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Metal Complexes of Sulfur Ylides Coordination Chemsistry Preparative Organic Chemistry and Biochemistry.

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(64) E. J. Shellard: Quantitatiue Paper and Thin-Layer Chromatography, Academic Press, New York 1968.
[65] G. Vernin: La Chromatographie en Couche Mince, Dunod, Pans 1970.
[66] A. Niederwieser, G. Pataki, Prog. Thin-Layer Chromatogr. Relat. Methods 1 (1970); 2 (1972), Ann Arbor-Humphrey Science Publ.
I671 E. Stahl: Chromatographische und mikroskopische Analyse uon Drogen.
Gustav Fischer Verlag, Stuttgan 1970 (suppl. reprint 1978).
1681 F. Geiss: Die Parameter der Diinnxhicht-Chromatographie, Vieweg,
Braunschweig 1972.
[69] K. Macek: Pharmaceutical Applications of Thin-Layer and Paper Chromatography, Elsevier, Amsterdam 1972.
[70] R. M. Scott: Thin-Layer Chromatography Abstracts 1968-1971, Ann Arbor Science Publ. 1972.
[7I] W. Christen: Diinnschicht-Chromatographie, GIT, Darmstadt 1975.
(721 H. Auterhoff, K. A. Kovar: Idenfifizienmg uon Arzneistoffen, Wissek
schaftliche Verlagsgesellschaft, Stuttgart 1971.
[73] S . Dominguez: Cromatografia en Papery en Capa Delgada, Selbstverlag,
Monterrey 1978.
I741 J. Gasparic, J. Churacek: Loboratory Handbook of Paper and 'Thin-Layer
Chromatography. Wiley, New York 1978.
[75] W. Gotz, A. Sachs, H. Wimmer: Diinnschichf-Chromatographie,Gustav
Fischer Verlag, Stuttgart 1978.
[761 J. Touchstone, M. Dobbins: Practice of Thin-Layer Chromatography. Wiley, New York 1978.
(771 E. Stahl, W. Schild: Pharmazeutische Bioiogie, Bd. 1. Gustav Fischer
Verlag, Stuttgan 1981.
1781 H. Jork, H. Wimmer: Quantitatiue Auswertung uon Diinnschicht-Chromatogrammen (Literatursammlung), GIT, Darmstadt 1982.
[79] P. Pachaly : Diinnschichtchromatographie in der Apotheke. Wissenschaftliche Verlagsgesellschaft, Stuttgart 1982.
(801 J. Touchstone: Advances in Thin-Layer Chromatography, Wiley, New
York 1982.
[81] H. Wagner, S. Bladt, E. M. Zgainski: Drogenanalyse, Diinnschicht-chromatographische Analyse uon Arzneidrogen, Springer-Verlag. Berlin
1983.
1821 A. Baerheim Svendsen, R. Verpoorte: Chromatography ofillkaloids, Part
A : Thin Layer Chromatography. Elsevier, Amsterdam 1983.
1831 D. Janchen: TLC-Abstracts 1965-1977. Selbstverlag Carnag, Muttenz
1977.
[841 0. H. Masek, M. J. Saxby: TLC-Abstracts 1971-1979, PRM Science and
Technology, London 1979.
[851 M. Lederer: Abstracts in J . Chromatogr., since 1964.
Metal Complexes of Sulfur Ylides : Coordination Chemistry,
Preparative Organic Chemistry, and Biochemistry
By Lothar Weber*
In recent years both acyclic and cyclic sulfur ylides have proved to be interesting and versatile ligands in preparative organometallic chemistry. In addition to paralleling the coordination chemistry of their phosphorus analogues, sulfur ylide complexes show specific structural and chemical features ; they are becoming more important in preparative inorganic
and organic chemistry, and may also be biochemically relevant as methylene transfer
agents. Recent studies of the complexes of the ylidic h4-thiabenzenes and h6-thiabenzene 1oxides have frequently demonstrated unexpected and novel reactions, and thereby enriched
the chemistry both of ylides and of carbonylmetab.
1. Introduction
Phosphorus ylides"' belonged to the synthetic armoury
of organic chemists for 20 years before inorganic chemists
began to take an increased interest in them. As powerful
electron donors, these exceptionally versatile ligands form
with almost all metals a wide range of complexes having
surprisingly stable metal-carbon bonds. Wide complexes
enrich our knowledge of structural chemistry; in addition,
several exhibit exceptional catalytic activity or are of pharmacological importance. The coordination chemistry of
phosphorus ylides has been reviewed by Schmidbaurr2',
and Kaskd4'.
A similar fate awaited sulfur ylides. Some fifteen years
after their introduction as synthetic reagents in organic
chemistry, Trost described them in a monograph as
[*] Priv.-Doz. Dr. L. Weber
Institut fur Anorganische Chemie der Universitat-Gesamthochschule
Postfach 103764, D-4300 Essen 1 (Germany)
516
0 Verlag Chemie GmbH. 6940 Weinheim. 1983
"emerging synthetic intermediate^"'^'. Only then did some
research groups begin to study the ligand properties of
these fascinating compounds, which had long since become indispensable reagents to the organic chemist16J.
This article reports on the synthesis, structure, and
chemical properties of sulfur ylide complexes, underlines
their relevance in preparative organic and organometallic
chemistry, and presents comparisons to, and contrasts
with, the chemistry of phosphorus ylides.
