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Disulfur Monoxide as Complex LigandЧPreparation and Molecular Structure of [(5-C5Me5)Mn(CO)2(S2O)].

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CAS Registry numbers:
Ib.CI 100-04-9; Zb, 58402-54-3; "N-Zb, 96445-25-9; 3b, 18523-44-9; I5N3b, 96445-26-0; LiN,, 19597-69-4.
~
[ I ] C. M. Addms, W. von Philipsborn, Magn. Reson. Cbem. 22 (1985) 130.
[2] R. Huisgen, I . Ugi, Chem. Ber. YO (1957) 2914; 1. Ugi, R. Huisgen, ibid.
91 (1958) 531.
[3] 1. Ugi, R. Huisgen, K. Clusius, M. Vecchi, Angew. Cbem. 68 (1956)
753.
[4] 1. Ugi, H. Perlinger, L. Behringer, Chem. Ber. 91 (1958) 2324.
[5] J. D. Wallis, J. I>. Dunitz, J. Chem. Soc. Cbem. Commun. 1983. 910.
[6] A signal at the same position and of similar width was obtained with a
saturated solution of gaseous N2 in CDCli containing Cr(acac), ( 0 . 0 7 ~ )
at 233 K.
[7] The "N resonance of labeled "N- I4N was reported to appear as a relatively sharp line at S= -70.5 (in cyclopropane, 233 K, recalculated rel.
to CHINO2 as ext. standard); cf. J. G. Green, G. R. Dubay, N. A. Porter,
J A m . Chem. Sor. 99 (1977) 1264. For a discussion of the chemical shifts
and line widths of N2 see also [13].
[S] J. Muller, Z . Nuturjiirsch. 8 3 4 (1979) 437.
[9] R. Muller, W. von Philipsborn, unpublished.
[lo] M. Witanowski, L. Stefaniak, G. A. Webb in G. A. Webb (Ed.): Annu.
Rept. NMR Specrrosc.. Yol. 118, Academic Press, London 1981, p. 77.
[ I l l 1. I . Schuster, C. Dyllick-Brenzinger, J. D. Roberts, J . Org. Chem. 44
(1979) 1765.
(121 Treatment of N.N-dimethyl-l,4-diaminobenzene
in C H 3 0 H / H 2 0( 5 :1)
at - 10°C with a molar equivalent of NaI5NO2(99% 15N)in a minimum
volume of H 2 0 gave, after stirring for 4 h, a solution of the corresponding diazonium chloride labeled with I5N at the ,B-N atom. Cooling to
-30 'C, dilution with an equal volume of cold C H 3 0 H , and treatment
with methanolic LiN3 yielded the desired pentazole as previously described. 14)
[I31 The signal of the labeled "N- I4N appears as a sharp line at S = -70. I
in good agreement with [7]. It is assigned to truly dissolved N 2 and is
only observed with labeled material because of the low concentration.
The broad NZ absorption centered at 6 = -73 in Figures I and 2b probably results from gaseous NZ in micro-bubbles and the associated local
field inhomogeneity.
(141 J. Dorie, B. Mechin, G. Martin, Org. Magn. Reson. 12 (1979) 229. T h e
published chemical shift data were recalculated relative t o CH,"NO2 as
an ext. standard.
[IS] The "N-NMR spectra were measured on a Bruker AM-400 w.b. spectrometer at 40.56 MHz in 20-mm tubes with Cr(acac), as a relaxation
reagent (AT=0.8 s , a=23", no proton decoupling).
coordinating properties of S20, since no structural investigations are available for the mononuclear complexes 1''I
and 2,[31and since the binuclear complex 3J4]whose structure has been confirmed by X-ray analysis, contains S20
bridges.
6(dppe)21r(Sz0)]C1 1 , dppe: bis(dipheny1phosphino)ethane
[Cp2Nb(SzO)Cl]2, Cp: $-cyclopentadienyl
[Mo(SzO)(SzC-NEt,)zl, 3
We have prepared the brown disulfur complex 5 by
reaction of the tetrahydrofuran(THF)-stabilized complex
fragment [Cp*Mn(CO),] (Cp* = I$-pentamethylcyclopentadienyl), which is formed via photolysis of 4 in THF,''I
with excess sulfur. 5 was then converted to the red complex 6 by air oxidation.'61 The mononuclear neutral complex 6 is a suitable model compound for the study of the
S,O ligand.
