Manganese(I) and rhenium(I) tricarbonyl (alkylthio)methyl and alkylidenesulfonium complexes

Article abstract of DOI:10.1021/om020522i

The reactions of Na[M(CO)₃(bipy)] (M = Mn, Re) compounds with ClCH₂SR (R = Me, Ph) afford the (alkylthio)alkyl complexes [Mn(CH₂SMe)(CO)₃(bipy)] (la), [Mn(CH₂SPh)(CO)_3- (bipy)] (1b), [Re(CH

Full text of DOI:10.1021/om020522i

5312
Organometallics 2002, 21, 5312-5319
Ma n ga n ese(I) a n d Rh en iu m (I) Tr ica r bon yl
(Alk ylth io)m eth yl a n d Alk ylid en esu lfon iu m Com p lexes
Eva Hevia, J ulio Pe´rez,* and V´ıctor Riera
Departamento de Quı´mica Orga´nica e Inorga´nica-IUQOEM, Facultad de Quı´mica,
Universidad de Oviedo-CSIC, 33071 Oviedo, Spain
Daniel Miguel
Departamento de Quı´mica Inorga´nica, Facultad de Ciencias, Universidad de Valladolid,
47071 Valladolid, Spain
Received J uly 2, 2002
The reactions of Na[M(CO)3(bipy)] (M ) Mn, Re) compounds with ClCH2SR (R ) Me, Ph)
afford the (alkylthio)alkyl complexes [Mn(CH2SMe)(CO)3(bipy)] (1a ), [Mn(CH2SPh)(CO)3-
(bipy)] (1b), [Re(CH2SMe)(CO)3(bipy)] (2a ), and [Re(CH2SMe)(CO)3(bipy)] (2b). Methylation
at sulfur of these compounds with methyl triflate affords the methylidenesulfonium cations
[Mn(CH2SMe2)(CO)3(bipy)]+ (5a ), [Mn(CH2SMePh)(CO)3(bipy)]+ (5b), [Re(CH2SMe2)(CO)3-
(bipy)]+ (6a ), and [Re(CH2SMePh)(CO)3(bipy)]+ (6b) as their triflate salts. These new
compounds were characterized by IR and NMR spectroscopy, and the crystal structures of
1b, 2a , 5b, and 6b have been determined by X-ray diffraction. The sulfonium complexes are
unreactive toward PPh3 and pyridine. The reactions of 5b and 6b with I-, PPh2-, and SEt-
anions afford the (phenylthio)methyl complexes 1b and 2b, resulting from nucleophilic attack
at the methyl group. 5b and 6b react with styrene to give phenylcyclopropane, free thio-
anisole, and the corresponding [M(OTf)(CO)3(bipy)] complex.
In tr od u ction
pertinent to the work described here are the d6 Re(I)
sulfonium complexes [CpRe(NO)(PPh3)(CH2SR2)]+, which
were synthesized by addition of dialkyl sulfides to the
highly electrophilic [CpRe(dCH2)(NO)(PPh3)]+ meth-
ylidene cation.6 This route exemplifies the reverse of the
in situ generation of carbenes mentioned above. Nor-
mally, sulfonium complexes, whose carbene-transfer
activity avoids the need for the difficult isolation of the
highly electrophilic alkylidene complexes, are conve-
niently prepared by addition of electrophiles to the
sulfur atom of (alkylthio)methyl complexes, in turn
obtained by reaction of chloromethyl alkyl sulfides with
suitable anionic complexes.7 However, such anions are
not available for the derivatives of the{CpRe(NO)-
(PPh3)} fragment.
Two families of electrophilic d6 complexes, namely,
octahedral chromium and tungsten Fischer alkoxycar-
benes [(CO)5MdC(R)OR′]1 and cationic iron complexes2
[Cp(CO)2FedC(R)R′]+, are among the transition-metal
compounds best studied regarding their ability to
transfer carbene moieties to olefins. Due to the lack of
heteroatom stabilization, the latter compounds show a
higher electrophilicity at the carbene carbon and, as a
result, cyclopropanate a broader range of olefins, and
these reactions can be conducted at lower temperatures.
Owing to their limited stability, these highly electro-
philic species are often generated in situ. The corre-
sponding sulfide-alkylidene adducts,3 i.e., salts of the
cationic alkylidenesulfonium complexes [Cp(CO)2FeCH2-
SR2]+, have been found to be stable yet active in olefin
cyclopropanation.4 Reagents of this kind have been
prepared with several other metal fragments.5 Most
Octahedral complexes of {M(CO)3(bipy)} (M ) Mn,
Re) fragments are robust and do not present steric
hindrance to the access of reagents to the ligand
occupying the remaining coordination position.8 More-
over, generation of [M(CO)3(bipy)]- anions can be ac-
complished by the reduction of easily available, stable
* Correspondence author. E-mail: japm@sauron.quimica.uniovi.es.
(1) (a) Wulff, W. D. Organometallics 1998, 17, 3116. (b) Sierra, M.
A. Chem. Rev. 2000, 100, 3591.
(2) Brookhart, M.; Studabaker, W. B. Chem. Rev. 1987, 87, 411.
(3) These compounds can, alternatively, be considered sulfur ylide
complexes. For a review of ylide complexes, see: (a) Weber, L. Angew.
Chem., Int. Ed. Engl. 1983, 22, 516. For leading references not included
in this review, see: (b) Seyferth, D.; Womack, G. B.; Cowie, M.; Hames,
B. W. Organometallics 1983, 2, 1696. (c) Wu, R. F.; Lin, I. J . B.; Lee,
G. H.; Cheng, M. C.; Wang, Y. Organometallics 1990, 9, 126. (d) Lin,
I. J . B.; Liu, C. W.; Liu, L.-K.; Wen, Y.-S. Organometallics 1992, 11,
1447. (e) Werner, H.; Mahr, N.; Frenking, G.; J onas, V. Organometallics
1995, 14, 619. (f) McCrindle, R.; Ferguson, G.; McAlees, A. J .;
Arsenault, G. J .; Gupta, A.; J ennings, M. C. Organometallics 1995,
14, 2741. (g) Vicente, J .; Chicote, M. T.; Guerrero, R.; J ones, P. G. J .
Am. Chem. Soc. 1996, 118, 699. (h) Feng, D.-F.; Tang, S. S.; Liu, C.
W.; Lin, I. J . B. Organometallics 1997, 16, 901. (i) Yakayama, C.;
Takeuchi, K.; Ohkoshi, S.; J anairo, G. C.; Sugiyama, T.; Kajitani, M.;
Sugimori, A. Organometallics 1999, 18, 2843.
(4) (a) Brandt, S.; Helquist, P. J . Am. Chem. Soc. 1979, 101, 476.
(b) Kremer, K. A. M.; Helquist, P.; Kerber, R. C. J . Am. Chem. Soc.