2. Suifur Ylides as a-Ligands
2.1. Metal Complexes of Acyclic Sulfur Ylides
Sulfur ylides are zwitterions in which a carbanion center
is stabilized by a directly neighboring sulfonium center.
Open-chain sulfur ylides can be coordinated as terminal ligands to a metal center (A), in the same way as phosphorus ylides. Their monoanions can coordinate as bridging
double ylides (B) or as chelating ligands (C).Chelate com-
0570-0833/83/0707-0816 S 02.50/0
Angew. Chem. Int. Ed. Engl. 22 (1983) 516-528
plexes are also formed if, in addition to the ylide function,
a further donor atom is present in the molecule (D). The
ylide function itself may be substituted with metal atoms at
the carbanion center (E), or a complexed metal may additionally act as substituent at the sulfonium center (F),
whereby in the last-mentioned case this substituent can
also function as an intramolecular coordination center.
E
D
halides, or even tertiary phosphanes. Exchange of CO is
usually achieved photochemically.
It is notable that even the very thermolabile sulfur ylide
Me2SCH2 can be trapped by reactive metal complexes
[reactions (4)and (5)]. By methods analogous to those outlined in (1)-(5), Me2S(0)CHZcan be introduced as a terminal ligand into complexes of Cu, Ag, Hg, Zn, Cd, TIri4],
and Pdi’51. Carbonyl-stabilized ylides of the form
R’RZSCHC(0)R3 are bonded through the ylidic carbon
atom to pdrIl.16-2OI pt[16,17,191, and €ig1’I1.
Bond Formation 0:
In the protecting coordination
spheres of transition metals, the synthesis and stabilization
of thermolabile Me2SCH2 is achieved by sulfane addition
to carbene
F
2.1.1. Teminal Ligands
Complexes of type ( A ) are generally synthesized by
forming the bonds @, @, or @ (cf. Scheme 1); the indirect
routes via @ and @ are not dependent on the ability of the
free ylide to exist separately. This enables unstable ylides
to be synthesized at a protecting metal center.
Here, the ylide complex 1 is in equilibrium with the
starting materials. The formation of complexes of this type
is determined, in general, by the size and basicity of the
sulfane and by the size and electrophilicity of the alkylidene ligand122a1.In contrast, only very electron-rich phosphorus ylide complexes tend to decompose to phosphane
and alkylidene complexes122b-“1
(for the reversible reaction
of Fischer carbene-metal complexes with phosphanes cf.
13.399.
Scheme 1. Routes to ylide complexes of type A
The rhodium-CH2SMe2unit can be synthesized by substitution of the corresponding iodomethyl complexi231.
Bond Formation 0:
Most complexes of the type discussed here are prepared by ligand exchange reactions,
normally of labile ligands such as ethers, alkenes, nitriles,
(CO),M(THF)
THF
ylide
M
ylide
+ ylide-
THF
I O T
(CO)5M(ylide) + T H F
(1)
= tetrahydrofuran
= M e 2 S ( 0 ) C H z ,Me(Me2N)S(0)CH2;
= C r , MO, w[7,*J
= Me,SCHC(O)Ph; M = Wf91
LnM
Cp(CO)2Fe1241
C1(Ph,P)z(CO)20s12*l
MeX
(Me,O)BF,, M e S 0 , F
MeS03CF,
L,M
C I L z P t ( L = PPh,, PPh,Me)[261
MeX M e S 0 , F
[(PhCH=CHz)PdClZJ, + 4 M e 2 S C H C ( 0 ) R
(3 )
2 trans-ClzPd[CH { C ( O ) R }SMe2J2
R = P h , p-C6H4Me, p-C,H,OMe,
Me,AuPPh3 + y l i d e
p-C,&Br,
THF
---+ P P h ,
P-CBH,NOZ~”]
+ Me,Au(ylide)[”1
y l i d e = Me2SCH2, MezS(0)CH2[13]
Angew. Chem. Int. Ed. Engl. 22 (1983) 514-528
(4)
Bonding and Molecular structure: In the compounds discussed in this section, the ylide ligand is always linked to
the metal atom by a o-bond. As in the analogous complexes of phosphorus ylides, the metal-carbon o-bond is
remarkably stable, both chemically and thermally. In general, phosphorus ylides are stronger donor ligands than the
corresponding sulfur ylides, as revealed by a comparison
of IR data for (CO),Cr(ylide) [ylide = Ph3PCHz,
Ph2MePCH2, PhMe2PCH2, (MeO)3PCH2, Me2S(0)CH2,
517
complexes in which it is bonded to the metal via the ylide
Me(MezN)S(0)CHz'271]and by ESCA measurements on
Me,Au(ylide) [ylide = Me3PCH2, Ph3PCH2, MezSCH2,
group and the pyridine N atom; in a tungsten complex,
Me,S(0)CH2"2bJJ.
however, the donor atoms are pyridine N and "carbonyl"
oxygen[9.
30.3 11
X-Ray structure analysis of Me,Au[CHzS(0)Mezl"Zbl,as
well as of [(tBuCH2)2SMeJs[(tBuCH2)zSCHzZn13]0f28J,
[($C, H 5)(CO)zFeCH2SMez]s[S03Fj"~24b1,
and
( k )-transCl2Pd[CH(C(0)Ph]SMe21," ' ] demonstrates the existence of
2. I . 3. Metal-Substituted Hides
metal-carbon single bonds.
