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Complex Stabilization of Disulfur Dioxide in the Fragmentation of Thiirane S-Oxide on Bis(triphenylphosphane)platinum(0).

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C 60; f) H. Werner, J . Gotzig, Organomerallics 2 (1983) 547; g) J. Gotzig,
R. Werner, H. Werner, J. Orgnnomet. Chem. 285 (1985) 99.
[S] a) J. Chatt, J. M. Davidson, J. Chem. SOC.1965. 843; b) F. A. Cotton, D.
L. Hunter, El A. Frenz, Inorq. Cliim. Acra 15 (1975) 155: c) C. A. Tolman,
S. D. Ittel, A. D. English, J . P. Jesson, J. A m . Chem. SOC.100 (1978) 4080,
7577; 10l (1979) 1742; d) H. Werner, J. Gotzig, J. Organomet. Chem. 284
(1985) 73.
161 a) M. Antberg, C. Prengel, L. Dahlenburg, Inorg. Chem. 23 (1984) 4170;
b) synthesis from [(pp?)FeCI2] [6c] and LiAIH,/tetrahydrofuran in analogy to [(pp,)RuH2] [6d]; c) M. Antberg, L. Dahlenburg, Inorq. Chim. Acta
104 (1985) 5 1 : d ) h i d . 1 1 1 (1986) 73.
171 a) Experimental conditions: 10-'-10-2 M solution of the complex, 4 h
irradiation (Philips HPK 125 W, Solidex filter) at ca. 293 K, gas-volumetric monitorin of H, evolution; b) 5 (yellow solid); IR (KBr): ;=I747
(FeH),
,
, X79
. i4al
. . cm-'. 'H-NMR (360.13 MHz, C7Dn. 297 K):
S = - O . 3 , -0.5 (br, each 1 H ; FeCH2), -12.2 (broad ABCDX spectrum;
J(PnH)= 16, J(PsH)=48, J(PcH)=51, J(P,H)=66 Hz; I H ; FeH) [7d].
"P-NMR (145.79 MHz, C6D,/C6H,, 297 K): ABCD spectrum with
6(PA)=39.3, fi(P~)=38.0, 6(Pc)=22.9, &(Po)=-6.9, J(P,P,)=O
and
J(PnP, ) = J( PAP,,) ir J(P"Pc) =J(PRP,) = J(PrPo) = 44 Hz [Yd]. "C-NMR
(90.56 MHz, C6D6, 297 K): 6=-25.4 (dt, J(PC)=13, J(CH)=148 Hz;
m H 2 ) ; c) 6 (colorless solid); IR (KBr): C=1808 (RuH), 3037, 1012,
733 (C,)H,) c m - '. 'H-NMR (360.13 MHz, C6D6, 280 K): 6:=7.95 (m, 2 H;
ortho), 7.18-7.10 (m, 3 H ; meta+para) [2g, 3c], -9.0.1 (ddt; fransJ(PH)=84.5, crs-J(PH)=20.7, cis-J(P2H)=28.4 Hz; 1 H ; RLIH)."P-NMR
(145.79 MHz, C,Do/CnH6, 297 K): 6=3.3 (dt; cis-J(PP)=24, cisJ(PP2)=34 Hz: Irons-PRuC), -0.6 (dd; cis-J(PP)=24 and 34 Hz; fransPRuP). -9.7 (9; czr-J(PP3)=24 Hz; trans-PRuH). "C-NMR (20.15 MHz,
C6D,. 297 K): 6=150.4 (dd; J(PC)=3 and 10 Hz; ipso), 131.9, 130.6 (each
s; ortho), 125.5. 124.5 (each s; meto), 119.9 ( s ; p a r a )I7el; d) ABCD assignment arhttrdry: e) B. E. Mann, B. F. Taylor: "C N M R Dutafor Organomeralhc Compoundr. Academic Press, London 1981; 9 the spectroscopic
data d o not allow a differentiation to be made between the coordination
models represented in the formulas and isomeric structures with exchanged MH and MC building bocks.