1981, 103, 1862. (c) O’Connor, E. J .; Helquist, P. J . Am. Chem. Soc.
1982, 104, 1869. (d) Kremer, K. A. M.; Helquist, P. J . Organomet.
Chem. 1985, 285, 231. (e) O’Connor, E. J .; Brandt, S.; Helquist, P. J .
Am. Chem. Soc. 1987, 109, 3739. (f) McCarten, P.; Barefield, E. K.
Organometallics 1998, 17, 4645.
(5) (a) Davidson, J . G.; Barefield, E. K.; Van Derveer, D. G.
Organometallics 1985, 4, 1178. (b) Barefield, E. K.; McCarten, P.;
Hillhouse, M. C. Organometallics 1985, 4, 1682.
(6) McCormick, F. B.; Gleason, W. B.; Zhao, X.; Heah, P. C.; Gladysz,
J . A. Organometallics 1986, 5, 1778.
(7) Steinborn, D. Angew. Chem., Int. Ed. Engl. 1992, 31, 401.
(8) Hevia, E.; Pe´rez, J .; Riera, V.; Miguel, D. Organometallics 2002,
21, 1966.
10.1021/om020522i CCC: $22.00 © 2002 American Chemical Society
Publication on Web 11/01/2002

Mn(I) and Re(I) (Alkylthio)methyl Complexes
Organometallics, Vol. 21, No. 24, 2002 5313
Ta ble 1. Selected Bon d Dista n ces a n d An gles for
Com p lexes 1b a n d 2a
Sch em e 1
1b
2a
M(1)-C(4)
M(1)-C(1)
M(1)-C(2)
M(1)-C(3)
M(1)-N(1)
M(1)-N(2)
C(4)-S(1)
S(1)-C(5)
C(1)-O(1)
C(2)-O(2)
C(3)-O(3)
2.125(4)
1.820(4)
1.772(5)
1.780(4)
2.045(4)
2.039(3)
1.763(4)
1.764(4)
1.124(4)
1.152(5)
1.162(5)
2.276(6)
1.943(7)
1.906(7)
1.902(7)
2.184(5)
2.187(7)
1.759(6)
1.797(5)
1.160(8)
1.171(8)
1.182(8)
[MX(CO)3(bipy)] halo complexes on these manganese
and rhenium systems.9 Here we report the employment
of these anions to prepare isolable (alkylthio)methyl
complexes, subsequent methylation of which with MeOTf
affords cationic alkylidenesulfonium compounds. The
reactivity of the latter toward nucleophiles and the
structural characterization of several new compounds
are also included.
C(1)-M(1)-C(4)
C(2)-M(1)-C(4)
C(3)-M(1)-C(4)
N(1)-M(1)-C(4)
N(2)-M(1)-C(4)
C(3)-M(1)-C(1)
C(3)-M(1)-C(2)
C(2)-M(1)-C(1)
C(3)-M(1)-N(1)
C(2)-M(1)-N(1)
C(1)-M(1)-N(1)
C(3)-M(1)-N(2)
C(2)-M(1)-N(2)
C(1)-M(1)-N(2)
N(1)-M(1)-N(2)
S(1)-C(4)-M(1)
C(4)-S(1)-C(5)
176.47(19)
86.98(19)
93.95(19)
83.76(14)
85.30(15)
89.0(2)
177.4(2)
91.6(2)
94.1(2)
83.1(2)
82.6(2)
87.6(3)
89.4(3)
90.5(3)
97.8(2)
171.3(2)
94.7(2)
171.5(2)
98.5(2)
95.5(2)
74.11(18)
110.9(3)
104.5(3)
89.0(2)
91.2(2)
173.91(18)
96.51(19)
93.45(17)
96.11(19)
171.02(2)
96.26(16)
78.12(16)
114.5(2)
106.9(2)
Resu lts a n d Discu ssion
A THF solution of the compound Na[Mn(CO)3(bipy)],9a
generated in situ by reaction of [MnBr(CO)3(bipy)] with
sodium amalgam, was added to an equimolar amount
of chloromethyl methyl sulfide. The disappearance of
the intense blue color of the anion indicated an instan-
taneous reaction. The νCO IR bands of the crude solution
showed the formation of the single fac-tricarbonyl
species 1a , with wavenumber values compatible with a
neutral formulation (1998 and 1890 cm-1 versus 1912,
1823, and 1782 cm-1 for the anion). These values are
shifted to lower frequencies with respect to the bromo
complex precursor (2022, 1934, and 1914 cm-1 in THF)
and are closer to those of known [Mn(R)(CO)3(bipy)]
alkyls (1988 and 1889 cm-1 in CH2Cl2 for R ) CH3).9a
This suggests a [Mn(CH2SCH3)(CO)3(bipy)] composition,
as depicted in Scheme 1. Pure 1a could be isolated in
good yield as a microcrystalline solid and was charac-
terized on the basis of its spectroscopic and analytical
data. The 1H NMR spectrum includes a four-signal
pattern for the bipy ligand, as expected for a molecule
with a mirror plane, and singlets at 1.82 and 1.27 ppm
assigned to the methyl and methylene groups of the
(methylthio)methyl ligand, respectively. These groups
occur as signals at 32.36 (CH2) and 24.29 (CH3) ppm in
the 13C NMR spectrum. In this spectrum two of the
carbonyl ligands appear as a single signal, and the bipy
ligand gives rise to five signals, further indicating the
presence of a molecular mirror plane.
proximately octahedral environment formed by three
mutually facial carbonyls, the two nitrogens of a
2,2′-bipyridine chelate, and a monodentate, C-bound
(phenylthio)methyl ligand. By similar procedures, the
rhenium complexes [Re(CH2SMe)(CO)3(bipy)] (2a ) and
[Re(CH2SPh)(CO)3(bipy)] (2b) were synthesized and
characterized (see Experimental Section). The structure
of 2a was determined by single-crystal X-ray diffraction
(Figure 1b and Table 1). The geometry of the molecule
is, with regard to the metal environment, like that
described for the manganese complex 1b, the major
deviation from idealized octahedral geometry being for
both compounds the acute N-M-N angles (<79°)
imposed by the natural bite angle of the rigid chelate.