Whereas numerous phosphorus ylides have a metal substituent at the carbanion centeri3', few metal-substituted
2.1.2. Bridging and Chelating Ligands
sulfur ylides (type E), such as 2a--2c, have been rep~rted'~',~~'.
In contrast to the analogous phosphorus ylide compounds, coordination compounds of sulfonium double-ylide
+nBuL,
Me2S(0)CH2
4 Me2S(0)CH2/2 Nal
[ ( P h C H=CH2) P d C l,],
*
- nBuH
Me\
<cHz
S(0
0" %H2
+ Me&Cl
Lio
- LlCl
DMSO
Me\ "CHGeMe,
2a
S
0" 'CH,
+
2 NaCl
+
2 (Me,SO)Cl
+
2 PhCH=CH,
3 Me(Me,N)S(O)CH, + 2 Me,MCl--,
2 [Me,(Me,N)S(O)]Cl
+
(13)
DMSO = d i m e t h y l s u l f o x i d e
Me2N\
derivatives (type B or C) are rare. The anions
[(CH2)zS(0)Me]e and [(CH2)2SMe2]Qcan act as bridging
o r chelating ligands. The deprotonation of the ylide occurs
by transylidation" 'I.
Metalalkyl compounds contain strongly basic ligands,
which can deprotonate coordinated Me2S(0)CHz. However, the products are usually coordination polymers,
whose structures could not be determinedI'4.291.
4c(MMe3)2
S
0" \CH,
2b, M = G e
212, M = Sn
Transition-metal-substituted sulfur ylide complexes of
the form 2d are unknown. They might be regarded as carbyne complexes stabilized by a sulfane and would be of interest synthetically as methylidyne transfer agents. This
would be analogous to alkylidene transfer by sulfur ylide
complexes (see Section 2.3).
R'
1
Me' ' 0
1,
2.1.4. q'-MethyIthiomethyl Complexes
A dinuclear rhenium complex with a bridging sulfur
double ylide can be synthesized indirectly by twofold addition of a methylene complex to a methanethiolate iodzZa1.
Compounds containing the structural group F can be
formally regarded as ylide complexes. A carbanion center
occupies the a-position to a sulfonium center, at which the
metal atom acts as a substituent (and as acceptor). Such
compounds are accessible by intramolecular ligand exchange from q '-methylthiomethyl complexes.
2
J
1
CH,
1
Chelate complexes of type D can also be formed if the
sulfur ylide carries a further donor atom. Dimethylsulfonio-2-picolinoylmethanide forms palladium and platinum
MezSI
L,M
( P P ~ , ) z P ~ [ (CO),Mn1351
~~]
L'
c1
co
Cp(CO),M (M =
MO,
W)'351
co
S-Methylation of q'-thioformaldehyde
leads to cationic complexes of type Fi251.
ligands also
0
C
M = Pd, Pt
518
Angew. Chem. Int. Ed. Engl. 22 (1983) 516-528
The existence of three-membered metallacycles with CS
single bonds has been confirmed by X-ray crystallographic anaI~sis[~",~~1.
[(q5-C5H,)Fe(CO),]@PFP
Transition-metal centers have an appreciable and varied
influence on organic molecules: they can behave as protecting groups by coordinating to polyfunctional species,
thus allowing selective reactions[381;thermolabile moieties
can be stabilized by complex formation, and hence made
available for directed reactions[391.Metal atoms can also
often activate ligands and catalyze many processes[4o1.The
reactions described in this section involve nucleophilic attack of sulfur ylides on the Lewis acid centers of a number
of molecules in the coordination sphere of metal complexes.
+
2 Me,S(O)CH,
-
(19)
(Me,SO)PF, + (r15-C,H5)(CO)2Fe[C(0)CHS(O)Mez]
2.2. Reactions of Coordinated Ligands with Acyclic Sulfur
Ylides
The products can be regarded as sulfonioacyl-metal
complexes or as sulfur ylides substituted by ferriocarbonyl
moieties.
Apart from the reaction of Me2S(0)CH2 with the SiCl
function of chlorosilyliron complexes'481,periphery reactions of sulfur ylides with small ligands remain largely uninvestigated. The results of reactions of carbene, carbyne,
olefin, and isocyanide complexes with phosphorus
y l i d e ~ ' ~may
~ ] serve as guidelines for the corresponding
reactions of sulfur ylides.
2.3. Sulfur Ylide Complexes as Synthetic Building Blocks
2.2.1. Aldehydic and Ketonic Carbonyl Groups
2.3.1. Cyclopropanation
Norbornadien-7-one is stabilized by the Fe(C0)3 fragment; the chemistry of its CO group can thus be studiedI4'].
Sulfur ylides normally form cyclopropane derivatives
only with activated alkenes; however, stereospecific alkylidene-transfer to electron-rich olefins is possible using
complexed y l i d e ~ " ~ . ~ ~ ~ .
r
Reactions of this type involving sulfur ylides have been
little studied, but seem very promising. It might be possible, for instance, to allow the 2,4-cyclohexadienone ligand
(isomeric with phenol) of tricarbonyl(cyc1ohexadien~ n e ) i r o n [ ~ to
~ ~react
- ~ I with ylides, a reaction impossible
with free phenol[42d1.
a,fl-Unsaturated carbonyl compounds
usually form cyclopropanes on reaction with sulfur ylides;
this reaction would be blocked by coordination at a metal
center, possibly opening the way for the alternative epoxidation. Acylferrocenes can be converted in good yield into
other derivatives using Me2SCHz[431.
