Diallyl sulfide complexes of chiral iron and ruthenium lewis acids: Ylide generation and diastereoselective [2,3] sigmatropic rearrangements to give thiolate complexes with new carbon stereocenters

Article abstract of DOI:10.1021/om960541q

Reactions of the racemic iron diallyl sulfide complex [(η⁵-C₅H₅)Fe(CO)(PPh₃)(S(CH ₂-CH=CH₂)₂)]⁺BF₄ ^- and t-BuOK (CH₂Cl₂ or THF, -80 to -60°C) give the thiolate complex (η⁵-C₅H₅)Fe(CO)(PPh ₃)(SCH(CH=CH₂)CH₂CH=CH₂) (65-92%) as 77-68:23-32 mixtures of SS,RR/SR,RS Fe,SC diastereomers. Reactions of the enantiomerically pure ruthenium diallyl sulfide complexes [(η⁵-C₅H₅)Ru(S,S-chiraphos)(S(CH ₂CR=CH₂)₂)]⁺PF₆ ^- (5⁺PF₆^-; R = a, H; R = b, CH₃) and t-BuOK (CH₂Cl₂, -98°C) give the thiolate complexes (η⁵-C₅H₅)Ru(S,S-chiraphos)(SCH(CR=CH ₂)CH₂CR=CH₂) as 78:22 (8a, >99%) and 87:13 (8b, 97%) mixtures of chromatographically separable SSS/SSR PC,P′C′,SC diastereomers. These transformations likely involve intermediate sulfur ylides as described in the title. Reactions of 8a,b with CH₃I or PhCH₂I and then NaI (acetone, reflux) give, via cationic methyl or benzyl sulfide complexes, enantiomerically enriched R′SCH(CH₂CR=CH₂)CR=CH₂ (R/R′ = H/CH₃, 75%; CH₃/CH₃, 71%; H/PhCH₂ and CH₃/PhCH₂, >99%) and (η⁵-C₅H₅)Ru(S,S-chiraphos)(I) (6, ≥97%). Complex 6 is readily recycled to enantiomerically pure 5a,b⁺PF₆^- (NH₄⁺PF₆^-, CH₃OH, S(CH₂CR=CH₂)₂; 94-97%).

Full text of DOI:10.1021/om960541q

Organometallics 1996, 15, 4695-4701
4695
Dia llyl Su lfid e Com p lexes of Ch ir a l Ir on a n d Ru th en iu m
Lew is Acid s: Ylid e Gen er a tion a n d Dia ster eoselective
[2,3] Sigm a tr op ic Rea r r a n gem en ts To Give Th iola te
Com p lexes w ith New Ca r bon Ster eocen ter s
Peter T. Bell, Phillip C. Cagle, Dominique Vichard, and J . A. Gladysz*
Department of Chemistry, University of Utah, Salt Lake City, Utah 84112
Received J uly 3, 1996X
Reactions of the racemic iron diallyl sulfide complex [(η5-C5H5)Fe(CO)(PPh3)(S(CH2-
CHdCH2)2)]+BF4 and t-BuOK (CH2Cl2 or THF, -80 to -60 °C) give the thiolate complex
-
(η5-C5H5)Fe(CO)(PPh3)(SCH(CHdCH2)CH2CHdCH2) (65-92%) as 77-68:23-32 mixtures
of SS,RR/SR,RS Fe,SC diastereomers. Reactions of the enantiomerically pure ruthenium
diallyl sulfide complexes [(η5-C5H5)Ru(S,S-chiraphos)(S(CH2CRdCH2)2)]+PF6- (5+PF6-; R )
a , H; R ) b, CH3) and t-BuOK (CH2Cl2, -98 °C) give the thiolate complexes (η5-C5H5)Ru(S,S-
chiraphos)(SCH(CRdCH2)CH2CRdCH2) as 78:22 (8a , >99%) and 87:13 (8b, 97%) mixtures
of chromatographically separable SSS/SSR PC,P′C′,SC diastereomers. These transforma-
tions likely involve intermediate sulfur ylides as described in the title. Reactions of 8a ,b
with CH3I or PhCH2I and then NaI (acetone, reflux) give, via cationic methyl or benzyl sulfide
complexes, enantiomerically enriched R′SCH(CH2CRdCH2)CRdCH2 (R/R′ ) H/CH3, 75%;
CH3/CH3, 71%; H/PhCH2 and CH3/PhCH2, >99%) and (η5-C5H5)Ru(S,S-chiraphos)(I) (6,
g97%). Complex 6 is readily recycled to enantiomerically pure 5a ,b+PF6 (NH4+PF6
,
-
-
CH3OH, S(CH2CRdCH2)2; 94-97%).
Sch em e 1. En a n tioselective Con ver sion of Ach ir a l
Dia llyl Su lfid es to Rea r r a n ged Ch ir a l Su lfid es
Med ia ted by th e Ch ir a l Rh en iu m Lew is Acid I
Chiral transition metal Lewis acids offer innumerable
possibilities as control elements in enantioselective
organic syntheses, and new methodologies are being
discovered at an ever increasing pace.1 We have
reported, in a series of papers over the last 3 years, that
the chiral rhenium Lewis acid [(η5-C5H5)Re(NO)(PPh3)]+
(I)2 readily binds diallyl, dipropargyl, and dibenzyl
sulfides.3-5 As exemplified in Scheme 1, subsequent
additions of t-BuOK generate sulfur ylides that undergo
highly diastereoselective [2,3] sigmatropic rearrange-
ments. The rhenium fragment efficiently directs the
configuration of the new carbon stereocenter in the
resulting thiolate ligand. The thiolate can be detached
as a thioether of high enantiomeric purity and the
rhenium moiety recycled without racemization. There
is currently no comparable means of controlling config-
uration in sigmatropic rearrangements of sulfur ylides
or any type of desymmetrization of diallyl or related
sulfides. Mechanisms that rationalize the observed
stereochemistry have been proposed.3
The above results engender a number of questions
regarding possible extensions. Can analogous depro-
tonations and rearrangements be effected in the coor-
dination spheres of other chiral (or achiral) transition
metal Lewis acids? Can even higher diastereoselectivi-
ties or thioether enantiomeric purities be achieved? Can
the metal fragment be recycled more efficiently or other
economies realized? Hence, we undertook a similar
investigation of diallyl sulfide complexes of the readily
available chiral iron and ruthenium Lewis acids [(η5-
C5H5)Fe(CO)(PPh3)]+ (II) and [(η5-C5H5)Ru(S,S-chira-
phos)]+ (III). The former provides an environment that
is approximately isosteric with I, whereas the latter
features ligand-based instead of metal-based chirality.