In both structures, the M-CO distance is significantly
longer for the carbonyl group trans to the (alkylthio)-
methyl ligand, revealing that the latter exerts a trans
influence larger than the bipy nitrogens. Unfortunately,
despite the abundance of complexes containing fac-
{M(CO)3(N-N)} (M ) Mn, Re) fragments whose struc-
tures have been determined by means of X-ray diffrac-
tion, the only simple alkyl derivative within this family
is [Re(CH3)(CO)3(iPr-DAB)] (iPr-DAB ) 1,4-diisopropyl-
1,4-diaza-1,3-butadiene), for which the disorder affecting
the methyl group precludes any meaningful compari-
son.10 The M-CH2SR distances in 1b (2.125(4) Å) and
2a (2.276(6) Å) do not show significant differences from
M-C(alkyl) distances found for other octahedral alkyl
carbonyl complexes of these metals. For instance, a Mn-
CH3 distance of 2.14(2) Å was found for the complex
[Mn(CH3)(P(OMe)3)(CO)2(iPr-DAB)].11
The reaction of Na[Mn(CO)3(bipy)] with chloromethyl
phenyl sulfide yielded [Mn(CH2SPh)(CO)3(bipy)] (1b) in
an analogous manner. As expected for the substitution
of methyl by the less electron-releasing phenyl group,
the IR νCO bands occur at frequencies slightly higher
than those of 1a . In addition to its spectroscopic and
analytical characterization (see Experimental Section),
the structure of 1b was determined by X-ray diffraction
(see Figure 1a and Table 1). The molecule of this
complex consists of a manganese atom in an ap-
In an attempt to synthesize cationic sulfonium com-
plexes, [Re(CH2SPh)(CO)3(bipy)] (2b) was allowed to
react with an equimolar amount of triflic acid in CH2-
(9) (a) Garc´ıa-Alonso, F. J .; Llamazares, A.; Vivanco, M.; Riera, V.;
Garc´ıa-Granda, S. Organometallics 1992, 11, 2826. (b) Stor, G. J .;
Hartl, F.; van Outerstep, J . W. M.; Stufkens, D. J . Organometallics
1995, 14, 1115.
(10) Rossenaar, B. D.; Kleverlaan, C. J .; van de Ven, M. C. E.;
Stufkens, D. J .; Oskam, A.; Goubitz, K. J . Organomet. Chem. 1995,
493, 153.

5314 Organometallics, Vol. 21, No. 24, 2002
Hevia et al.
F igu r e 1. Thermal ellipsoid (30%) plots of 1b (a) and 2a (b).
Sch em e 2
Cl2. The instantaneous formation of the triflato complex
[Re(OTf)(CO)3(bipy)] (IR νCO: 2035, 1935, and 1914
cm-1 12
revealed that the metal-alkyl bond, instead of
)
the sulfur atom, was the site of the attack of the strong
acid. This was confirmed by the observation of 1 equiv
of thioanisole (aromatic multiplet at 7.25 ppm and
singlet at 2.47 ppm), in addition to the signals of the
triflato complex, when the reaction was carried out in
CD2Cl2 in an NMR tube. We have found a related result
in earlier work; thus, in an attempt to obtain the
cationic methylidene complex [Re(dCH2)(CO)3(bipy)]+,
we reacted equimolar amounts of [Re(CH3)(CO)3(bipy)]
(3)13 and [Ph3C][PF6]. The resulting solution showed an
IR spectrum consistent with the formulation [Re(L)-
(CO)3(bipy)]+ (2038 and 1934 cm-1),14 but no signal
attributable to a methylidene complex could be detected
in the NMR.15 We reasoned that if an unstable meth-
ylidene complex was being formed, it could be trapped
as the more stable methylidenesulfonium derivative (see
above) by generating the electrophilic complex in the
presence of a dialkyl sulfide. However, the reaction of
the methyl complex, the trityl salt, and thioanisole led
to [Re(SMePh)(CO)3(bipy)]PF6 (4) (see Scheme 2) as the
only organometallic species spectroscopically observed,
indicating abstraction by the trityl cation of the entire
methyl group instead of the hydride. The fact that
thioanisole is coordinated in compound 4, while the
triflato complex [Re(OTf)(CO)3(bipy)] and free thioani-
sole are obtained from the reaction of 2b with HOTf,
results from the lower coordinating ability of the
hexafluorophosphate anion compared with triflate.
Next, methylation of 1a was attempted. Methyl iodide
failed to react (see below). Thus, the stronger methyl-
ating agent methyl triflate was used, and an instanta-
neous reaction led to the single product 5a , as indicated
1
by the IR and H NMR monitoring. The IR νCO bands
of 5a still feature the pattern typical of a fac-tricarbonyl
moiety but occur at wavenumbers some 20 cm-1 higher
than the neutral (alkylthio)methyl complex precursor.
While this shift has the sign expected for a conversion
of a neutral complex into a cationic one, its magnitude
is rather small. In fact, the νCO IR bands of 5a are very
close to those of the neutral complex [MnBr(CO)3(bipy)]
(see above). The 1H NMR spectrum of 5a includes a two-
hydrogen singlet at 1.18 ppm attributed to the meth-
ylene group, and a six-hydrogen singlet at 2.71 ppm,
corresponding to two equivalent methyl groups. These
data are consistent with a [Mn(CH2SMe2)(CO)3(bipy)]-
OTf formulation for 5a , as depicted in Scheme 3. The
IR νCO bands at frequencies relatively low for a cationic
complex (see above) can be, thus, taken as indicative of
a strong donor character for the sulfur ylide ligand.
Complex [Mn(CH2SPh)(CO)3(bipy)] (1b) underwent a
similar methylation to yield the compound [Mn(CH2-
(11) The two CO groups are in cis disposition, and CH3 and P(OMe)3
ligands are mutually trans in this complex: Rossenaar, B. D.; Stufkens,
D. J .; Oskam, A.; Fraanje, J .; Goubitz, K. Inorg. Chim. Acta 1996, 247,
215.
(12) Guerrero, J .; Pino, O. E.; Wolcan, E.; Feliz, M. R.; Ferraudi,
G.; Moya, S. A. Organometallics 2001, 20, 2842.
(13) Lucia, L. A.; Burton, R. D.; Schanze, K. S. Inorg. Chim. Acta
1993, 208, 103.
(14) Hevia, E.; Pe´rez, J .; Riera, V.; Miguel, D.; Rheingold, A.; Kassel,
S. Inorg. Chem. 2002, 41, 4673.
(15) For a successful generation of a cationic methylidene complexes
by this route see: (a) Gunnoe, T. B.; White, P. S.; Templeton, J . L.;
Casarrubios, L. J . Am. Chem. Soc. 1997, 119, 3171. (b) Gunnoe, T. B.;
Surgan, M.; White, P. S.; Templeton, J . L.; Casarrubios, L. Organo-
metallics 1997, 16, 4865. (c) Le Bras, J .; J iao, H.; Meyer, W. E.; Hampel,
F.; Gladysz, J . A. J . Organomet. Chem. 2000, 616, 54.

Mn(I) and Re(I) (Alkylthio)methyl Complexes
Organometallics, Vol. 21, No. 24, 2002 5315
F igu r e 2. Thermal ellipsoid (30%) plots of 5b (a) and 6b (b).