MezSCHl
Fc-C(O)R
DMSOiTHF
Fc-CHR-CHO
Fc = (q5-C5HS)Fe(~'-CSH,);R = H, M e , P h
2.2.2. Carbony1 Ligands
In contrast to the more strongly nucleophilic phosphorus ylides, such as Ph,PCH2 or Me3PCH,[&', sulfur ylides
do not add to the CO ligands of M(CO), (M = Cr, Mo, W).
The force constants of the CO stretching vibrations provide a measure of the electrophilicity of coordinated carbon monoxide (k=16.49, 16.42, 16.41 mdyn/A for
[M(CO),], M = Cr, Mo, W, respectively[451).The higher
electrophilicity of the CO ligands in Fe(CO), (kax= 17.0,
keg= 16.4 mdyn/& and [(q5-C5H5)Fe(C0)3]@(k= 17.6
mdyn/AfGJ), allows MezS(0)CH2 to add to the carbonyl
group, followed by its rapid t r a n ~ y l i d a t i o d ~ ~ . ~ ' ~ .
Angew. Chem. Int. Ed. Engl. 22 (1983) 516-528
2
1"
R' = Me, Ph; R2 = H,M e
Unlike other reagents for cyclopropanation, ylide-iron
complexes are readily accessible and easy to handle. The
reaction conditions are largely determined by the leaving
group properties of the sulfane.
McCormick and Gladysz[2Za1
have shown that sulfur ylide
complexes are in equilibrium with the free sulfanes and
reactive alkylidene complexes. It is, therefore, reasonable
to assume that the reactive species in cyclopropanation is a
carbene complex: cyclopropanations using carbene complexes have been described frequently in the literature[51!
In this context, analogies between sulfur ylide complexes and diazoalkanes are apparent[s21.Salomon and Kochi152a1
use a sulfur ylide complex as a model for cyclopro1demonstrated
.
~
~a re-~
panation reactions[52a1.Tamblyn et ~
lationship between formation of sulfur ylides and catalytic
cyclopropanation with ethyl diazoacetate, both of which
occur via carbenemetal complexes[531.Porter et ~ 1 . [ ' ~ re1
ported that the metal-catalyzed (Cu, Rh)cyclopropanation
of olefins with a sulfur ylide is appreciably more efficient
than with the corresponding dimethyl diazomalonate.
The ease and safety in preparing and handling sulfur
ylides make them, in combination with copper salts, attrac519
~
tive cyclopropanation reagents. Furthermore, unlike NZ,
the sulfane leaving group can be modified to control the
reactivity of the ylide-copper complex. There is evidence
that sulfonium salts and sulfur ylides are important in the
Cohen et al. discovbiosynthesis of cycl~propanes‘~~-~’~.
ered that (diphenylsulfonio)methanide, which is inert to
olefins such as cis- and trans-2-octene, forms the corresponding cyclopropanes stereospecifically in the presence
of copper saltsf’*].
and ketones to give oxiranes. The coordination of the arene moiety of Ph(Me)SCH2 to the Cr(CO)3 group drastically alters this behavior of the ylide: with diary1 ketones
the main products are alkenes‘601.
0
DMSO
R
Since ylide formation is possible even under physiological conditions, a metabolic pathway involving sulfur ylide
complexes of copper has been proposed for the biosynthesis of presqualene pyrophosphatef5”.
n
R2C=CH2 + R,C-CH,
/-\
KOtBu
(27)
+....
= Ph, p-C,H,NMe,
Electron withdrawal by the Cr(CO), group increases the
electrophilicity of the sulfonium center and allows deoxygenation of the primary adduct. This synthetic method is,
however, confined to benzophenone derivatives, because
of the reduced carbanion activity in the ylide complex. In
addition, it is believed that the transition state leading to
olefin formation is considerably stabilized by two aryl substituents.
2.3.4. Coordination Compounds of Unstable Hides
Alkylidenemetal fragments can be transferred from sulfur ylide complexes to phosphanes and arsanes[611.
(C0)5Cr[CHzS(0)Me,j
+ ER3
-
MezSO + (CO),Cr(CH2ER3) (28)
ER3 = PPh3, PPh,Me, PPhRile,, P(OMe),, AsPh,
R = g e r a n y l ; P P O = pyrophosphate
2.3.2. Synthesis of Heterocycles
Although fbnitrostyrenes are converted into resins by
free Me2S(0)CH2,they react with a copper complex of the
ylide to give good yields of 2-isoxazoline N - o x i d e ~ [ ~ ~ ” .
,R
This process is relevant to the synthesis of complexes of
unstable ylides, such as (MeO),PCH,. Compounds of the
form (R:E),CR: give chelate complexes of ylide ligands
that are unstable in the free state and subject to rearrangements16za.bl
+ (R;E)~cR$
(CO),Cr[ CH2S(0)Me2] - CO,
-MezSO
[Me2S(0)CH2]&I
P h C H=C,
NOz
Ph
R
R = H, Me
ER;
Johnson et al. have reported the conversion of carbonylstabilized [(dialkylamino)methyI(oxo)sulphonio]methanides into 1,3-oxathiol S-oxides, catalyzed by CuSO,. Here,
again, an ylide complex is postulated as reactive intermediate‘’9h!
L
O
R-C-CH$-CH,
I
NMe,
R
-w
CuSOn
= Me, Ph, p-C,H,Cl,
A
o so
+ ...