In this paper, we demonstrate that the answers to two
of the preceding questions are “yes”, an outcome that
X Abstract published in Advance ACS Abstracts, October 1, 1996.
(1) Noyori, R. Asymmetric Catalysis in Organic Synthesis; Wiley:
New York, 1994.
(2) Lead reference for functional equivalents and substitution
mechanisms: Dewey, M. A.; Zhou, Y.; Liu, Y.; Gladysz, J . A. Organo-
metallics 1993, 12, 3924.
(3) (a) Cagle, P. C.; Arif, A. M.; Gladysz, J . A. J . Am. Chem. Soc.
1994, 116, 3655. (b) Cagle, P. C.; Meyer, O.; Weickhardt, K.; Arif, A.
M.; Gladysz, J . A. J . Am. Chem. Soc. 1995, 117, 11730. (c) Cagle, P.
C.; Meyer, O.; Vichard, D.; Weickhardt, K.; Arif, A. M.; Gladysz, J . A.
Organometallics 1996, 15, 194.
(4) Related papers: (a) Quiro´s Me´ndez, N.; Arif, A. M.; Gladysz, J .
A. Organometallics 1991, 10, 2199. (b) Meyer, O.; Arif, A. M.; Gladysz,
J . A. Organometallics 1995, 14, 1844.
(5) Brief review: Meyer, O.; Cagle, P. C.; Weickhardt, K.; Vichard,
D.; Gladysz, J . A. Pure Appl. Chem. 1996, 68, 79.
S0276-7333(96)00541-9 CCC: $12.00 © 1996 American Chemical Society

4696 Organometallics, Vol. 15, No. 22, 1996
Bell et al.
was characterized as described for 1+BF4- (Experimen-
tal Section). NMR analyses showed that 3 was a 75:25
mixture of Fe,C configurational diastereomers (C6D6;
cyclopentadienyl 1H or PPh3 31P signals).10,11 The
configuration of the major diastereomer was tentatively
assigned by analogy to that obtained in the correspond-
ing reaction involving the structurally related rhenium
Lewis acid I (Scheme 1; SS,RR).
Sch em e 2. Syn th esis a n d Rea ction of a Dia llyl
Su lfid e Com p lex of a Ch ir a l Ir on Lew is Acid
-
Complex 1+BF4 and t-BuOK (1.5 equiv) were simi-
larly combined at -98 °C. A nonchromatographic
workup gave spectroscopically pure 3 in 92% yield as a
68:32 mixture of diastereomers. THF solutions of
1+BF4- gave comparable diastereomer ratios, and NMR
experiments (THF) did not show any appreciable reac-
tion below -60 °C or detectable intermediates. Amide
(R2N-) bases could also be used. In side-by-side reac-
tions, CH2Cl2 solutions of 1+BF4- were treated with 0.6
equiv of t-BuOK, (Me2CH)2NLi, or (Me3Si)2NLi in
darkened rooms and foil shielded NMR tubes at -80
°C. In all cases, 3 formed as a 77:23 mixture of
diastereomers. In contrast, the diallyl sulfide complex
of I gave widely divergent diastereoselectivities with
these bases.3b Some Lewis base adducts of II epimerize
at iron under ambient light,12 but the umbral conditions
exclude this possibility here. The spread in diastere-
omer ratios (77-68:23-32; 65:35 in experiments not
described) precludes any rapid thermal equilibration.
Regardless, under none of the conditions investigated
does 3 form with high diastereoselectivity.
augers well for the breadth, generality, and continued
development of this new methodology.
Resu lts
1. Ir on Com p lexes. A racemic dimethyl sulfide
complex of the iron Lewis acid II has been previously
synthesized by thermal or photochemical reactions of
PPh3 and the achiral precursors [(η5-C5H5)Fe(CO)-
(SMe2)2]+X- or [(η5-C5H5)Fe(CO)2(SMe2)]+X-.6,7 These
are in turn prepared from substitution-labile cationic
THF complexes, which are generated in situ from the
corresponding neutral iodide complexes. We sought to
similarly access a diallyl sulfide complex of II. Hence,
(η5-C5H5)Fe(CO)2(I) and AgBF4 were combined in THF
to generate the THF complex [(η5-C5H5)Fe(CO)2-
(THF)]+BF4- as described earlier.8 Subsequent addition
of diallyl sulfide gave the substitution product [(η5-
C5H5)Fe(CO)2(S(CH2CHdCH2)2)]+BF4- in moderate yield.
However, photolysis with PPh3 (5 equiv, CH2Cl2) gave
numerous species.
Complex 3 exhibited an IR νCO value close to that of
the previously reported iron allyl thiolate complex (η5-
C5H5)Fe(CO)(PPh3)(SCH2CHdCH2) (1936 vs 1932 cm-1
,
KBr).13 The NMR properties of the thiolate ligand were
generally similar to those of the analogous adduct of I.3b
However, 3 was much more air sensitive. Other com-
pounds of the formula (η5-C5R5)Fe(CO)(PR′3)(SR′′) (R′′
) alkyl, aryl) have been observed to undergo facile one
electron oxidations,14 as well as alkylation at sulfur
(CH3CH2Br, 21 °C, CHCl3).15 However, in view of the
modest diastereoselectivities, no elaboration of the
thiolate ligand of 3 was attempted.
Thus, the previously reported, chiral, racemic, PPh3-
substituted iodide complex (η5-C5H5)Fe(CO)(PPh3)(I)9
was similarly converted to the THF complex [(η5-
C5H5)Fe(CO)(PPh3)(THF)]+BF4- as shown in Scheme 2.
Reaction with diallyl sulfide (1.5 equiv, CH2Cl2) gave
the blood red target complex [(η5-C5H5)Fe(CO)-
(PPh3)(S(CH2CHdCH2)2)]+BF4- (1+BF4- ) in 80% yield.