Ta ble 2. Selected Bon d Dista n ces a n d An gles for
Com p lexes 5b a n d 6b
Sch em e 3
5b
6b
M(1)-C(4)
M(1)-C(1)
M(1)-C(2)
M(1)-C(3)
M(1)-N(1)
M(1)-N(2)
C(4)-S(1)
S(1)-C(5)
S(1)-C(21)
C(1)-O(1)
C(2)-O(2)
C(3)-O(3)
2.122(6)
1.804(6)
1.792(6)
1.803(7)
2.055(5)
2.040(5)
1.755(6)
1.806(7)
1.787(6)
1.130(7)
1.148(7)
1.143(8)
2.243(6)
1.921(7)
1.919(7)
1.912(8)
2.187(5)
2.173(5)
1.744(7)
1.787(7)
1.786(7)
1.140(7)
1.145(8)
1.152(8)
C(1)-M(1)-C(4)
C(2)-M(1)-C(4)
C(3)-M(1)-C(4)
N(1)-M(1)-C(4)
N(2)-M(1)-C(4)
C(3)-M(1)-C(1)
C(3)-M(1)-C(2)
C(2)-M(1)-C(1)
C(3)-M(1)-N(1)
C(2)-M(1)-N(1)
C(1)-M(1)-N(1)
C(3)-M(1)-N(2)
C(2)-M(1)-N(2)
C(1)-M(1)-N(2)
N(1)-M(1)-N(2)
S(1)-C(4)-M(1)
C(21)-S(1)-C(5)
C(4)-S(1)-C(21)
C(4)-S(1)-C(5)
173.9(3)
96.1(3)
92.4(3)
82.3(2)
86.7(2)
87.4(3)
88.7(3)
90.0(3)
97.0(2)
174.2(2)
91.7(2)
175.9(2)
95.5(2)
93.0(2)
78.90(19)
118.3(3)
101.1(3)
105.7(3)
105.6(4)
173.6(3)
96.9(3)
94.4(3)
81.2(2)
83.7(2)
87.0(3)
88.3(3)
89.4(3)
99.6(2)
172.0(2)
92.4(2)
174.1(2)
97.6(3)
94.2(2)
74.6(2)
116.8(3)
102.0(3)
105.8(3)
105.8(3)
SMePh)(CO)3(bipy)]OTf (5b), and parallel results were
encountered with the rhenium complexes 2a and 2b,
which afford the sulfonium salts [Re(CH2SMe2)(CO)3-
(bipy)]OTf (6a ) and [Re(CH2SMePh)(CO)3(bipy)]OTf
(6b), respectively (see Scheme 3). As expected, diaste-
reotopic methylene hydrogens are observed for the
methylphenylsulfonium complexes 5b and 6b, in which
the sulfur atoms are stereocenters. Accordingly, asym-
metric bipy patterns are observed in the 1H NMR
spectra of these compounds. Low solubility precluded
the acquisition of significant 13C NMR spectra for
complexes 5a and 6a , whereas for their more soluble
methylphenylsulfonium counterparts, whose 13C NMR
data could be obtained, the methylene singlets occur at
chemical shift values (34.30 ppm for 5b and 25.79 ppm
for 6b) close to those found for the neutral precursors
1b (23.57 ppm) and 2b (26.39 ppm). Ten signals for the
bipy carbons and three carbonyl signals are seen in the
13C NMR for each of the chiral complexes 5b and 6b.
The structures of 5b and 6b were determined by
X-ray diffraction, and the results are shown in parts a
and b, respectively, of Figure 2 and in Table 2. These
results confirm that the new complexes consist of a
triflate anion (not shown in Figure 2) and a [M(CH2-
SMePh)(CO)3(bipy)]+ cation (M ) Mn, 5b; M ) Re, 6b),
resulting from the methylation at sulfur of the (alkyl-
thio)methyl precursor. For the first time, the structures
of neutral (alkylthio)alkyl complexes and those of the
corresponding cationic alkylidenesulfonium complexes
are available. A comparison between the neutral and
cationic complex for each metal reveals, as the most
salient feature, virtually identical M-CH2 distances.
This is somewhat unexpected; thus, some shortening of
the M-C bond would be anticipated to occur upon
methylation, given that the methylidenesulfonium com-
plex can be considered the adduct of a dialkyl sulfide
and a methylidene complex and, therefore, should have
some incipient carbene character.4c In the structure of
both cationic complexes, the three M-CO distances are
virtually identical; thus, in contrast with akylthioalkyl
groups (see above), the alkylidenesulfonium ligand has
a trans influence indistinguishable from that of the
bipyridyl chelate. The geometries around the sulfur
atoms of 5b and 6b are pyramidal, and the sums of the
three C-S-C angles, 312.4 and 313.6°, respectively, and
the C-S distances are similar to the values previously
found for other alkylidenesulfonium complexes.4c

5316 Organometallics, Vol. 21, No. 24, 2002
Hevia et al.
iodide (2.16 ppm) was observed in the 1H NMR spectrum
of the resulting solution. This reactivity of the sulfonium
cation toward iodide anion explains the lack of reactivity
shown by [Mn(CH2SCH3)(CO)3(bipy)] (1a ) toward meth-
yl iodide (see above), since the expected products for this
reaction would be the sulfonium cation and iodide,
which have now been shown to react to generate the
reagents of the unobserved reaction. Therefore, the
strength of our sulfonium complexes as methylating
agents is intermediate between methyl iodide and
methyl triflate.17 Likewise, MePPh2 (-26.33 ppm in 31P
NMR) was observed as the product in the reaction of
5b with KPPh2.
Sch em e 4
We wanted to study the reactivity of the cationic
sulfonium complexes toward olefins and chose styrene
as an olefin for which cyclopropanation experiments
have been described.18 Since methylphenylsulfonium
complexes have been reported to be more reactive than
their dimethyl counterparts,4e we studied the reactivity
of compounds 5b and 6b toward styrene. No reaction
was observed upon mixing the reagents in CH2Cl2, THF,
or toluene and allowing the mixtures to stand at room
temperature for several hours. Heating equimolar
amounts of 5b and styrene in THF at 65 °C led to
conversion of the sulfonium complex to [Mn(OTf)(CO)3-
(bipy)] over a period of 5 h (IR monitoring). The nature
of the manganese product, which could be isolated by
in vacuo evaporation of volatiles followed by washing
We have explored the reactivity of the new sulfonium
complexes toward nucleophiles. No reaction was ob-
served with either triphenylphosphine or pyridine (3
equiv, THF as solvent, 24 h, room temperature).16
Furthermore, the complexes [M(CH2SMePh)(CO)3(bipy)]-
OTf (M ) Mn, 5b; M ) Re, 6b) did not react with
dimethyl sulfide under the same conditions. These
results contrast with those found for other sulfonium
complexes. Thus, [CpRe(NO)(PPh3)(CH2SMe2)]+ revers-
ibly loses dimethyl sulfide (to give the methylidene
complex [CpRe(dCH2)(NO)(PPh3)]+), which can also be
displaced by neutral nucleophiles such as PPh3 and
pyridine.6 On the other hand, the complex [Cp(CO)2Fe-
(CH2SMe2)]+ exchanged dimethyl sulfide with other
dialkyl sulfides, yielding new alkylidenesulfonium
complexes.4e The geometry of our [M(CH2S(Me)R)(CO)3-
(bipy)]+ complexes is octahedral, and, considering that
the alkylidenesulfonium group occupies an axial posi-
tion, the planar ring of the bipy chelate and the two
carbonyl groups lie in a equatorial plane. Therefore, the
above-mentioned lack of reactivity toward neutral nu-
cleophiles cannot be due to steric hindrance. Most likely,
then, the low electrophilicity at the metal and methylene
carbon results from the presence of the strongly donat-
ing bipyridine ligand.