PPh,
R ’ H
PMe,
P(NMe,),
AsPh,
PPh,
H
H
H
c H3
(26)
H
p-C6H,N0,,
PhCH,
Me,_,Me
[62d1
2.3.3. W t t i g Reactions
Unlike phosphorus ylides, which react with carbonyl
groups to afford olefins, sulfur ylides react with aldehydes
520
CH\
PPh,
Angew. Chem. I n t . Ed. Engl. 22 (1983) 516-528
The use of non-symmetrically substituted reagents allows regioselectivity of chelate synthesis by suitable choice
of the sulfur ylide complex.
0
SMe,
The h4-thiabenzenesFw1(X = lone pair) and their oxides
(X = 0) differ from the sulfoniocyclopentadienides'63' in
that the onium center is a ring member. The nature of h4-
The first step in reaction (31a) is the displacement of
Me,SO by E'R:, the more nucleophilic end group of
R:EICHZEZR$; formation of product in reaction (31b)
consists of attack of E'R: on the chromium atom of the coordinatively unsaturated species {(CO)4Cr[CH2S(0)Me2])'62b1.
The use of diphosphino-substituted ylides[62f,g1
facilitates
the synthesis of novel polyfunctional ylide ligands (react ion (32))[""].
thiabenzenes was formerly disputed. Price et al. considered
h4-thiabenzenes[66a~c~",
h4-thianaphthalenes[66b.d1,
and h4thiaanthracenes[66b1
to be novel aromatic species, but Hortmann et
and Mislow et aZ.[64b,c1
showed that at least
some of Price's compounds were polymers, and that arylsubstituted h4-thiabenzenes are extremely thermolabile
species with ylidic character. MO calculations on the parent compound[671,and NMR[64b,",681
and X-ray crystallographic data'6g1 on substituted thianaphthalenes confirm
the ylidic nature of these non-planar heterocycles.
3.1. q3-Sulfoniopropenide Ligands
(Dialkylsulfonio)-2-propenides(-"allylides") are unstable and undergo [2,3]sigmatropic rearrangements with allylic inversionf5'. Nishiyama managed to fix and stabilize
species of this type at a palladium template[''].
0
-
(R2SCH2-CH=CH2)zPdBr4ZG
NaOAciMeOH
+ . . . (34)
R2S".";"_
PdBr,
R = Me
Rz = (CH2)4
These complexes decompose at 70 "C in [&]-MezSO to
afford 1,3,5-hexatriene.
2.3.5. a-Haloalkyl Complexes
Both the ylide complex 3 and the isomeric chelate complex 4, with the (2-picolinoyl)chloromethyl ligand, can be
isolated from the reaction of PtClZ(SMe2)Z with
Me2SCHC(0)-C5H4N. Compound 4 is formed from 3 by
removal and complexation of Me2S, and 1,Z-migration of a
chloride ion from the metal to the neighboring carbon
atom.
ex\ ez,
3.2. q5-Sulfoniocyclopentadienide Ligands
The different electronic shielding of the ring protons in
C5H4SMeZare balanced out by complexation to M(C0)3
(M=Cr, Mo, W, MnC, Ref). The synthesis of the complexes proceeds by exchange of labile acetonitrile ligands
in the corresponding starting materials.
(35)
(33)
,H
+
-N\ P t /c\
\ SMe,
c1
c1
3
/H
-N\
/c\
/Pt, C l
C1
SMe2
4
This corresponds to the retrosynthesis of sulfur ylide
complexes from halomethyl complexes and sulfanes (cf.
reaction (7)).
M = C r , Mo, W; n = 0
M = Mn, Re; n = 1
The crystal structure of the chromium complex shows
that there are no bonding interactions between the metal
and the sulfonium center["'.
3.3. Preparation and Structure of
k6-Thiabenzene 1-Oxide Complexes
3. Sulfur Ylides as 11-Ligands
If the carbanion function is stabilized by mesomerism
with vinyl substituents or by incorporation into a cyclic
diene system, the resulting sulfur ylide can behave as an
q3-or q5-ligand in n-interactions with metal centers.
Angew. Chem. Int. Ed. Engl. 22 (1983) 516-528
The h6-thiabenzene 1-oxides 5a-5d act as q5-6n-ligands
towards M(CO)3 fragments (M = Cr, Mo, W). The formation of two isomers, differing in the relative orientation of
metal and oxosulfonium center, is observed only for
~hromium[~*.'~~.
52 1
a)
a
b
c
d
e
6,9: M = C r
7,lO: M = M o
8,ll: M = W
R' P h M e M e tBu tBu
Ra Ph Ph M e P h tBu
In contrast, the di-tert-butyl derivative 5e affords only
the anti-isomer 9e"' with Cr(CO)3, but both syn- and antiisomers 7e, 8e, 10e, and l l e with Mo(CO)~ and
W(CO)3"31.
The formation of the anti-complexes probably starts
with attack of coordinatively unsaturated species, such as
(MeCN)ZM(CO),, on the "hard" oxygen of the oxosulfonium center (Scheme 2, pathway
whereas attack on the
"soft" n-system leads to the syn-configurated compound
(pathway 0).
bi
a),
Me
R'
$0
0
13
+ 2 L
"syn "
Scheme 2. Reaction pathways leading to syn- and anti-isomers of X"-thiabenzene I-oxide complexes.