2. Ru th en iu m Com p lexes. The chiral, enantio-
merically pure ruthenium chloride complex (η5-C5H5)-
Ru(S,S-chiraphos)(Cl) (4) is easily prepared from (η5-
C5H5)Ru(PPh3)2(Cl) and commercially available S,S-
chiraphos.16 However, when 4 was treated with AgBF4,
THF, and diallyl sulfides in procedures similar to that
-
Complex 1+BF4 was stable for prolonged periods as a
-
used for 1+BF4 in Scheme 2, much lower yields of
solid but decomposed in aerobic solutions. It was
characterized by microanalysis and IR and NMR (1H,
13C, 31P) spectroscopy, as summarized in the Experi-
mental Section. Properties were similar to those of the
dimethyl sulfide complex of II.6
sulfide complexes were obtained. Thus, a method
reported by Schenk for the synthesis of the correspond-
(10) All diastereomer and enantiomer ratios are normalized to 100.
The error limits on each component are (2 for diastereomer ratios
and (4 for enantiomer ratios.
(11) The configuration of the chiral transition metal Lewis acid is
specified first (rhenium, iron, or chiraphos ligand stereocenters),
followed by that at carbon.
(12) (a) Davies, S. G.; Metzler, M. R.; Yanada, K.; Yanada, R. J .
Chem. Soc., Chem. Commun. 1993, 658. (b) Davies, S. G.; Watkins,
W. C. J . Chem. Soc., Chem. Commun. 1994, 491.
(13) Weigand, W. Z. Naturforsch., B: Anorg. Chem., Org. Chem.
1991, 46b, 1333.
(14) (a) Treichel, P. M.; Komar, D. A. J . Organomet. Chem. 1981,
206, 77. (b) Treichel, P. M.; Rosenhein, L. D. J . Am. Chem. Soc. 1981,
103, 691. (c) Treichel, P. M.; Rosenhein, L. D.; Schmidt, M. S. Inorg.
Chem. 1983, 22, 3960.
-
A CH2Cl2 solution of 1+BF4 and a THF solution of
t-BuOK (1.0 equiv) were combined at -80 °C. The
thiolate
complex
(η5-C5H5)Fe(CO)(PPh3)(SCH-
(CHdCH2)CH2CHdCH2) (3) was isolated in 65% yield
following column chromatography on alumina, consis-
tent with the initial generation of ylide 2 as shown in
Scheme 2. This dark green, analytically pure material
(6) Kuhn, N.; Schumann, H.; Zauder, E. J . Organomet. Chem. 1987,
327, 17.
(7) Kuhn, N.; Schumann, H. J . Organomet. Chem. 1984, 276, 55.
(8) Reger, D. L.; Coleman, C. J . Organomet. Chem. 1977, 131, 153.
(9) Treichel, P. M.; Shubkin, R. L.; Barnett, K. W., Reichard, D.
Inorg. Chem. 1966, 5, 1177.
(15) Treichel, P. M.; Schmidt, M. S.; Koehler, S. D. J . Organomet.
Chem. 1983, 258, 209.
(16) Consiglio, G.; Morandini, F.; Bangerter, F. Inorg. Chem. 1982,
21, 455.

Diallyl Sulfide Complexes of Fe and Ru
Organometallics, Vol. 15, No. 22, 1996 4697
Sch em e 3. Syn th esis a n d Rea ction s of Dia llyl Su lfid e Com p lexes of a Ch ir a l Ru th en iu m Lew is Acid
ing dialkyl sulfide complexes was investigated.17 As
shown in Scheme 3, reactions of 4 with NH4+PF6- and
then diallyl or dimethallyl sulfide in refluxing methanol
gave the target complexes [(η5-C5H5)Ru(S,S-chira-
than the iron analog 3 but did decompose upon pro-
longed exposure to air, chlorinated solvents, or silica gel.
A low-temperature NMR experiment showed that
5a +PF6- and t-BuOK rapidly reacted in CH2Cl2 at -98
°C to give 8a without any detectable intermediates.
NMR experiments were also conducted in other solvents
in hopes of enhancing diastereoselectivity. However,
diastereomer ratios were always lower than those
obtained in CH2Cl2 (CH3CN, -45 °C, 67:33; DMF, -60
°C, 63:37; THF, -90 °C, 62:38; EtOAc, -90 °C, 59:41;
diglyme, -66 °C, 57:43; acetone, -90 °C, 52:48).
-
phos)(S(CH2CRdCH2)2)]+PF6 (5+PF6-; R ) a , H; R )
b, CH3) as analytically pure powders in >90% yields.
-
Complexes 5a ,b+PF6 were characterized as described
for 1+BF4-. They could also be isolated in similar yields
from analogous reactions with the iodide complex (η5-
C5H5)Ru(S,S-chiraphos)(I) (6).17,18
A CH2Cl2 solution of 5a +PF6- and a THF solution of
t-BuOK were combined at -98 °C. A nonchromato-
graphic workup gave the spectroscopically pure thiolate
complex (η5-C5H5)Ru(S,S-chiraphos)(SCH(CHdCH2)CH2-
CHdCH2) (8a ) in >99% yield as a 78:22 mixture of SSS/
Attention was turned to detaching the thiolate ligands
from the ruthenium. Previous reports have shown that
cyclopentadienylruthenium thiolate complexes are eas-
ily alkylated at sulfur to give cationic sulfide com-
plexes,19 analogous to the rhenium chemistry in Scheme
1. Furthermore, Schenk has shown that sulfoxide
complexes of III and NaI react in refluxing acetone to
give free sulfoxides and iodide complex 6.17 Accordingly,
8a and CH3I were combined in acetone or acetone-d6.
1
SSR PC,P′C′,SC diastereomers, as assayed by H and
31P NMR.10 As illustrated in Scheme 3, this product is
consistent with the intermediacy of ylide 7, and con-
figurations were assigned as described below. Pure
samples of each diastereomer were soughtsan objective
for which less diastereoselective conditions can be
A
31P NMR experiment showed the slow conversion of
8a to a new compound (83.8 and 66.6 ppm, 2 d, J PP
-
advantageous. Thus, a THF solution of 5a +PF6 was
)
similarly reacted at -80 °C. Flash chromatography
gave (SSS)-8a and (SSR)-8b in 52% and 44% yields (54:
46), respectively. Both diastereomers were dextrorota-
40 Hz), presumably a cationic methyl allyl sulfide
complex. For convenience, preparative reactions were
refluxed for 1 h. With longer reflux times, another new
compound could be detected. However, the addition of
excess NaI greatly accelerated the formation of this
species (complete within 5 h at 50 °C with 5 equiv).