We next studied the reactivity of 5b and 6b toward
anionic nucleophiles. The reactions of 5b with potassium
diphenylphosphide (generated in situ by reaction of
diphenylphosphine with K[N(SiMe3)2]),potassium ethane-
thiolate (from EtSH and K[N(SiMe3)2]), or tetraethyl-
ammonium iodide afforded the complex [Mn(CH2SPh)-
(CO)3(bipy)] (1b) as the single organometallic product
(see Scheme 4). Parallel results were found when these
reactions were carried out with the rhenium complex
6b. Thus, anions attack the methyl carbon of 5b and
6b, cleaving the S-CH3 bond, in contrast with the
sulfide elimination observed for [CpRe(NO)(PPh3)(CH2-
SMe2)] complexes6 or with attack at the metal with
M-C cleavage, as found for [CpNi(L)(CH2SMe2)]+ (L )
P(OMe)3).5a When the reaction of Et4NI with 6b was
carried out in CD2Cl2 in an NMR tube, free methyl
1
with hexane, was ascertained by H and 19F NMR. To
minimize the reaction time, we then employed toluene
as solvent. Thus, the reactions of complexes 5b and 6b
with styrene in toluene at 110 °C took 20 min and 1 h,
respectively (IR monitoring of the conversion to the
1
triflato complex). To make possible a H NMR analysis
of the mixtures obtained as products, the reactions
were repeated using deuterated toluene as solvent, and
the resulting solutions, once filtered, were found to
consist of mixtures of the corresponding triflato com-
plex, phenylcyclopropane, unreacted styrene, and thio-
anisole (see Scheme 5).
The complexes [M(OTf)(CO)3(bipy)] (M ) Mn, Re) are
only slightly soluble in toluene at room temperature;
as a result, significant precipitation occurred as they
form and upon subsequent cooling at room temperature
and are thus separated as solids in the filtration. This
solid accounted for 80-90% of the manganese or rhe-
nium complex used as precursor.19 The presence of
thioanisole indicates that, under the reaction conditions
used, the S-CH2 bond is cleaved, the CH2 unit is
transferred from the metal fragment to the olefin, and
the triflate ion, initially present as counterion of the
cationic sulfonium complex, coordinates the metal,
recycling the metal fragment (since the treatment of the
triflato complexes with Na/Hg affords the Na[M(CO)3-
(bipy)] salts). The typical ratio of cyclopropane to
unreacted styrene obtained either with [Mn(CH2SMePh)-
(17) For an example of the employment of organic sulfur ylides as
alkylating agents, see: Matsuyama, H.; Nakamura, T.; Iyeda, M. J .
Org. Chem. 2000, 65, 4796.
(18) See for instance: (a) Brookhart, M.; Nelson, G. O. J . Am. Chem.
Soc. 1977, 99, 6097. (b) Kegley, S. E.; Brookhart, M.; Husk, G. R.
Organometallics 1982, 1, 760. (c) Kuo, G.-H.; Helquist, P.; Kerber, R.
C. Organometallics 1984, 3, 806.
(19) When the mixture obtained from the reaction of styrene and
either 5b or 6b is extracted with CH2Cl2 and washed with hexane,
the triflato complexes [Mn(OTf)(CO)3(bipy)] and [Re(OTf)(CO)3(bipy)],
respectively, are obtained in nearly quantitative yield.
(16) No reaction was observed between 5b and PPh3 in toluene at
110 °C over 1 h, conditions chosen to establish a comparison with the
reaction with styrene, discussed in the text.

Mn(I) and Re(I) (Alkylthio)methyl Complexes
Organometallics, Vol. 21, No. 24, 2002 5317
Ta ble 3. Cr ysta l Da ta a n d Refin em en t Deta ils for Com p lexes 1b, 2a , 5b, a n d 6b
1b
2a
5b
6b
formula
fw
C
20H15MnN2O3S‚1/4CH2Cl2
C
15H13N2O3ReS
C22H18F3MnN2O6S2
582.44
C
22H18F3N2O6ReS2
439.57
487.53
713.70
cryst syst
space group
a, Å
b, Å
c, Å
monoclinic
P21/n
13.6409(19)
16.735(2)
17.352(2)
90
99.517(2)
90
3906.6(9)
8
triclinic
P1h
monoclinic
C2/c
28.751(2)
12.3958(10)
15.3655(13)
90
114.397(2)
90
4980.9(7)
8
monoclinic
C2/c
28.484(3)
12.5962(11)
15.3112(14)
90
113.469(2)
90
5039.0(8)
8
6.925(4)
8.634(5)
15.094(8)
78.728(8)
81.920(9)
70.037(8)
829.3(8)
2
R, deg
â, deg
γ, deg
V, Å3
Z
T, K
298(2)
1.495
17960
298(2)
1.953
464
293(2)
1.553
2368
298(2)
1.882
2768
Dc, g cm-3
F(000)
λ(Mo KR), Å
cryst size, mm
µ, mm-1
scan range, deg
no. of rflns measd
no. of indep rflns
no. of data/restraints/params
goodness of fit on F2
R1/wR2 (I > 2σ(I))
R1/wR2 (all data)
0.710 73
0.06 × 0.07 × 0.23
0.875
1.70 e θ e 23.35
24 517
5639
5639/0/511
1.016
0.0461/0.0560
0.1068/0.0632
0.710 73
0.16 × 0.14 × 0.04
7.464
1.38 e θ e 23.64
5187
2412
2412/0/200
1.001
0.0248/0.0647
0.0278/0.0659
0.710 73
0.10 × 0.24 × 0.30
0.761
1.56 e θ e 23.28
15 561
3586
3586/0/326
1.015
0.0794/0.2434
0.0893/0.2578
0.710 73
0.08 × 0.14 × 0.16
5.051
1.56 e θ e 23.27
11 092
3613
3613/0/327
1.007
0.0305/0.0785
0.0392/0.0812
Sch em e 5
reactions were conducted. Similar cyclopropanation
experiments conducted with [Mn(CH2SMePh)(CO)3-
(bipy)]BF4 (7; prepared by reaction of 1b with tri-
methyloxonium tetrafluoroborate) afforded a mixture of
phenylcyclopropane, unreacted styrene, and thioanisole
in a ratio indistinguishable (1H NMR integration) from
that obtained using compound 5b, along with an uni-
dentified metal species.22 Thus, in contrast with the
results obtained by Helquist, cyclopropanation of sty-
rene with the cationic complexes reported here shows
noappreciable dependence ofthe nature ofthe counterion.4c
Exp er im en ta l Section
General procedures were given elsewhere.8
Cr ysta l Str u ctu r e Deter m in a tion for Com p ou n d s 1b,
2a , 5b, a n d 6b. A suitable crystal was attached to a glass fiber
and transferred to a Bruker AXS SMART 1000 diffractometer
with graphite-monochromatized Mo KR X-radiation and a CCD
area detector. A hemisphere of the reciprocal space was
collected up to 2θ ) 48.6°. Raw frame data were integrated
with the SAINT23 program. The structure was solved by direct
methods with SHELXTL.24 A semiempirical absorption cor-
rection was applied with the program SADABS.25 All non-
hydrogen atoms were refined anisotropically. Hydrogen atoms
were set in calculated positions and refined as riding atoms
with a common thermal parameter. All calculations and
graphics were made with SHELXTL. Crystal and refinement
data are presented in Table 3.