This would also explain why chromium, as the hardest
metal, also forms anti-complexes. In 5e the small chromium atom of [(MeCN)2Cr(CO)3]is sterically blocked from
the n-system, and thus only the anti-compound 9e is
formed. The spatial demands of the bulky terf-butyl groups
in 5e force the larger and "softer" molybdenum and tungsten also to proceed by the otherwise unfavorable reaction
pathway @, again leading to anti-isomers.
The crystal structures of the free ylide 5a1743and the
isomeric chromium complexes 6a and 9ac7']confirm the
$-coordination of all five coplanar carbon atoms of the
non-planar heterocycle at the metal center. 5a adopts the
'Syn "-configuration in the crystal, the sulfur atom laying
39.5 pm above the plane of the carbon atoms[751.In the two
Cr(C0)3 complexes the sulfur atoms move a further 36 and
23 pm, respectively, away from this plane.
['I
Complexes with thesyn-configuration have the I-alkyl group and the metal atom on the same side of the ring: in the nnti-configuration, they are
on opposite sides.
522
Fig. 1. Structures of molecules Sa, 68 and 9a in the crystal. Selected bond
parameters (distances [pm], angles "7):
~~
Cr ...S
S-04
s-c2
S-C6
s-c7
C2-C3
c3-c4
c4-c5
C5-C6
planar (C, - C,)
Interplanar angle
5a
-
147.6(5)
166.2(6)
169.3(6)
182.1(7)
142.9(8)
136.6(9)
139.8(9)
141.0(9)
39.5
157.8"
6a
9a
289.8(2)
144.6(7)
171.1(8)
169.5(8)
181.1(9)
142.2( 10)
141.1(9)
140.7( 10)
143.2(10)
76
146'
280.7( 1)
144.9( 1)
172.0(2)
170.6(2)
177.1(2)
142.5(3)
141.2(3)
140.8(3)
142.8(3)
63
137"
These structures are noteworthy in view of the coordination behavior of h5-phosphabenzenes[761.The loss of planarity of the free heterocycles on complexing to
Cr(CO)3"6q shows that in their complex chemistry hs-phosphabenzenes, like h6-thiabenzene 1 -oxides, behave as
Angew. Chem. In!. Ed. Engl. 22 (1983) 516-528
ylidic ligands, whose onium centers are not involved in
bonding with the metal atom[771.
3.4 Chemical Properties of
k6-Thiabenzene 1-Oxide Complexes
Na,[Fe(CO),], LiPPh2, Li[BHEt3]; the products can be converted into stable tetraethylammonium salts by metathesis with [Et,N]Cl. The anions contain the novel thiacyclohexadienyl 1-oxide ligand[79,801,
which is a weaker donor
than the familiar $-cyclopentadienyl ligand.
Reports on h6-thiabenzene 1-oxides have mostly been
restricted to the preparation of the rings, but their chemistry has not been intensively investigated: reports have
included their reduction~64a~c~65i1
, H/D exchange[6sb*h-k1,
bromination and nitratior~'~~".'',
and reactions at substitM'NU = Na,[Fe(CO),j, L i P P h , , Li[ BHEt,]
kl.
The electron density of the ring is appreciably reduced
by coordination to the M(CO)3 group and transferred to
the metal. This electronic modification of both structural
elements of the complexes makes possible a series of reactions that cannot be carried out with the free ligand or with
the M(CO), group in other chemical environments. The
chemical properties of polyfunctional h6-thiabenzene l-oxide complexes are usually investigated with the 3,5-diphenyl derivatives; here reactions at positions 8-@
are possible (Scheme 3).
Scheme 3. Reactive centers of h6-thiabenzene 1-oxide complexes.
3.4.3. Deoxygenation to L'-T71iabenzene Complexes
The complex hydride Na[AIH2(0CH2CH,0Me)2] reacts
differently than LiIBHEt,] with h6-thiabenzene 1-oxide
complexes : whereas the syn-complexes, in an uncharacteristic way, decompose, the anti complexes are reduced to
h4-thiabenzene complexes 12[s11.
The reduction of 5a with C13SiH or LiAlH4, however,
gives thiopyrans and not the unstable h4-thiabenzenedma1.
The presence of the M(CO), protecting group is necessary
to stabilize the cyclic ylide.
3.4.1. Alkylation of the SCH, Group
The influence of the electron-withdrawing M(CO), unit
markedly increases the acidity of the hydrogen atoms of
the SCH, group (Scheme 3:
facilitating alkylations in
the two-phase system aqueous NaOH/CH,C12[781. The
SCH3 group can also be lithiated with n-C4H9Li, and the
resulting organolithium compound treated with a variety
of electrophiles RX1781.
a),
3.4.4. Protonation
The relatively long wavelength v(C0) absorption bands
indicate appreciable accumulation of electron density at
the metal carbonyl groups in h6-thiabenzene I-oxide complexes 6-817". In order to investigate the basicity of the
metal atoms, the complexes were dissolved in CF3C02H;
the molybdenum and tungsten derivatives were protonated
at the a-position of the ring (relative to the oxosulfonium
center)"*'. Deuteration experiments indicate endo-addition
to the ring, presumably via prior protonation of the metal.
In the tricarbonyl(cyclopentadieny1ide) complexes, on the
other hand, the metal-hydrogen bond remains stable[831.
m
-,
r
R X = MeI, C,H,Br, P h C H 2 B r , Me,SiCl, Me,GeCl, Me,SnCl,
MeHgCl
0
0
I-
I 9
n = 1.2
Chlorination of the S-alkyl group can be achieved by
reaction of the lithium derivatives with C13CCNL781.