Chromatography gave the iodide complex 6 in 98% yield,
and distillation gave the previously characterized free
methyl sulfide CH3SCH(CHdCH2)CH2CHdCH2 (9a )3a
in 75% yield. An analogous reaction sequence with 8b
afforded 6 (90%) and the known methyl sulfide
CH3SCH(C(CH3)dCH2)CH2C(CH3)dCH2 (9b,3a 71%).
As is readily visualized from Scheme 3, the preceding
reactions allow an extremely efficient recycling of the
chiral ruthenium Lewis acid III. The formation of 6
and 9 was quantitative by NMR. Thus, we attributed
the lower isolated yields of 9a ,b to volatility-related
tory ([R]25 384° ( 2°, 257° ( 2°) and were character-
589
ized by 1H, 13C, and 31P NMR. A combined sample gave
a correct microanalysis.
-
The dimethallyl sulfide complex 5b+PF6 behaved
similarly. When CH2Cl2 solutions of 5b+PF6- and THF
solutions of t-BuOK were combined at -98 °C, the
thiolate complex (η5-C5H5)Ru(S,S-chiraphos)(SCH-
(C(CH3)dCH2)CH2C(CH3)dCH2) (8b) formed as a 87:
13 mixture of SSS/SSR diastereomers. A nonchromato-
graphic workup gave 8b in >99% yield. When a similar
reaction was conducted at -80 °C, the diastereomer
ratio decreased to 68:32. Curiously, with 8a the dia-
stereomer ratio varied only slightly under comparable
conditions. Complexes 8a ,b were much more robust
(17) Schenk, W. A.; Frisch, J .; Adam, W.; Prechtl, F. Angew. Chem.,
Int. Ed. Engl. 1994, 33, 1609.
(18) For prior characterization of the ruthenium iodide complex 6,
see: Frisch, J . Ph.D. Thesis, University of Wu¨rzburg, 1994.
(19) (a) Hachgenei, J . W.; Angelici, R. J . J . Organomet. Chem. 1988,
355, 359. (b) Schenk, W. A.; Stur, T. Z. Naturforsch., B: Anorg. Chem.,
Org. Chem. 1990, 45, 1495. (c) Treichel, P. M.; Schmidt, M. S.; Crane,
R. A. Inorg. Chem. 1991, 30, 379.

4698 Organometallics, Vol. 15, No. 22, 1996
Bell et al.
Sch em e 4. P ossible Tr a n sition Sta te Mod els for
Com p etin g [2,3] Sigm a tr op ic Rea r r a n gem en ts
handling losses. Accordingly, an analogous sequence
involving a heavier alkylating agent, PhCH2I, was
investigated. Preparative reactions were worked up
chromatographically and gave 6 in >99-97% yields and
the previously characterized free benzyl sulfides PhCH2-
SCH(C(R)dCH2)CH2C(R)dCH2 (10a,b)3a in >99% yields.
It has been previously shown that the enantiomeric
purities of methyl and benzyl sulfides 9a ,b and 10a ,b
can be assayed by 13C NMR in the presence of Ag(fod)
and Eu(hfc)3.3a,20 Also, the absolute configurations of
9a and 10a have been established by a crystal structure
of the rhenium thiolate complex precursor shown in
Scheme 1.3a Configurations were assigned to 9b and
10b by analogy this and two other structurally charac-
terized rhenium thiolate complexes.3a,b
A
13C NMR
assay of the sample of 9a obtained in Scheme 3
established that the dominant configuration was S,
identical with the result obtained with the rhenium
Lewis acid I in Scheme 1 (71:29 S/R). The dominant
configuration of 10b was similarly shown to be S (88:
12 S/R). Importantly, the enantiomer ratios are within
experimental error of the 8a ,b diastereomer ratios.10
Hence, the carbon stereocenter is not affected by the
alkylation/substitution sequence.
Discu ssion
The above data establish that the deprotonation/
rearrangement sequence shown for diallyl sulfide com-
plexes of the chiral rhenium Lewis acid I in Scheme 1
can be extended to the chiral iron and ruthenium
fragments [(η5-C5H5)Fe(CO)(PPh3)]+ (II; Scheme 2) and
[(η5-C5H5)Ru(S,S-chiraphos)]+ (III; Scheme 3). Thus, we
believe that such transformations will prove general for
d6 cyclopentadienyl transition metal Lewis acids of the
formula [(η5-C5R5)M(L)(L′)]+. We also suggest that
other types of formally octahedral d6 metal fragments
will behave similarly and would not be surprised to see
this chemistry reduced to practice across the entire
transition metal series. In this context, metal sulfide
complexes are commonly air stable, thermally robust,
and experimentally forgiving compounds.
However, we were disappointed that the iron Lewis
acid II did not give higher diastereoselectivities than
the rhenium Lewis acid I. Although these might at first
glance seem to provide isosteric environments, metal-
ligand bonds in iron complexes are typically 6-9%
shorter than in rhenium homologs.21 We had antici-
pated that the more congested iron coordination sphere
would enhance the energy differences between the
competing diastereomeric transition states. With I,
diastereoselection has been previously analyzed in the
context of transition state models IV (favored) and V
(disfavored), as illustrated in Scheme 4.3,5 In the
former, a slight stabilizing interaction between the
cyclopentadienyl ligand hydrogens and the CdC π cloud
of the deprotonated allyl group has been proposed.
Perhaps the attraction is diminished by the shorter
contacts in II. It should also be emphasized that the
configurations assigned to the resulting iron thiolate
complexes (3, Scheme 2) are provisional, and V may in
fact represent the dominant pathway.
The ruthenium Lewis acid III gives somewhat higher
diastereoselectivities than II, and the configurations of
the resulting thiolate complexes (8, Scheme 3) have been
rigorously established. However, only scant information
is available concerning the preferred conformations of
ruthenium-sulfur or sulfur-carbon bonds in sulfide or
thiolate complexes of III or related compounds.22 Hence,
we feel that it is premature to propose a transition state
model at this time. For the moment, we simply note
that VI (Scheme 4), which is an arbitrary adaptation of
the rhenium/iron model IV, would lead to the major
diastereomer of the thiolate complex. It is nonetheless
apparent from VI that the energy differences between
the various competing transition states will largely
depend upon the following two factors: (1) the PPh2
phenyl ring orientations and (2) the PCHCH3 methyl
group that is directed toward the sulfide ligand.