181 J:Y. Saillard, R. Hoffmann, J. Am. Chem Sac. 106 (1984) 2006.
(k?')
Complex Stabilization of Disulfur Dioxide
in the Fragmentation of Thiirane S-Oxide
on Bis(triphenyiphosphane)platinum(o)**
By Ingo-Peter Lorenz* and Jiirgen Kull
Complex stabilization of sulfur monoxide has been
achieved by several methods. Particularly favorable is the
fragmentation of thiirane S-oxide in the presence of coordinatively unsaturated or substitutionally labile transition-
metal c ~ m p l e x e s . ~ Two
' - ~ ~ reaction mechanisms are conceivable: (1) initial fragmentation of C Z H 4 S 0with in situ
complex stabilization of SO; (2) initial coordination of
C2H4S0 with subsequent elimination of ethylene (Scheme
1). It was suggested that the second mechanism of reaction
is operative in the synthesis of [((CsHs)(CO)2Mn)2SO];131
this is further supported by 31P-NMR data.12b1We have
now succeeded in isolating the first thiirane S-oxide complex 2 as a n intermediate in the synthesis of the disulfur
dioxide complex 4 from the ethylene complex 1. This is
strong support for the second reaction mechanism discussed above.
L,M
+
CH
,S
,O
-
Scheme I.
Reaction of equimolar amounts of [(Ph3P),Pt(C2H4)] 1
and C,H,SO affords the yellow complex 2 in nearly quantitative yield; complex 2 is stable in air u p to 70°C. In toluene at l 10°C, 2 undergoes fragmentation to form not the
q 2 - S 0 complex 3 but rather the S,02 complex 4 (Scheme
2).14]SzOzhas been suggested as the unstable, initial product of SO decomposition in the gas phase"] (cf. Scheme 3 ) ;
SzOzhas only been prepared as a ligand via an oxidative
pathway starting from the q2-S2ligand.16.71
The compositions and structures of the new compounds
2 and 4 were determined by elemental analysis and by
mass, IR, 'H-NMR, and "P-NMR spectroscopy. For comparison, the spectroscopic data for the thiirane complex 5 ,
which is accessible by a reaction analogous to that used to
prepare 2, is also given in Table 1. However, 5 cannot be
0
/20 OC
+
-
'ZH4
2
Ph3P
\
Ph3P
/
L
1/2
- 1/2 (Ph3PfZPt
F't-
0
sH
Ph3P,
Pt-It
s\
Ph3P'
11
4
0
+
/$\
/ 2 0 ~
Ph3P
b
5
Scheme 2.
[*I Pror. Dr. L P . Lorenz, cand. chem. J. Kull
lnstitut fur Anorganische Chemie der Universitat
Auf der Morgenstelle 18, D-7400 Tiibingen (FRG)
[**I This work was supported by the Deutsche Forschungsgemeinschaft,
NATO (R.G. 116/81), and the Fonds der Chemischen Industrie. We
thank Prof. Dr. G . van Karen. Amsterdam, for valuable discussions.
Angeu.. Chern. I n t . Ed. Enyl. 2s
(1986) No 3
converted into the S2 complex 6 .
The FD mass spectra of 2, 4, and 5 exhibit peaks for the
respective molecular ions. In the 1R spectra of 2 and 4, the
v(S0) bands lie at surprisingly long wavelength compared
with those of S-coordinated dimethylsulfoxide (DMSO)
0 VCH Verlagsgesell.vchaflmbH, 0-6940 Weinheim.1986
0570-0833/86/0303-0261 $ 02.50/#
26 I
complexes of platinum(ii)[81and the only known S 2 0 2comple~.[".'~
This is presumably due to the better n-donor ability of the [(Ph,P),Pt"] fragment. The PtS stretching vibrations of 2 , 4 , and 5 give bands between 300 and 400 cm-'.
v ( S S ) of 4 is unequivocally assigned to the band at
657 cm-'.