X = H,D
3.4.2. Demethylation to
11'- Thiacyclohexadienyl 1-Oxide Complexes
h6-Thiabenzene 1-oxide complexes having the syn-configuration are demethylated by "soft" nucleophiles such as
Angew. Chem. Int. Ed. Engl. 22 (1983) 514-528
Silylation of the Ring
The reaction of 6a with excess n-C4H9Li, followed by
reaction with Me,SiCl and chromatographic separation on
523
SiOz, leads, in a manner analogous to reaction (37), to
complex 13, with the silyl group in the a-position of the
ring.
of the phenyl group (Scheme 3: 0)
prior to that of the central heterocycle is never
3.4.6. Rupture of the Metal-Ring Bond
Ph’
If the electron density of the ib-thiabenzene 1-oxide has
been modified by coordination to a metal, and the activated species subsequently allowed to react further, the
last step in the cycle is often the removal of the chemically
altered ligand. 5a is quantitatively displaced from complexes by excess PhPMez in boiling THFLZ7].
I ‘SiMe,
CdCO),
endo-Hydride Addition
The coordination of the hb-thiabenzene 1-oxide to the
(CO),Cr(NO) cation (see Scheme 3: @) brings about a
marked decrease in electron density at the 3- and 5-positions of the ring; these thus acquire electrophilic characteristics. Complexes of novel double ylide sulfonium comp o u n d ~ [ can
~ ~ ]then be formed by endo-hydride addition
reactions of unusual reaction type[841.Figure 2 shows the
molecular structure of 14d.
B
PhPMez
p
h
-
~
P
+h (PhPMe,),Mo(CO),
5a
3.4.7. Displacement of CO
In the syn-configurated (hb-thiabenzene 1-0xide)chromium complexes 6, a CO ligand can easily be replaced by
the isoelectronic NO+ ion, without breaking the metalring bonds1861.
Ql
Fig. 2. Molecular structure of 1 4 with selected bond lengths.
Cationic arene(dicarbony1)nitrosyl complexes of molybdenum and tungsten are, as yet, unknown; all attempts to
prepare them have led to loss of the arene ligand[871.Use of
electron-donating or bulky groups (R’ = RZ= Ph; R3 =
CH(SiMe&., CH(CH2Ph)Z;R’ = R2=tBu, R3= Me) on the
h6-thiabenzene 1-oxide ligand stabilizes the metal-ring
bond to such an extent that cationic dicarbonyl(nitr0sy1)molybdenum and -tungsten complexes with organic 6nligands become accessible[8b!
3.5. Preparation and Structure of
ItThiabenzene Complexes
l a
b
c
d
14
h4-Thiabenzene complexes of type 12 are accessible by
deoxygenation of h6-thiabenzene 1-oxide complexes (cf.
Section 3.4.3). This process is, however, dependent on the
existence of complexes, such as 9-11, having the anti-
3.4.5. Complex Formation at Phenyl Substituents
The phenyl substituents of h6-thiabenzene 1-oxide ligands also exhibit donor properties, although coordination
9
L3M(COh
___,
R = Me, Et; M = C r , L = MeCN; M = Mo, W, L, = C,H8
524
Angew. Chem. I n f . Ed. Engl. 22 (1983) SI6-52%
(43)
configuration. In some cases the synthesis can be achieved
by trapping h4-thiabenzenes generated in sitdSg1.
Structural changes associated with the coordination of
the h6-thiabenzene I-oxide 5a to the Cr(C0)3 group are
known. Information on the structure of the therrnolabile
h4-thiabenzene derivative analogous to 5a can be obtained
from the X-ray structure analysis of its Cr(CO)3 complex
12a and by comparison with data for 5a, 6a, and 9a. In
the stable, crystalline 12a (Fig. 3) the heterocycle is
bonded to the chromium atom through the five coplanar
carbon atoms (as in the anti-complex 9a). The sulfur atom
lies 75 pm above this plane and is directed away from the
chromium (d(Cr-S)=288 pm). The methyl group occupies
the axial “anti”-position at the pyramidal sulfur: syn/anti
isomerism has not been detected. The ylidic nature of
these heterocycles is thus established by means of their
coordination chemistry. It is possible that the free ligand
has a similar configuration.
3.6.2. Nitrosylation
Cationic h4-thiabenzene complexes are obtained by substitution of CO by NO * ; the ring ligand exhibits electrophilic properties and, in preliminary studies, has been
shown to add hydride ion (cf. reaction (41))19”.
P3
3.7. Chemical Properties of
q5-Thiacyclohexadienyl1-Oxide Complexes
The q5-thiacyclohexadienyl 1 -oxide complexes synthesized as described in Section 3.4.2 possess structures similar to those of the corresponding syn-h6-thiabenzene l-oxide complexes 6-8. Demethylation appreciably increases
the nucieophilicity of the complexes. Like other complex
anions, they are valuable synthetic building blocks in organometallic chemistry.
3.7. I . Ligand Displacement
Fig. 3. Molecular structure of 1Za with selected bond lengths.
The chromium complexes are easily nitrosylated to give
neutral complexes[93’.
p+..
::
3.6. Chemical Properties of b4-Thiabenzene Complexes
Because of their thermolability, the Chemistry of h4-thia-+ co
MeC&SO~NtMe)NO
.. ( 4 8 )
benzene complexes has been little i n v e ~ t i g a t e d [ ~ ~ “ , ~ ~ - ~ ’ ~ .