Probably the most significant aspect of the ruthenium-
based chemistry in Scheme 3 is the efficient recycle
protocol. First, the thiolate ligand is easily detached
in a one-flask alkylation/substitution sequence (R′I/NaI).
Second, the starting ruthenium diallyl sulfide complex
can then be regenerated in a single step, as opposed to
the three steps required with the rhenium Lewis acid
I. Third, all yields are essentially quantitative. Curi-
ously, iodide ion does not readily displace sulfide ligands
from the coordination sphere of I. Thus, the continued
investigation of chiral cyclopentadienyl ruthenium Lewis
acids would seem to hold particular promise. Although
no fragments have yet been found that give diastereo-
selectivites as high as I, considerable structural diver-
sity is clearly possible with Lewis acids of the formula
[(η5-C5R5)M(L)(L′)]+. Thus, it should be possible to
develop an auxiliary that is optimized from both the
diastereoselectivity and recycling standpoints.
(20) Offermann, W.; Mannschreck, A. Tetrahedron Lett. 1981, 22,
3227.
(21) For comparisons of iron and rhenium dimethyl sulfide com-
plexes, see ref 4a.
(22) Ohkita, K.; Kurosawa, H.; Hirao, T.; Ikeda, I. J . Organomet.
Chem. 1994, 470, 179.

Diallyl Sulfide Complexes of Fe and Ru
Organometallics, Vol. 15, No. 22, 1996 4699
J CP ) 45, i-Ph), 132.1 (d, J CP ) 1, p-Ph), 129.8 (d, J CP ) 10,
m-Ph), 130.6 (s, CHd), 123.3 (s, dCH2), 85.0 (s, C5H5), 43.0
(d, J CP ) 1, SCH2), CO signal not observed; 31P{1H} 62.8 (s).
(η5-C5H5)Fe(CO)(P P h 3)(SCH(CHdCH2)CH2CHdCH2) (3).
Meth od A. An oven-dried Schlenk flask was charged with
1+BF4- (0.566 g, 0.924 mmol) and CH2Cl2 (30 mL) and cooled
to -80 °C. Then t-BuOK (1.0 M in THF; 924 µL, 0.924 mmol)
was added with stirring. After 5 min, the cold bath was
removed. Volatiles were immediately removed by oil pump
vacuum. Then ether/hexane (1:1 v/v, 40 mL) was added, and
the mixture was filtered via cannula (no. 1 paper). The filtrate
was chromatographed on an alumina column (14 × 2.5 cm)
with hexane (100 mL) and ether (100 mL). The green band
was concentrated by oil pump vacuum (30 mL), and hexane
(30 mL) was added. The sample was slowly concentrated by
oil pump vacuum. This gave green microcrystals of 3, which
were rapidly washed with hexane (5 mL) and dried by oil pump
vacuum (0.315 g, 0.601 mmol, 65%; 75:25 SS,RR/SR,RS).
Calcd for C30H29FeOPS: C, 68.71; H, 5.57. Found: C, 68.47;
H, 5.62.28 IR (cm-1, KBr): νCO 1936 vs.
Finally, this study adds to a growing body of data
involving R carbon-hydrogen bond activation in neutral
heteroatomic donor ligands. In the case of cationic
transition metal Lewis acids, deprotonation will give
reactive ylidic species. In our opinion, these have
numerous potential applications in synthesis, as il-
lustrated by the carbon-carbon bond-forming [2,3]
sigmatropic rearrangements above. Although the lit-
erature examples cited in our previous papers have
emphasized sulfide and sulfoxide ligands,23 it is clear
that ether24 and phosphine25 ligands can react similarly.
Current efforts in our laboratory also include attempts
to generate ylides of the types in Schemes 1-3 by
alternative pathways that do not require base addition.
Exp er im en ta l Section
Gen er a l P r oced u r es. IR and NMR spectra were recorded
on Mattson Polaris and Varian FT spectrometers.26 Micro-
analyses were conducted by Atlantic Microlab. Melting points
were determined in evacuated capillaries using calibrated
thermometers.27 Reactions were conducted under dry N2
atmospheres. Solvents were utilized as follows: CH2Cl2,
CD2Cl2, distilled from CaH2; THF, ether, hexanes, toluene,
benzene, distilled from (Na or K)/benzophenone; pentane,
distilled from activated 4 Å molecular sieves; C6D6, acetone,
methanol, used as received. The following reagents were used
as received (Aldrich unless noted): S(CH2CHdCH2)2, t-BuOK
(1.0 M in THF), (Me2CH)2NLi‚THF (1.5 M in cyclohexane),
(Me3Si)2NLi (1.0 M in THF), AgBF4, Ag(fod), (+)-Eu(hfc)3, CH3I
Meth od B. A flame-dried Schlenk flask was charged with
1+BF4- (0.1080 g, 0.1765 mmol) and CH2Cl2 (20 mL) and cooled
to -98 °C (CH3OH/liquid N2). Then t-BuOK (1.0 M in THF;
0.265 mL, 0.265 mmol) was added with stirring. After 1 h,
volatiles were removed by oil pump vacuum as the cold bath
was allowed to warm to room temperature. The residue was
extracted with benzene (5 mL) and the extract passed through
a frit. Volatiles were removed from the filtrate by oil pump
vacuum to give 3 as a green syrup (0.0852 g, 0.163 mmol, 92%
1
and >95% purity by H NMR; 68:32 SS,RR/SR,RS).
NMR for (SS,RR)-3:26 1H (CD2Cl2) 7.61-7.53 (m, 3 Ph), 5.78,
5.58 (2 m, 2 CHd), 4.90 (m, 2 dCH2), 4.50 (d, J HP ) 1, C5H5),
-
(Mallinckrodt), PhCH2I (AESAR), NH4+PF6 (Strem), (S,S)-
1
2.50 (m, SCH), 2.32 (m, SCHCHH′), 2.19 (m, SCHCHH′); H
chiraphos (Strem), S(CH2C(CH3)dCH2)2 (prepared as described
earlier).3b Alumina (80-200 mesh, Fisher) was activated (300
°C, 0.05 Torr, 12 h) and silica gel (230-400 mesh, 60 Å,
Aldrich) was degassed prior to use.