Table I . Selected spectroscopic data for the complexes 2, 4, and 5
Com- FD-MS [a]
1R [cm-'][b]
'H-NMR
"P-NMR [d]
plex m/z ( M + )v ( S 0 ) v(SS) v(PtS) (6 values) [c] 6 values J [Hz]
~~
2
795
953
-
329
4.4-5.7
4
815
882
870
657
398
-
5
779
-
-
315
4.1-5.2
18.75;
20.25;
5.66;
2518 (PtP)
1960 (PtP)
10 (PP)
4009 (PtP)
14.30;
4042 (PtP)
[a] Relative to I9'Pt. [b] KBr. [c] C,D,, 20°C. [d] Toluene, -40°C.
In the 'H-NMR spectrum of the adduct 2, the AA'BB'
multiplet, which is unresolved owing to complicated coupling relationships, appears at 6 = 4.4-5.7. Such a multiplet
is also found for the thiirane complex 5 at 6=4.1-5.2.
Such a large low-field shift in comparison to those of the
free ligands (6=2.02 (m) and 2.29 (s) in CDCI3) is not observed for the complexation of DMSO and dimethyl sulfide and rules out the formation of the thiaplatinacyclobutane [(Ph3P)2hS(0),,CH2kH2(n=O, 1).
The unequivocal structural confirmation was provided
by the "P('H)-NMR spectra, which exhibit only one signal
for 4 and 5 but an AB quartet with the expected '95Ptsatellites and the usual R - P coupling ons st ants''^ for 2. For
5, no evidence of a hindering of rotation around the R-S
bond or of a n inversion of the pyramidal sulfur is observed. In 2, on account of the nonequivalence of the P
atoms and the equivalence of the CH2 units, the SO group
must lie in the P 2 R S plane. The driving force for formation
of this structure could be the favorable orbital overlap in
the n-system P t 4 - 0 . The spectroscopic findings could
also be interpreted, on the other hand, in terms of q2-S0
coordination. The 3'P-NMR data of the S 2 0 2complex 4
are comparable with those of the q2-02 complex
[(Ph3P)2Pt02](6= 16.4, JP,,=4059 Hz"']); S202is presumably, therefore, q2-coordinated in 4 as in the complex cation [ ( d i p h o ~ ) ~ I r S ~ O(diphos
~ ] + ' ~=~Ph2P-CH2CH2-PPhZ)
~~
and-for steric and electronic (n-donor) reasons-twisted.
According to microwave spectroscopic investigations, free
S202is planar and cis-configurated." 'I
r
1
s, + so2
2
so
d s,02
I
Scheme 3.
+so,
Received: November I I , 1985 [Z 1529 IE]
German version: Angew. Chem. 98 (1986) 276
[I] K. S. Arulsamy, K . K. Pdndey, U. C. Agarwala, Inorg. Chim. Acta 54
(1981) L51.
121 a) W. A. Schenk, J. LeiRner, C. Burschka, Angew Chem. 96 (1984) 787;
Angew. Chem. Inr. Ed. Engl. 23 (1984) 806; b) 2. Naturforsch. B40
(1985) 1264.
[3] I.-P. Lorenz, J. Messelhauser, W. Hiller, K. Haug, Angew. Chem. 97
(1985) 234; Angew. Chem. I n / . Ed. Engl. 24 (1985) 228.
141 Experimentalprocedure: 2 : Upon addition of C,H,SO (91 mg, 1.2 mmol)
to 897 rng (1.2 mmol) of 1 in 50 mL of toluene, the solution turned from
yellow to orange; it was then stirred for 2 h at room temperature, concentrated in vacuum, and treated with 100 m L of petroleum ether (30/
50°C). resulting in the precipitation of light yellow, finely crystalline 2.
Compound 2 was filtered off, washed with diethyl ether and petroleum
ether, and dried in vacuum. M.p.=91"C (dec.); yield: 868 mg ( 9 1 % 4 : 2 (868 mg, 1.1 mmol) was dissolved in 40 mL of toluene and the
solution was stirred for 5 h at 1 IO"C, resulting in the gradual formation
of a deep color and precipitation. After cooling of the finally red sohtion to room temperature, the reaction was worked up as described
above, resulting in the precipitation of orange, air stable 4.