The stabilizing influence of the M(CO), template should,
C r(C 0 )zNO
as with h6-thiabenzene 1-oxide complexes, allow a wide
variety of reactions of h4-thiabenzenes to be investigated;
some preliminary results have been obtained.
A further ligand L can be introduced by the amine oxide
method to give chiral complexes[931.
3.6.1. Metalation and Alkylation of the SCH, Group
The hydrogen atoms of the SCH, group are sufficiently
acidic to allow lithiation and subsequent reaction with
electrophiles. The h4-thiabenzene ligands thus formed
have not yet been obtained by other methods[88bJ.
0
149)
R/Z
L
+
...
0
=
I
C r ( CO),NO
P P h 3 , P P h z M e . P P h M e 2 , C5H5N
3.7.2. Halogenation
T h e molybdenum and tungsten complexes are halogenated by PhICI,, CsHsN. Br,, or 12rso1.
Angew. Chem. Int. Ed. Engl. 22 (1983) S16-528
525
(50)
M = Mo, W
[ H a l l = PhIC12, C5H,N.Br,, I,;
X =
3.7.3. Alkylation
“Hard” alkylating agents attack the oxosulfonium center. A 2H-thiopyran complex is isolated, rather than the
expected isomeric S-methoxylated h4-thiabenzene comple~‘~~].
OMe
OMe
Ph
3.7.4. Amination
by analogy to the work of Kresze et aE.[951,it should be
possible to synthesize 1-amino-h4-thiabenzene complexes
by reaction with [Me,NSO]+BF;. Here also, however,
only the isomeric 2H-thiopyran complex can be isolated,
whose structure is confirmed by X-ray crystallography[941.
NMe,
I
Ph
S
\ / I
Et4N0
NMe,
Ph
1
The rearrangements described in reactions (51) and (52)
are novel in organometallic chemistry and may perhaps
best be compared with the Pummerer rearrangement. The
chirality of the complexes obtained from reactions (48),
(49), (51), and (52) raises the question of whether asymmetric syntheses are possible.
4. Summary and Prospects
The coordination chemistry of open-chain sulfur ylides
show similarities to, but also clear differences from. the
526
chemistry of phosphorus ylides. The differences arise, as in
the organic chemistry of these compounds, from the
greater leaving-group tendency of diorganosulfanes or sulfoxides. Thus, some sulfur ylide complexes function as metal-alkylidene transfer reagents. Whereas free sulfur ylides
can cyclopropanate only activated olefinic double bonds,
they undergo an umpolung upon complexing to metals; in
so doing they acquire electrophilic properties, and are then
able to cyclopropanate electron-rich olefins. This reaction
type is also feasible in vivo and may be of biochemical relevance. The tendency of sulfoxides to act as good leaving groups enables (formally) the [(CO),Cr=CH,] fragment to be transferred from the ylide complexes
(CO),Cr[CH,S(O)Me], and (C0)5Cr[CH,S(0)Me2] to methylenebisphosphanes and -arsanes, thus forming coordination compounds of unstable phosphorus ylides. The regiospecificity of this reaction is clearly determined by the
nature of the organometallic complex. The thermolabile
h4-thiabenzenes can act as ylidic $-ligands at suitable metal centers, and can thus be stabilized. This is achieved by
trapping the free rings in situ or by reduction of anti-h6thiabenzene I-oxide complexes. The crystal structure of
the Cr(CO)3 complex rules out any heteroaromaticity of
the ligand ring and suggests a structure similar to that of
the corresponding oxide for the free ylide ligand.
h6-Thiabenzene 1-oxides form a series of structurally
fascinating complexes with M(C0)3 (M=Cr, Mo, W);
these undergo a variety of interesting reactions, which enrich our knowledge of organometallic chemistry. qs-Thiacyclohexadienyl 1-oxide complexes display an interesting
rearrangement of the coordinated ligand, comparable to
the Pummerer rearrangement, on reaction with “hard”
electrophiles.
The chemistry of organometallic complexes and sulfur
ylides as reaction partners is, hence, far from exhausted;
indeed, the reactions with coordinated ligands have been
scarcely investigated. It should also be noted that, despite
the wide range of known sulfur ylides, only a few have
been studied as ligands. This is clearly due, at least in part,
to their high reactivity; but this also suggests the possibility of generating reactive metal ylide complexes and thus
extending the synthetic tools of the preparative chemist.
I should like to thank Prof. Dr. Giinter Schmidfor generous support of our work. Frau D . Vehreschild-Yzermann,
Frl. M . StoHeI, Frl. M . Utzat, Herr D . Wewers, and Herr U.
Meyer are thanked for committed and conscientious collaboration; Dr. R . Boese and Prof. Dr. C. Kriiger (Miilheim a . d .
Ruhr) and their co-workers for X-ray analyses; and ProJ Dr.
B. M . Trost for hospitality during my stay a t the University
of Wisconsin, Madison. The Deutsche Forschungsgemeinschaft, the Fonds der Chemischen Industrie, and Degussa
(Hanau) and Hoechst AG (Werk Knapsack) provided financial support.
Received: April 25, 1983 [A 460 IEI
German version: Angew. Chem. 95 (1983) 539
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I781 L. Weber, Chem. Ber. 112 (1979) 3828.
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1891 Under mild conditions thiabenzenes, -naphthalenes, and anthracenes
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