(C6D6) 7.78-6.97 (m, 3 Ph), 6.14, 5.85 (2 m, 2 CHd), 5.28-
4.90 (m, 2 dCH2), 4.35 (d, J HP ) 1, C5H5), 2.85 (m, SCHCHH′),
2.70-2.47 (m, SCH, SCHCHH′); 13C{1H} (CD2Cl2) 136.3 (d,
J CP ) 43, i-Ph), 133.9 (d, J CP ) 9, o-Ph), 130.4 (d, J CP ) 3,
p-Ph), 128.6 (d, J CP ) 10, m-Ph), 146.1, 138.5 (2 s, 2 CHd),
114.9, 111.0 (2 s, 2 dCH2), 84.6 (d, J CP ) 2, C5H5), 49.9 (d, J CP
) 4, SCH), 44.6 (s, SCHCH2), CO signal not observed; 31P{1H}
(CD2Cl2/C6D6) 68.1/71.2 (s). NMR for (SR,RS)-3 (partial): 1H
(CD2Cl2/C6D6) 4.50/4.28 (d, J HP ) 1, C5H5); 13C{1H} (CD2Cl2)
136.1 (d, J CP ) 43, i-Ph), 134.0 (d, J CP ) 9, o-Ph), 144.8, 138.6
(2 s, 2 CHd), 115.1, 111.5 (2 s, 2 dCH2), 84.8 (d, J CP ) 2, C5H5),
49.4 (d, J CP ) 4, SCH), 44.3 (s, SCHCH2); 31P{1H} (CD2Cl2/
C6D6) 68.1/71.1 (s).
(η5-C5H5)Ru (S,S-ch ir a p h os)(Cl) (4).16 A flame-dried flask
was charged with (η5-C5H5)Ru(PPh3)2(Cl) (1.79 g, 2.46 mmol),29
(S,S)-chiraphos (1.16 g, 2.72 mmol), and benzene (200 mL) and
fitted with a condenser. The mixture was refluxed for 4 h and
cooled. Volatiles were removed by rotary evaporation. The
residue was dissolved in a minimum of CH2Cl2 and chromato-
graphed on a silica gel column (30 × 2.5 cm) with CH2Cl2 (until
phosphine elution) and then acetone/CH2Cl2 (6:94 v/v). Vola-
tiles were removed from the orange-red band by rotary
evaporation and oil pump vacuum to give 4 as an orange
powder (1.34 g, 2.13 mmol, 87%).
-
[(η5 -C 5 H 5 )F e (C O )(P P h 3 )(S (C H 2 C H dC H 2 )2 )]+B F 4
(1+BF 4-). A Schlenk flask was charged with (η5-C5H5)Fe(CO)-
(PPh3)(I)9 (1.231 g, 2.287 mmol) and AgBF4 (0.459 g, 2.36
mmol) and cooled to -80 °C (2-propanol/CO2). Then THF (30
mL) was added with stirring. After 2 min, the cold bath was
removed. After 30 min, volatiles were removed by oil pump
vacuum. The residue was dissolved in CH2Cl2 (30 mL), and
S(CH2CHdCH2)2 (530 µL, 4.12 mmol) was added with stirring.
After 6 h, volatiles were removed by oil pump vacuum (1 h).
Then CH2Cl2 (80 mL) was added, and the mixture was filtered
via cannula (no. 1 paper). The filtrate was concentrated by
oil pump vacuum (ca. 20 mL), and ether (30 mL) was added
dropwise (15 min), giving a red-brown solid. The supernatant
was removed by cannula, and the solid was washed with ether
(50 mL). Then CH2Cl2 (40 mL) was added, and the mixture
was filtered via cannula (no. 1 paper). The filtrate was
concentrated by oil pump vacuum (ca. 20 mL), and ether (50
mL) was added dropwise (15 min). This gave red microcrystals
of 1+BF4-, which were washed with ether (30 mL) and pentane
(30 mL) and dried by oil pump vacuum (1.12 g, 1.82 mmol,
80%), mp 180 °C dec. Calcd for C30H30BF4FeOPS: C, 58.85;
H, 4.94. Found: C, 58.67; H, 4.96. IR (cm-1, CH2Cl2): νCO
1978 vs.
NMR (CDCl3):26 1H 7.60-6.50 (m, 4 Ph), 4.30 (s, C5H5), 2.66,
2.06 (2 m, 2 PCH), 1.02, 1.00 (2 dd, J HP ) 11, J HH ) 7; 2
PCHCH3); 31P{1H} 85.7, 64.6 (2 d, J PP ) 40). These data
matched literature values.16
NMR (CD2Cl2):26 1H 7.60-7.31 (m, 3 Ph), 5.56 (m, 2 CHd),
5.33 (m, 2 dCH2), 4.90 (d, J HP ) 2, C5H5), 3.23 (m, 2 SCHH′),
2.81 (m, 2 SCHH′); 13C{1H} 133.4 (d, J CP ) 9, o-Ph), 132.4 (d,
-
[(η5-C5H 5)R u (S,S-ch ir a p h os)(S(CH 2CH dCH 2)2)]+P F 6
(5a +P F 6-). Meth od A. A flame-dried flask was charged with
4 (0.208 g, 0.331 mmol), NH4+PF6 (0.360 g, 2.21 mmol),
-
(23) Bennett, M. A.; Goh, L. Y.; Willis, A. C. J . Am. Chem. Soc. 1996,
118, 4984.
(24) Yi, C. S.; Wo´dka, D.; Rheingold, A. L.; Yap, G. P. A. Organo-
metallics 1996, 15, 2.
CH3OH (20 mL), and S(CH2CHdCH2)2 (0.170 mL, 1.32 mmol)
and fitted with a condenser. The orange solution was refluxed
and became a mustard yellow suspension (0.5 h). After 18 h,
the mixture was cooled. Volatiles were removed by rotary
(25) Cagle, P. C. Unpublished results with diallylphosphine com-
plexes of I, University of Utah, 1994.