Table 1. Spectroscopic data for the complexes 4 - 6
IR
v(C0) [cm
~
7 [a]
k(C0) [ N . c m - ' ] [b]
By Max Herberhoid,* Bertram Schmidkonz,
Manfred L. Ziegler, and Thomas Zahn
Dedicated to Professor Helmut Behrens on the occasion
of his 70th birthday
Free disulfur monoxide, S20, wltich is stable in the gas
phase below 1 torr for several days, decomposes to SO,
and polysulfur oxides."] Like the isovalent and isoelectronic SO,, it is non-linear."]
188.4
s
146.5
1180
S 2 0 can be formed as a complex ligand by the oxidation
of S2 ligands. However, the S 2 0 complexes reported so far
only allow tentative conclusions to be made regarding the
[*] Prof. Dr. M. Herberhold, DipLChem. B. Schmidkonz
Laboratorium fur Anorganische Chemie der Universitat
Universitatsstrasse 30, D-8580 Bayreuth
Prof. Ur. M. L. Ziegler, DipLChem. T. Zahn
Anorganisch-chemisches lnstitut der Universitat
Im Neurnheimer Feld 270, D-6900 Heidelberg (FRG)
[**I This work was supported by the Deutsche Forschungsgemeinschaft and
the Fonds der Chemischen Industrie.
Angew Chem Int Ed Engl 24 (1985) No. 6
I3C-NMR [c]
S(Cs(CH,h)
&Cs(CH?)s)
6
2002 s
1917 vs
15.28
1993 vs
1946 vs
15.67
2000 vs
1952 vs
15.77
1.85
1.76
1.71
'H-NMR [c]
S(CdCH3)5)
Disulfur Monoxide as Complex LigandPreparation and Molecular Structure of
I(~s--CsMes)Mn(C~)~(S~~~l**
5
4
10.2
95.4
9.8
102.0
9.3
100.9
[a] In THF. [b] Calculated according to F. A. Cotton, C. S. Kraihanzel, J . Am.
Chem. Soc. 84 (1962) 4432. [c] In CDC13, 0°C.
Table 1 summarizes the characteristic I R and NMR data
of the complexes 4-6. According to the force constants
k ( C 0 ) of the carbonyl vibrations, which can be calculated
from the v ( C 0 ) frequencies, the back-bonding from the
metal to the CO ligands decreases upon replacement of a
CO group in 4 with S, or S,O. The acceptor character of S2
is higher than that of CO; this observation was also made
in a n earlier study on [CpRe(CO)2S2].171Apparently, S, is
able to withdraw more charge from the complex fragment
[Cp*Mn(CO),] than carbon monoxide. A further, but
somewhat smaller increase in the acceptor ability occurs
upon oxidation of the S, ligand to S20.
According to the X-ray structure determination of 6
(Fig. I), the disulfur monoxide ligand is coordinated to the
metal via both sulfur atoms. The Mn-S bonds are long
and somewhat different; the sulfur atom bearing the oxygen, S(2), exhibits pyramidal geometry and is further away
from the metal than the terminal S(1). The S-S axis is
roughly parallel to the ring plane of the Cp* ligand. The
oxygen atom of the S,O ligand is directed away from the
Cp* ring; the dihedral angle S20/CSMe, is 54.3". In comparison to free S20, the S-S and S-0 bonds of coordi-
0 VCH Verlugsgesellschafl mbH, D-6940 Wernhetm, 1985
0570-0833/85/0606-0515 $ 02 80/0
51 5
012)
[5] a) W. A. Herrmann, R. Serrano, J. Weichmann, J . Organomet. Chem. 246
(1983) C 57; b) J. D. Korp, I. Bernal, W. A. Herrmann, R. Serrano, Chem.