(CO)3(bipy)]OTf (5b) or with [Re(CH2SMePh)(CO)3-
(bipy)]OTf (6b) as cyclopropanating reagent was 1:1.
Since the triflato complex [M(OTf)(CO)3(bipy)] (M ) Mn,
Re) is obtained in high yield as the product (with respect
to 5b or 6b), but a conversion of only about 50%20 is
found for the cyclopropanation of styrene, it must be
assumed that the transient carbenoid species has more
pathways for evolution than olefin cyclopropanation.
Decomposition of some of the carbene complex in stoi-
chiometric cyclopropanation reactions has been previ-
ously noted,2 and accordingly, excesses of these com-
plexes or the substituted sulfonium salts in their
reactions with olefins are commonly used.4e A plausible
decomposition product for our sulfonium compounds
would be ethylene, resulting from the formal coupling
of two methylene moieties;21 however, we have been
unable to detect it in our reaction mixtures, likely due
to its low solubility at the temperature at which the
[Mn (CH2SMe)(CO)3(bip y)] (1a ). An oven-dried Schlenk
flask was charged with [MnBr(CO)3(bipy)] (0.300 g, 0.800
mmol) and a PTFE-coated stirbar. The flask was subjected to
three vacuum-nitrogen cycles. Under a strong stream of
nitrogen, THF (25 mL) was added. After the mixture was
(22) This compound showed IR νCO bands at 2041 and 1938 cm-1 in
CH2Cl2 and was only slighly soluble in CH2Cl2, THF, or toluene. These
wavenumber values are consistent with a cationic formulation, but we
have been unable to further characterize this species.
(23) SAINT+: SAX area detector integration program, version 6.02;
Bruker AXS, Inc., Madison, WI, 1999.
(24) Sheldrick, G. M. SHELXTL, An integrated system for solving,
refining, and displaying crystal structures from diffraction data,
version 5.1; Bruker AXS, Inc., Madison, WI, 1998.
(25) Sheldrick, G. M. SADABS, Empirical Absorption Correction
Program; University of Go¨ttingen, Go¨ttingen, Germany, 1997.
(20) The yield of phenylcyclopropane, evaluated by 1H NMR integra-
tion using ferrocene as internal standard, was found to be 44((5)%
with compound [Mn(CH2SMePh)(CO)3(bipy)]OTf (5b).
(21) For instance, the olefins resulting from formal carbene coupling
are formed as byproducts in metal-catalyzed cyclopropanations using
diazo compounds as the primary carbene source: Doyle, M. P.; Forbes,
D. C. Chem. Rev. 1998, 98, 911.

5318 Organometallics, Vol. 21, No. 24, 2002
Hevia et al.
1
stirred to ensure complete dissolution, the flask was open
under nitrogen, and 15 g of 0.5% sodium amalgam was added
to the orange solution. Three new vacuum-nitrogen cycles
were applied, and a vigorous magnetic stirring was maintained
for 2 h at room temperature. Although a deep blue-violet color
developed in about 15 min, IR monitoring showed that the
longer time was necessary for the reaction to reach completion.
1883, 1878. H NMR (CD2Cl2): δ 9.09, 8.25, 8.02, 7.46 (m, 2H
each, bipy), -0.91 (s, 3H, CH3). 13C{1H} NMR (CD2Cl2): δ
204.58 (2CO), 192.81 (CO), 155.01, 152.85, 137.57, 126.63,
123.38 (bipy), -0.35 (CH3).
[Re(SP h Me)(CO)3(bip y)]P F 6 (4). SPhMe (12 µL, 0.104
mmol) was added to a solution of [Re(CH3)(CO)3(bipy)] (0.046
g, 0.104 mmol) in CH2Cl2 (10 mL) and the solution was cooled
at -78 °C. A solution of [CPh3][PF6] (0.040 g, 0.104 mmol) in
CH2Cl2 (10 mL), previously cooled to -78 °C, was added. The
color of the solution changed from orange to yellow. Volatiles
were removed under vacuum, and the solid residue was
washed with diethyl ether (2 × 5 mL). The solid was redis-
solved in CH2Cl2 (5 mL). Slow diffusion of hexanes at room
temperature into this solution afforded 4 as yellow crystals.
The anion showed IR νCO bands at 1912, 1823, and 1782 cm-1
.
After it was allowed to settle, the solution was transferred onto
a solution of ClCH2SCH3 (67 µL, 0.800 mmol) in THF (10 mL),
previously cooled to -78 °C, using a cannula tipped with filter
paper. The color of the solution changed to red. The solution
was filtered through Florisil. The solvent was removed under
vacuum to afford complex 1a as an orange solid. Yield: 0.199
g, 70%. IR (THF, cm-1): 1996, 1896. 1H NMR (CD2Cl2): δ 9.05,
8.09, 7.90, and 7.38 (m, 2H each, bipy), 1.82 (s, 3H, CH3), 1.27
(s, 2H, CH2). 13C{1H} NMR (CD2Cl2): δ 227.04 (2CO), 213.33
(CO), 154.53, 153.10, 136.92, 125.33, 122.12 (bipy), 32.36 (CH2),
24.29 (CH3). Anal. Calcd for C15H13MnN2O3S: C, 50.69; H,
3.67; N, 7.86. Found: C, 50.45; H, 3.62; N, 7.78.
1
Yield: 0.072 g, 87%. IR (CH2Cl2): 2042, 1951, 1936. H NMR
(CD2Cl2): δ 8.81 (m, 2H, bipy), 8.25 (m, 4H, bipy), 7.63 (m,
2H, bipy), 7.32 (m, 1H, Ph), 7.15 (m, 3H, Ph), 6.67 (m, 2H,
Ph), 2.99 (s, 3H, CH3). 13C{1H} NMR (CD2Cl2): δ 197.26 (2CO),
194.64 (CO), 155.60, 153.62, 141.43 (bipy), 130.52 (Ph), 130.38
(bipy), 129.01, 128.36, 127.01 (Ph), 124.99 (bipy), 23.74 (CH3).
