oxidation of the corresponding S2
complex.
The new complex (1 ),a yellow crystalline compound which
is very stable to air, shows only one SO band a t 1043cmin the IR spectrum. In all probability the molecular structure
of the S 2 0 complex is as shown below, i.e. similar to that
of (2). whose structure has already been confirmed by X-ray
analysis[I].
The iridium is coordinated to four P and two S atoms
in a distorted octahedral structure. As in the S 2 0 2complex
(2) an S-S single bond is also present, while the S - 0
bond, according to the IR spectrum, exhibits double bond
character.
Experimental:
Method 1 : To a solution of [(dppe)21r(S2)]Cl (0.425g,
0.37mmol) in C H 3 0 H (70ml) is added N a I 0 4 (O.O8g,
0.37 mmol), also dissolved in methanol. 0.38 g (0.3mmol) of
the [(dppe)Jr(S2)]1O4 thus prepared is dissolved in 30ml
methanol/l ml H 2 0 and the resulting solution stirred for 24h
at room temperature. BaCl, (O.lOg, 0.4mmol) is added to
the solution and precipitated Ba(I03)2 is filtered off. The
filtrate is evaporated to dryness and the resulting residue
extracted with toluene (60ml) and methanol (10ml). Concentration of the extract affords 0.25 g (70 %) of crude product,
which still contains some 10;. Double recrystallization from
toluene/methylene chloride yields analytically pure (1 ).
Method 2: A mixture of (2) (0.41 1 g, 0.367mmol) and
P(C,H,), (0.193g, 0.73mmol) in toluene (50ml) and CH2C12
(15ml) is heated under reflux for 1 h. Concentration of the
ocher yellow solution affords 0.277g (68%) of ( l ) , which
after recrystallization from toluene/methylene chloride is analytically (C, H, C1, 0, S) and spectroscopically identical with
the product prepared by Method 1.
Received: June 11, 1975 [Z 268 IE]
German version: Angew. Chem. 87, 673 (1975)
CAS Registry numbers
( I 1, 56391-52-7: ( 2 % 56391-51-6; P(C,H,),,
31603-13-1: NaIO,,, 7790-28-5
603-35-0; [(dppe),lr(S,)]Cl,
[ I ] G. Sd7mid and G. R i f r r r , Chem. Ber., in press.
[2] W Gun- and P. W Schunk. Z. Anorg. AHg. Chem. 379. 300 (1970).
[3] E. Tientarin, J . Hocff. F . J. Lozias, and D . R . Johnson, J. Chem. Phys.
60. 5000 (1974): H. Bock. 6. Soloukr. P. Rosrnus. and R. S f n r d d , Angew.
Chem. 8.5. 987 (1973): Angew. Chem. internat. Edit. 12. 933 (1973); literature cited therein.
[4] 4. P. Ginsbny and W E. Liiide//,Chem. Commun. 1971. 232.
646
[2n,6n]-Spirenes. Synthesis of the First Member of
a New Class of Compoundsl"]
By Heinz Diirr and Bernd Weissr'l
Dedicated to Professor Eugen Miiller on the occasion of his
70th birthday
Hitherto only members of the series of preparatively and
theoretically interesting [2n,4n]-, [4n,4n]-, and [4n,6n]-spirenes have been synthesized. Derivatives of the [2~,6x]-spirene
type (2) were unknown['] or only postulated as unisolable
intermediatesl2j.
We have now succeeded in the first synthesis of a [2~,6n]spirene stabilized by benzo groups. Photolysis of the also
unknown diaza-[4rr,6n]-spirene ( I ) seemed to offer a route
for this purpose['!
1,3-Dipolar cycloaddition of 5-diazodibenzo[a,d]cycloheptene to cyclooctyne proceeded smoothly, affording an 80%
yield of ( l a ) as colorless needles [m.p. 183-184°C (dec.)].
An analogous reaction with dimethyl acetylenedicarboxylate
led to ( I b ) (53% yield; m.p. 1SOOC) whose structure was
proved by X-ray analysisf3! Irradiation of ( I a ) in benzene
with a high-pressure Hg lamp (Pyrex filter) and subsequent
working up of the photolysate by column chromatography
afforded spiro[5H-dibenzo[a,d]cycloheptene-5,1'-2,3,4,5,6,7hexahydro-1 H-cyclopropacyclooctene] ( 2 a ) , m. p. 130131 "C, in 10 % yield. Photolysis of ( I b ) did not give a [2rr,6rr]spirene.
Experimental
500mg of ( l a ) (1.53mmol) were dissolved in anhydrous
benzene (1 50ml) and irradiated (high-pressure Hg lamp, GW,
filter) for 6 h, during which 18ml (52%) of nitrogen were
evolved and the solution assumed a pale yellow color. By
column chromatography on silica gel with CH2C12as eluant
and two recrystallizations from ether/methanol 47 mg (10 %)
of ( 2 a ) was isolated as colorless crystals.
Received: May 30, 1975 [Z 272a IE]
German version: Angew. Chem. 87, 674 (1975)
CAS Registry numbers:
( l a ) . 56008-67-4; i l b ) , 56008-68-5; ( 2 ~ ) 56008-69-6:
.
5-diazodihenzo[a.d]cycloheptene. 6141-56-6: cyclooctyne. 1781-78-8;
dimethyl acetylenedicarboxylate. 762-42-5.
[*I Prof. Dr. H. Diirr and Dipl.-Chem. 9. Weiss
Fachbereich 14, Organische Chemie der Universitat
66 Saarbrucken (Germany)
[**I [2x,6n]-Spirenes are unsaturated monospiro compounds containing one
double bond in one ring and three in the other.
H . Diirr and L. Srhrader, Z. Naturforsch. 24b, 536 (1969): Chern. Ber.
103, 1334 (1970); H . Diirr and R . Sergio, Tetrahedron Lett. 1972, 3479;
C. Eye, ibid. 1963. 1667.
[ 2 ] E. E. Wadi and W M. Jones. J. Org. Chem. 38, 2572 (1973).
[3] 6. Weiss, Diplomarheit, Universitat Saarhriicken 1974; K . H. Puu/v,
Diplomarbeit, Universitat Saarbrucken 1975.
[I]
Anguw. Chum. internat. Edit.
I Vol. 14 ( 1 9 7 5 ) I No. 9
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