Ber. 117(1984) 434: c) W. A. Herrmann, R. Serrano, A. Schifer, U. Kusthardt, J . Organomel. Chem. 272 (1984) 5 5 , Ref. 11.
[61 Experimentalprocedure: A solution of 4 (600 mg, 2.2 mmol) in 150 m L of
A
,121
Fig. 1. Molecular structure o f 6 in the crystal. Pbn2,-CY,. 2 = 4 , a =843.1(4),
h=1229.9(4),c=1394.3(1.1)pm;R,,,,=0.139,R,~,,,,=0.056,R,=O.O48.-Selected structural data ([pm] and ["I, respectively): Mn-S(I) 232.8(5),
Mn-S(2) 240.0(5), S(I)-S(2) 201.3(8), S(2)-0(1) 152.1(13): S(I)-Mn-S(Z)
50.4(2), Mn-S(I)-S(2)
66.7(2), Mn-S(2)-S(I)
63.0(2), Mn-S(2)-O(I)
1 14.6(5), S( I)-S(2)-0( I) I17.4(6). Further details of the crystal structure investigation are available on request from the Fachinformationszentrum Energie Physik Mathematik. D-75 14 Eggenstein-Leopoldshafen2, upon quoting
the depository number CSD 51 386, the names of the authors, and the journal
citation.
nated S 2 0 in the complex 6 are longer, whereas the SSO
angle remains unchanged. The S-S distance (201.3(8) pm),
however, is markedly shorter in 6 than for the S 2 0 bridges
in 3 (mean value 210.0(5) pm), which were interpreted tentatively as S 2 0 anions in a molybdenum(iri) complex.[41l n
the manganese complex 6 , S 2 0 can be looked upon as a
side-on rc-bound ligand.
Scheme I. Left: part of 6 ; right: part of [CpMn(CO),S02)1 7 (81.
In contrast, the SO, ligand in 7 is only bonded via the
central sulfur atom. The involvement of multiple bonding
must be assumed for the Mn-S bond because of the trigonal-planar sulfur geometry and the short Mn-S dist a n ~ e . ~ ' .The
~ ' SO, plane lies perpendicular to the ring
plane of the C p ligand. The S-0 distances are somewhat
shorter than those of free SO2 and the OSO angle is smaller.@]
Received: March 8, 1985;
revised: April 3, 1985 [Z 1209 IEl
German version: Angew. Chem. 97 (1985) 517
CAS Registry numbers:
4, 34807-89-1 ; 5, 96482-53-0: 6, 96502-41-9; sulfur, 7704-34-9.
[I]a) P. W. Schenk, R. Steudel, Angew. Chem. 77 (1965) 437; Angew. Chem.
In(. Ed. Engl. 4 (1965) 402; b) Gmelin Handbuch der Anorganischen
Chemie. 8th Ed.. Schwefel, Erganzungshand 3 (Schwefeloxide). Springer,
Berlin 1980, p. 40ff.
[21 G . Schmid, G. Ritter, Angew. Chem. 8 7 (1975) 673; Angew. Chem. Inr. Ed.
Engl. 14 (1975) 645.
131 J . E. Hoots, D. A. Lesch, T. B. Rauchfuss, Inorg. Chern. 23 (1984) 3130.
[41 J. Dirand-Colin. M. Schappacher, L. Ricard, R. Weiss, J. Less Common
Me/. 54 (19771 91.