31P{1H} NMR (CD2Cl2): δ -143.07 (m (711.48), PF6). Anal.
Calcd for C20H16F6N2O3PSRe: C, 34.53; H, 2.31; N, 4.02.
Found: C, 34.57; H, 2.19; N,4.11.
[Mn (CH2SP h )(CO)3(bip y)] (1b). Following the procedure
described for 1a , the reaction of [MnBr(CO)3(bipy)] (0.300 g,
0.800 mmol) with sodium amalgam (15 g, 0.5%), followed by
the reaction with ClCH2SPh (107 µL, 0.800 mmol) afforded
1b as an orange solid. Slow diffusion of hexanes into a solution
of 1b in THF at room temperature afforded orange crystals,
one of which was used for X-ray analysis. Yield: 0.241 g, 72%.
[Mn (CH2SMe2)(CO)3(bip y)]OTf (5a ). MeOTf (32 µL, 0.280
mmol) was added to a solution of 1a (0.100 g, 0.280 mmol) in
CH2Cl2 (20 mL) at -78 °C. The solution was allowed to reach
room temperature and stirred for 15 min. The solvent was
removed under vacuum to afford complex 5a as a yellow solid.
1
IR (THF, cm-1): 1999, 1901. H NMR (CD2Cl2): δ 9.11, 8.13,
Yield: 0.134 g, 92%. IR (CH2Cl2, cm-1): 2019, 1930, 1906. H
1
7.93, and 7.43 (m, 2H each, bipy), 7.03 (m, 5H, Ph), 1.27 (s,
2H, CH2). 13C{1H} NMR (CD2Cl2): δ 226.31 (2CO), 223.14
(CO), 154.63, 153.24 (bipy), 147.88 (Ph), 137.28, 128.23 (bipy),
125.59 (Ph), 124.74 (bipy), 123.00, 122.35 (Ph), 23.57 (CH2).
Anal. Calcd for C20H15MnN2O3S: C, 57.42; H, 3.61; N, 6.69.
Found: C, 57.37; H, 3.78; N, 6.56.
NMR (CD2Cl2): δ 9.03, 8.35, 8.11, and 7.58 (m, 2H each, bipy),
2.71 (s, 6H, CH3), 1.18 (s, 2H, CH2). 19F NMR (CD2Cl2): δ
-77.81. Anal. Calcd for C17H16F3MnN2O6S2: C, 39.23; H, 3.09;
N, 5.38. Found: C, 39.37; H, 3.12; N, 5.40.
[Mn (CH 2SMeP h )(CO)3(b ip y)]OTf (5b). Following the
procedure described for 5a , complex 1b (0.100 g, 0.239 mmol)
reacted with MeOTf (27 µL, 0.239 mmol) to afford 5b as a
yellow solid. Slow diffusion of hexanes into a solution of 5b in
THF at room temperature afforded yellow crystals, one of
which was used for X-ray analysis. Yield: 0.130 g, 94%. IR
[Re(CH2SMe)(CO)3(bip y)] (2a ). A solution of [ReBr(CO)3-
(bipy)] (0.300 g, 0.592 mmol) in THF (25 mL) was kept
vigorously stirred with 15 g of 0.5% sodium amalgam for 24 h
at room temperature. Given the long reaction time, a flask
provided with a PTFE Young stopcock (rather than a greased
glass stopcock) was used. The resulting blue-violet solution
was transferred with a cannula tipped with filter paper to a
solution of ClCH2SCH3 (50 µL, 0.593 mmol) in THF (10 mL),
previously cooled to -78 °C. The color of the solution changed
to orange. Subsequent workup as described for 1a ,b afforded
2a as an orange solid. Slow diffusion of hexanes into a solution
of 2a in CH2Cl2 at -20 °C afforded orange crystals, one of
which was used for X-ray analysis. Yield: 0.179 g, 62%. IR
(THF, cm-1): 1998, 1890. 1H NMR (CD2Cl2): δ 9.04, 8.22, 8.07,
7.99 (m, 2H each, bipy), 1.76 (s, 3H, CH3), 1.03 (s, 2H, CH2).
13C{1H} NMR (CD2Cl2): δ 202.44 (2CO), 192.53 (CO), 155.36,
153.28, 134.12, 126.84, 123.27 (bipy), 25.86 (CH3), 23.25 (CH2).
Anal. Calcd for C15H13N2O3ReS: C, 36.95; H, 2.68; N, 5.74.
Found: C, 36.87; H, 2.62; N, 5.68.
(CH2Cl2, cm-1): 2019, 1931, 1909. H NMR (CD2Cl2): δ 8.98,
1
8.75 (m, 1H each, bipy), 8.36, 8.10 (m, 2H each, bipy), 7.65-
7.33 (m, 7H, 2H, bipy, and 5H, Ph), 2.89 (s, 3H, CH3), 1.74,
1.70, 1.44, 1.40 (AB, 2H, CH2). 19F NMR (CD2Cl2): δ -77.89.
13C{1H} NMR (CD2Cl2): δ 224.69 (CO), 222.77 (CO), 214.86
(CO), 156.31, 154.54, 154.27, 140.72, 140.59 (bipy), 135.33,
132.93, 132.47, 130.39 (Ph), 128.63, 128.41, 125.51, 125.48
(bipy), 121.92 (q(322.15), CF3SO3), 37.28 (CH3), 34.30 (CH2).
Anal. Calcd for C22H18F3MnN2O6S2: C, 45.36; H, 3.11; N, 4.80.
Found: C, 45.41; H, 3.26; N, 4.69.
[Re(CH2SMe2)(CO)3(bip y)]OTf (6a ). MeOTf (23 µL, 0.205
mmol) was added to a solution of 2a (0.100 g, 0.205 mmol) in
CH2Cl2 (20 mL) at -78 °C. The solution was allowed to reach
room temperature and then stirred for 15 min. The solvent
was removed under vacuum to afford 6a as a yellow solid.
[Re(CH2SP h )(CO)3(bip y)] (2b). Following the procedure
described for 2a , complex 2b was obtained by reaction of
[ReBr(CO)3(bipy)] (0.300 g, 0.592 mmol) with sodium amalgam
(0.5%), followed by the reaction with ClCH2SPh (80 µL, 0.592
Yield: 0.118 g, 89%. IR (CH2Cl2, cm-1): 2017, 1916, 1898. H
1
NMR (CD2Cl2): δ 8.97, 8.44, 8.19, 7.61 (m, 2H each, bipy), 2.69
(s, 6H, CH3), 1.28 (s, 2H, CH2). 19F NMR (CD2Cl2): δ -78.71.