M.p. = 17 I "C (dec.); yield. 290 mg (65%).
151 P. W. Schenk, R. Steudel, Angew. Chem. 77 (1965) 437; Angew. Chem.
Inr. Ed. Engl. 4 (1965) 402; Inorg. SuIfur Chem. 1968. 367; J. T. Herron,
R. E. Huie, Chem. Phys. Left. 76 (1968) 322.
[6l G. Schmid, G . Ritter, T. Debaerdemaeker, Chem. Ber. 103 (1975) 3008.
(71 J. E. Hoots, D. A. Lesch, T. B. Rauchfuss, Inorg. Chem. 23 (1984)
3 130.
[8] C. Eaborn, K. Kundu, A. Pidcock, J. Chem. Soc. Dalton Trans. 1981,
933.
[9] P. S. Pergosin, R. W. Kunz: Phosphorus-31 and Carbon-13 N M R of Transition Metal Phosphine Complexes. Springer, Berlin 1979.
[lo] A. Sen, J. Halpern, Inorg. Chem. 19 (1980) 1073.
[ I I] F. J. Lovas, E. Tiemann, D. R. Johnson, J. Chem. Phys. 60 (1974)
5005.
1121 J. Messelhauser, ILP. Lorenz, K. Haug, W. Hiller, Z.Natuforsch. 840
(1985) 1064.
Synthesis of [ C U ~ O S ~ H ~ ( P M a~ ~
Bimetallic
P~)~],
Raft, by Reductive Elimination of Alcohol or H,**
By Timothy H . Lemmen, John C. Huffman, and
Kenneth G . Cauifon*
Among heteronuclear clusters, polyhydrides are particularly important because they bear transferable hydrogen
reducing equivalents and because they permit determination of hydrogen migrational preferences on model alloy
phases. We report here the synthesis and structural characterization of a neutral complex with a Cu30s3 framework;
the raftlike geometry leaves the metals open on two sides.
Equally important, the synthesis employs two unprecedented"' methods for the formation of metal-metal bonds,
alcohol elimination and H2 elimination.
Reaction of [CuOtBu], with [H40s(PMe2Ph),] proceeds
without hydrogen evolution to yield a product that bears a
stoichiometric resemblance to the alkali metal analogue
[KOsH,(PM,Ph),] [(Eq.
1/4[CuOtBu],
+ [H40s(PMe2Ph),]
s,o + so,
0 VCH Verlagsge,~ell.~cha~
mbH. 0-6940 Weinheim, 1986
--t
(a)
l / x [ C ~ 0 s H , ( P M e ~ P h ) , ]+~ fBuOH
1
It has thus been possible to expand the role of thiirane
S-oxide as a source of SO in organometallic chemistry.
Starting from C,H4S0, we and Rauchfuss et al. have identified, in addition to the SO complexes,"-31 C2H4S0 (2),
S 2 0 2(4), S,0,'7' and C2H4S2complexes.['21The course of
262
SO decomposition shown in Scheme 3 has, therefore, an
analogy in the complex chemistry in solution.
[*I Prof. Dr. K. G. Caulton, Dr. J. C. Huffman, T. H. Lemmen
Department of Chemistry and Molecular Structure Center,
Indiana University
Bloomington, I N 47405 (USA)
[**I This work was supported by US. National Science Foundation (CHE
83-05281), by award o f a Lubrizol Fellowship to T. H. L . . and by gifts of
chemicals from Johnson Matthey Co. We thank Scott Horn for skilled
technical assistance.
0570-0833/86/0303-0262 $ 02.50/0
Angew. Chem. l n t . Ed. Engl. 25 (1986) No. 3
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triphenylphosphate, platinum, complex, oxide, dioxide, fragmentation, disulfur, bis, thiirane, stabilization
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