(26) Chemical shift references: 1H (300 MHz), TMS (δ 0.00); 13C{1H}
(75.5 MHz), CD2Cl2 (53.8 ppm); 31P{1H} (121.5 MHz), external 85%
H3PO4 (0.0 ppm). All J values are in Hz.
(28) Melting points are not reported for mixtures of diastereomers.
(29) Bruce, M. I.; Hameister, C.; Swincer, A. G.; Wallis, R. C. Inorg.
Synth. 1990, 28, 270.
(27) Tiers, G. V. D. J . Chem. Educ. 1990, 67, 258.

4700 Organometallics, Vol. 15, No. 22, 1996
Bell et al.
evaporation. The residue was extracted with CH2Cl2 (10 mL).
The extract was passed through a frit and added dropwise to
ether (100 mL, 0 °C). The precipitate was collected on a frit,
washed with ether (3 × 10 mL), and dried by oil pump vacuum
over Drierite to give 5a +PF6- as a bright yellow powder (0.265
evaporation and oil pump vacuum to give (SSS)-8a (0.0430 g,
[R]25
384° ( 2° (c 0.860 mg/mL, toluene)30) and (SSR)-8a
589
(0.0370 g, [R]25
257° ( 2° (c 0.745 mg/mL, toluene)30) as
589
orange syrups (combined yield 0.0800 g, 0.113 mmol, 97%; 54:
46 SSS/SSR).
Meth od C. An analogous reaction was conducted in which
both diastereomers of 8a were collected as one fraction. Anal.
g, 0.311 mmol, 94%), mp 216-220 °C dec, [R]25 341° ( 3° (c
589
0.470 mg/mL, CH2Cl2).30 Anal. Calcd for C39H43F6P3RuS: C,
54.99; H, 5.09. Found: C, 54.85; H, 5.31.
Calcd for
C39H42P2RuS: C, 66.36; H, 6.00; exact mass
Meth od B. The iodide complex (η5-C5H5)Ru(S,S-chira-
706.151 96. Found: C, 66.27; H, 6.05; exact mass 706.152 46.28
NMR for (SSS)-8a (C6D6):26 1H 8.21, 7.62, 7.27, 7.30-7.00,
6.93 (5 m, 4 Ph), 5.98 (dt, J HH ) 17, 10, CHCHd), 5.72 (ddt,
J HH ) 17, 10, 6, CH2CHd), 5.00-4.91 (m, dCHH′), 4.82 (dd,
J HH ) 10, 2, dC′HH′), 4.71 (s, C5H5), 4.64 (dd, J HH ) 17, 2,
dC′HH′), 3.36, 1.98 (2 m, 2 PCH),31 2.42 (m, SCHCHH′),31 1.47
phos)(I) (6, preparation below; 0.186 g, 0.258 mmol), NH4+PF6
-
(0.233 g, 1.43 mmol), CH3OH (25 mL), and S(CH2CHdCH2)2
(68 µL, 0.53 mmol) were combined in an analogous procedure.
An identical workup gave 5a +PF6- as a bright yellow powder
(0.213 g, 0.250 mmol, 97%)
NMR (CDCl3):26 1H 7.64-7.21, 7.01 (2 m, 4 Ph), 5.10 (ddt,
J HH ) 17, 9, 7; 2 CHd), 4.96 (br d, J HH ) 9; 2 dCHH′), 4.75
(d, J HH ) 17; 2 dCHH′), 4.71 (s, C5H5), 2.58, 2.30 (2 m, 2 PCH),
2.54 (dd, J HH ) 14, 8; 2 SCHH′), 2.15 (dd, J HH ) 14, 5; 2
SCHH′), 0.78, 0.72 (2 dd, J HP ) 12, J HH ) 6; 2 PCHCH3);
13C{1H} 134.1 (d, J CP ) 45, i-Ph), 133.8 (d, J CP ) 11, Ph), 132.4,
131.6 (2 d, J CP ) 9, Ph), 131.4 (d, J CP ) 4, Ph), 130.8 (br s,
Ph), 129.8, 129.4, 129.1 (3 d, J CP ) 9, Ph), 128.7 (d, J CP ) 10,
Ph), 132.0 (s, CHd), 121.0 (s, dCH2), 84.1 (s, C5H5), 44.4 (t,
J CP ) 6, SCH2), 38.0, 36.7 (2 dd, J CP ) 32/31, 18/16; 2 PCH),
15.0, 14.6 (2 br d, J CP ) 20/19; 2 PCHCH3), other Ph signals
obscured; 31P{1H} 85.1, 63.2 (2 d, J PP ) 40).
(td, J HH ) 9, 4, SCH),31 0.98, 0.87 (2 dd, J HP ) 11/12, J HH
)
7/7; 2 PCHCH3); 13C{1H} 144.1 (d, J CP ) 45, i-Ph), 138.7 (d,
J CP ) 43, i-Ph), 137.5, 136.7 (2 d, J CP ) 11, Ph), 133.1, 131.7,
127.6, 127.5 (4 d, J CP ) 9, Ph), 149.4, 139.6 (2 s, 2 CHd), 114.4,
111.4 (2 s, 2 dCH2), 82.9 (s, C5H5), 49.4 (t, J CP ) 6, SCH), 47.7
(s, SCHCH2), 38.0, 37.6 (2 dd, J CP ) 34/27, 19/17; 2 PCH), 17.5,
16.3 (2 dd, J CP ) 17/15, 3/5; 2 PCHCH3), other Ph signals
obscured; 31P{1H} 87.5, 74.7 (2 d, J PP ) 35). NMR for (SSR)-
8a (C6D6):26 1H 8.19, 7.65, 7.49, 7.30-6.88 (4 m, 4 Ph), 5.88
(ddt, J HH ) 18, 9, 7, CH2CHd),31 5.67 (ddd, J HH ) 19, 10, 9,
CHCHd),31 4.95-4.73 (m, 2 dCHH′), 4.62 (s, C5H5), 2.94, 2.06
(2 m, 2 PCH),31 2.62 (m, SCHCHH′),31 2.39 (m, SCHCHH′),31
[ ( η 5 - C 5 H 5 ) R u ( S , S - c h i r a p h o s ) ( S ( C H 2 C -
2.22 (td, J HH ) 9, 4, SCH),31 0.87, 0.76 (2 dd, J HP ) 11, J HH
)
(CH3)dCH2)2)]+P F 6 (5b+P F 6-). Complex 6 (0.654 g, 0.909
7; 2 PCHCH3); 13C{1H} 142.1, 138.8, 138.7 (3 d, J CP ) 43, i-Ph),
136.2 (d, J CP ) 10, Ph), 135.4 (d, J CP ) 11, Ph), 133.4, 131.8 (2
-
-
mmol), NH4+PF6 (1.16 g, 7.12 mmol), CH3OH (70 mL), and
S(CH2C(CH3)dCH2)2 (0.517 g, 3.64 mmol) were combined in a
procedure analogous to those for 5a +PF6-. The orange extract
was passed through a frit and added dropwise to pentane (300
mL, 0 °C). The precipitate was collected on a frit, washed with
pentane (3 × 30 mL), and dried by oil pump vacuum over
d, J CP ) 9, Ph), 129.6, 129.3 (2 d, J CP ) 2, Ph), 127.7 (d, J CP )
9, Ph), 147.9, 139.4 (2 s, 2 CHd), 114.4, 110.7 (2 s, 2 dCH2),
83.6 (s, C5H5), 49.8 (t, J CP ) 4, SCH), 45.9 (s, SCHCH2), 40.3,
37.5 (2 dd, J CP ) 29/32, 20/19; 2 PCH), 16.6, 16.4 (2 dd, J CP
)
12/12, 4/5; 2 PCHCH3), other Ph signals obscured; 31P{1H}
89.4, 71.8 (2 d, J PP ) 40).