5 16
0 VCH Verlaqsye~eikchaftmbH. 0-6940 Weinheim. 1985
anhydrous N2-saturated T H F was irradiated with a high-pressure mercury lamp (Q700 Original Hanau) until the v(C0) absorptions of 4 had
vanished (ca. 3 h). After addition of sulfur (200 mg, 6.3 mmol), the solution was stirred for I h, its color changing from the original wine-red to
dirty green. Subsequently, air was passed through the solution for 30 min,
followed by an additional 5-8 h of stirring under air. The resulting
brownish red solution was evaporated and the residue chromatographed
on a silica gel column (CCR 60 Grace, 20 x 1.5 cm). The column was first
washed with pentane and then the sulfur-containing complexes (including 5 ) were eluted as a greenish brown band with CH2CIZand 6 as a red
band with THF. Recrystallization from THF/diethyl ether at -78°C afforded red crystals of 6 (150 mg, 21%), which decompose at 140145"C.--IR (KBr) 1995 (vs), 1950 (vs) (v(CO)), 1056 (m) (v(S0)). 546 (m)
(t'(SS)) c m - ' . - FD-MS: m / z 326 ( M ' L - E I - M S : m ' z 326 (4%. M").310
((>''<>,Cp*Mn(COhS ! I , 270 ( 3 6 h Cp*Mn(S?O)'), 2.54 (16"., Cp'MnS?),
238 (3%. Cp*MnSO+), 222 (37"/0, Cp*MnS+), 206 (17% C p * M n O + ) , 190
(4%, C p * M n + ) , I19 (100%, C,HT,).-Correct elemental analysis (C, H,
0, S, Mn).
(71 a ) M. Herherhold, D. Reiner, U. Thewalt, Angew. Chem. 95 (1983) 1028;
Angew. Chem. Int. Ed. Engl. 22 (1983) 1000; b) M. Herberhold, D. Reiner, U. Thewalt, T. Dehaerdemaeker, K. Ackermann, 2. Naturforsch. 8 3 9
(1984) 1199.
[S] C. Barbeau, R. J. Dubey, Can. J . Chem. 57 (1973) 3684.
[91 1:P. Lorenz, J . Messelhauser, W. Hiller, K. Haug, Angew. Chem. 97
(1985) 234: Angew. Chem. I n f . Ed. Engi. 24 (1985) 228.
Reaction of Small Molecules with the Binuclear
Complex I(p-C5H,)(p-Br)Pd2(PR,),1: Addition
without Cleavage of the Metal-Metal Bond**
By Peter Thometzek, Karin Zenkert, and Helmut Werner*
The addition of small molecules such as CO, COz, or
SO2 to compounds containing metal-metal bonds and the
possible reversibility of this process is of current interest,
e.g., in connection with the removal of these molecules
from gas mixtures. We chose as a model system the sandwich-type binuclear complexes l a , b,"] in which the bridging bromide can be easily replaced, for example, by a thiolate or carbonylmetalate anion.I2l
The reaction of l a , b with C O in pentane or toluene
produces nearly quantitatively in a few minutes the novel
CO-bridged binuclear complexes 2a, b.I3' These ruby-red,
rather air-stable solids are soluble in all the standard organic solvents except alkanes. In contrast to the reactions
of [(~-dppm)2MrX2](dppm=CH2(PPh2)2; M = Pd, Pt;
X = CI, Br)I4"l and [(~-dppm)2Rh,(CO)2][4h1
with CO, the
addition of carbon monoxide to l a , b is not accompanied
by cleavage of the metal-metal bond ; however, the cyclopentadienyl and bromide ligands rearrange from bridging
to terminal positions. A similar rearrangement also occurs
in the addition of allene to l b , but with cleavage of the
Pd -Pd bond.15]
The reactivity of methyl isocyanide and SO, towards l b
and l a , respectively, is similar to that of CO. The reaction
of l b with CNCH, occurs rapidly in toluene even below
0°C to give 3b in high yield.I3] The spectroscopic data for
3b are consistent with a structure similar to that of the CObridged complexes 2a,b and 2b, CI instead of Br.l6] According to the 'H- and '-'C-NMR spectra of 2a,b and 3b
[*I
["'I
Prof. Dr. H. Werner, Dipl.-Chem. P. Thornetzek,
Dipl.-Chem. K. Zenkert
Institut fur Anorganische Chemie der Universitat
Am Huhland, D-8700 Wiirzburg (FRG)
This work was supported by the Deutsche Forschungsgemeinschaft, the
Fonds der Chemischen Industrie. and Heraeus GmhH.
0570-0833/85/0606-0516 S 02.50/0
Angew. Chem. Int. Ed. Engl. 24 (1985) No. 6
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