Anal. Calcd for C17H16F3N2O6ReS2: C, 33.33; H, 2.47; N, 4.29.
Found: C, 33.27; H, 2.54; N, 4.33.
1
mmol). Yield: 0.101 g, 65%. IR (THF, cm-1): 2001, 1891. H
NMR (CD2Cl2): δ 9.08, 8.20, 8.07, 7.50 (m, 2H each, bipy), 6.90
(m, 5H, Ph), 1.22 (s, 2H, CH2). 13C{1H} NMR (CD2Cl2):
δ
[Re(CH2SMeP h )(CO)3(bip y)]OTf (6b). Following the pro-
cedure described for 6a , the reaction of 2b (0.100 g, 0.182
mmol) with MeOTf (20 µL, 0.182 mmol) afforded 6b as a yellow
solid. Slow diffusion of hexanes into a solution of 6b in THF
at room temperature afforded yellow crystals, one of which
was used for X-ray analysis.Yield: 0.109 g, 92%. IR (CH2Cl2,
201.79 (2CO), 192.74 (CO), 155.41, 153.44 (bipy), 149.44 (Ph),
138.44, 128.20 (bipy), 127.03 (Ph), 124.30 (bipy), 123.42, 122.86
(Ph), 26.39 (CH2). Anal. Calcd for C20H15N2O3ReS: C, 43.70;
H, 2.75; N, 5.09. Found: C, 43.64; H, 2.70; N, 5.01.
[Re(CH3)(CO)3(bip y)] (3). Complex 3 was prepared as
described in ref 13 by reaction of [ReBr(CO)3(bipy)] (0.100 g,
0.198 mmol) with methylmagnesium chloride (66 µL of a 3.0
M solution in Et2O, 0.198 mmol) in THF (20 mL). The color of
the solution changed from yellow to orange. The solution was
filtered through silica, and the solvent was removed under
vacuum, affording an orange solid. IR (THF, cm-1): 1991,
cm-1): 2017, 1915, 1900. H NMR (CD2Cl2): δ 8.95, 8.68, (m,
1
1H each, bipy), 8.51, 8.18 (m, 2H each, bipy), 7.67-7.22 (m,
7H, 2H, bipy, and 5H, Ph), 2.88 (s, 3H, CH3), 1.77, 1.73, 1.52,
1.48 (AB, 2H, CH2). 19F NMR (CD2Cl2): δ -78.72. 13C{1H}
NMR (CD2Cl2): δ 199.14 (CO), 198.74 (CO), 190.64 (CO),
155.58, 153.15, 152.84, 140.25, 140.09 (bipy), 133.93, 132.02,

Mn(I) and Re(I) (Alkylthio)methyl Complexes
Organometallics, Vol. 21, No. 24, 2002 5319
131.09, 128.99 (Ph), 128.22, 127.99, 125.16. 125.18 (bipy),
121.33 (q (321.07), CF3SO3), 35.99 (CH3), 25.79 (CH2). Anal.
Calcd for C22H18F3N2O6ReS2: C, 37.02; H, 2.54; N, 3.92.
Found: C, 37.11; H, 2.34; N, 3.79.
was added to the mixture of the reagents. Integration of [Fe-
(η5-Cp2)] (4.05 ppm) and the styrene signal at 5.07 ppm
confirmed the 10:1 ratio of the olefin and the standard. After
completion of the reaction, the integration of the phenylcyclo-
propane signal at 0.72 ppm against that of ferrocene indicated
a 44% yield of the cyclopropane.
Rea ction of [M(CH2SMeP h )(CO)3(bip y)]OTf (5b) w ith
KP P h 2. To a solution of 5b (0.050 g, 0.085 mmol) in THF (10
mL) cooled to -78 °C was added a solution of KPPh2 (prepared
by reaction of HPPh2 (15 µL, 0.085 mmol) with K[N(SiMe3)2]
(0.170 mL of a 0.5 M solution in toluene, 0.085 mmol)) in THF.
The mixture was stirred for 20 min.26 Volatiles were removed
under vacuum, and the solid residue was extracted with CH2-
Cl2 (2 × 10 mL). The solvent was evaporated, and the solid
was redissolved in THF (10 mL). Slow diffusion of hexanes
(15 mL) into this solution in THF at room temperature
afforded orange crystals of 1b.
[Mn (CH2SMeP h )(CO)3(bip y)]BF 4 (7). Me3OBF4 (0.035 g,
0.239 mmol) was added to a solution of 1b (0.100 g, 0.239
mmol) in THF (20 mL). Workup similar to that described for
5b afforded 7 as a yellow solid. Yield: 0.113 g, 89%. IR (CH2-
1
Cl2, cm-1): 2018, 1930, 1909. H NMR (CD2Cl2): δ 8.99, 8.78
(m, 1H each, bipy), 8.34, 8.10 (m, 2H each, bipy), 7.64-7.38
(m, 7H, 2H bipy and 5H Ph), 2.90 (s, 3H, CH3), 1.73, 1.71, 1.44,
1.41 (AB, 2H, CH2). Anal. Calcd for C22H18BF4MnN2O3S: C,
49.65; H, 3.40; N, 5.26. Found: C, 49.59; H, 3.34; N, 5.20.
Cyclopr opan ation of Styr en e. [M(CH2SMePh)(CO)3(bipy)]-
OTf (0.100 mmol) was dissolved in d8-toluene (1 mL), and
styrene (11 µL, 0.100 mmol) was added. The mixture was
heated at 110 °C for 20 min for M ) Mn or 1 h for M ) Re. An
1H NMR spectrum was recorded and showed the presence
of [M(OTf)(CO)3(bipy)],27 SPhMe, unreacted styrene, and
phenylcyclopropane (7.22 (m, 5H, Ph), 1.78 (m, 1H), 0.93 (m,
2H), 0.72 (m, 2H)). For the cyclopropanation with compound
5b, 10 µL of a 1 M solution of ferrocene in CH2Cl2 (0.010 mmol)
Ack n ow led gm en t. We thank the Ministerio de
Ciencia y Tecnolog´ıa, Ministerio de Educacio´n, and
Principado de Asturias for support of this work (Projects
MCT-00-BQU-0220, BQU2002-03414, and PR-01-GE-
7) and a predoctoral fellowship (to E.H.).
Su p p or tin g In for m a tion Ava ila ble: Tables giving posi-
tional and thermal parameters and bond distances and bond
angles for 1b, 2a , 5b, and 6b. This material is available free
of charge via the Internet at http://pubs.acs.org.
(26) A 31P NMR spectrum of the crude reaction mixture showed the
presence of free PMePPh2 (-26.33 ppm in THF using an internal
capillary tube containing D2O).
(27) Hevia, E.; Pe´rez, J .; Riera, L.; Riera, V.; Miguel, D. Organo-
metallics 2002, 21, 1750.
OM020522I