-
Drierite to give 5b+PF6 as a green powder (0.748 g, 0.850
mmol, 94%), mp 135-147 °C dec, [R]25 294° ( 1° (c 0.470
(η5-C5H 5)R u (S,S-ch ir a p h os)(SCH (C(CH 3)dCH 2)CH 2C-
589
mg/mL, CH2Cl2).30 Anal. Calcd for C41H47F6P3RuS: C, 55.97;
-
(CH3)dCH2) (8b). Meth od A. Complex 5b+PF6 (0.0771 g,
H, 5.38. Found: C, 54.65; H, 5.36.
0.0876 mmol), CH2Cl2 (10 mL), and t-BuOK (1.0 M in THF;
0.10 mL, 0.10 mmol) were combined in a procedure analogous
to method A for 8a . An identical workup gave 8b as a red-
orange powder (0.0623 g, 0.0849 mmol, 97% and >95% purity
NMR (CD2Cl2):26 1H 7.74-7.55, 7.50-7.28, 7.02 (3 m, 4 Ph),
4.69 (s, 2 dCHH′), 4.67 (s, 2 dCHH′), 4.56 (s, C5H5), 2.81 (d,
J HH ) 14; 2 SCHH′), 2.58 (d, J HH ) 14; 2 SCHH′), 2.62, 2.38
(2 m, 2 PCH), 1.31 (s, 2 dCCH3), 0.85, 0.73 (2 dd, J HP ) 12/13,
J HH ) 7/7; 2 PCHCH3); 13C{1H} 134.5 (d, J CP ) 47, i-Ph), 133.8,
by
1H NMR; 87:13 SSS/SSR).
-
Meth od B. Complex 5b+PF6 (0.100 g, 0.114 mmol),
129.6, 128.8 (3 d, J CP ) 10, Ph), 132.9, 130.2, 129.4 (3 d, J CP
)
CH2Cl2 (20 mL), and t-BuOK (1.0 M in THF; 0.136 mL, 0.136
mmol) were combined in a procedure analogous to method B
for 8a . The residue was extracted with benzene (5 mL). The
extract was passed through a frit, and volatiles were removed
by oil pump vacuum to give 8b as a red-orange powder (0.0830
g, 0.114 mmol, >99%; 68:32 SSS/SSR).
9, Ph), 131.4-130.9 (m, Ph), 139.5 (s, dCCH3), 116.6 (s, dCH2),
84.8 (s, C5H5), 38.6, 36.9 (2 dd, J CP ) 32/31, 18/17; 2 PCH),
21.6 (s, dCCH3), 15.0, 14.5 (2 dd, J CP ) 17/18, 5/4; 2 PCHCH3),
other Ph and SCH2 signals obscured; 31P{1H} 81.2, 66.2 (2 d,
J PP ) 42).
( η5 -C 5 H 5 ) R u ( S , S -c h i r a p h o s ) ( S C H ( C H dC H 2 ) -
CH2CHdCH2) (8a ). Meth od A. A flame-dried Schlenk flask
was charged with 5a +PF6- (0.0531 g, 0.0623 mmol) and CH2Cl2
(10 mL) and cooled to -98 °C (CH3OH/liquid N2). Then
t-BuOK (1.0 M in THF; 0.10 mL, 0.10 mmol) was slowly added
with stirring. After 1 h, volatiles were removed by oil pump
vacuum as the cold bath was allowed to warm to room
temperature. The residue was extracted with benzene (5 mL).
The extract was passed through a frit. Volatiles were removed
by oil pump vacuum to give 8a as an orange syrup (0.0453 g,
0.0637 mmol, >99% and >95% purity by 1H and 31P NMR;
78:22 SSS/SSR).
Meth od C. The preceding reaction and workup was
repeated, and the sample was flash chromatographed as
described in procedure C for 8a . Anal. Calcd for C41H46P2-
RuS: C, 67.09; H, 6.32. Found: C, 67.09; H, 6.60.28
NMR for (SSS)-8b (C6D6):26 1H 8.31, 7.66, 7.27-7.00, 6.93
(4 m, 4 Ph), 4.75, 4.67, 4.57 (3 m, 2 dCHH′), 4.72 (s, C5H5),
3.40, 1.99 (2 m, 2 PCH), 2.55 (t, J HH ) 13, SCHCHH′), 2.27
(dd, J HH ) 14, 5, SCHCHH′), 2.21, 1.52 (2 s, 2 dCCH3), 2.08
(dd, J HH ) 12, 5, SCH), 0.98, 0.90 (2 dd, J HP ) 11/12, J HH
)
7/7; 2 PCHCH3); 13C{1H} 144.4 (d, J CP ) 43, i-Ph), 139.1, 139.0
(2 d, J CP ) 44; 2 i-Ph), 137.9, 136.7 (2 d, J CP ) 11, Ph), 133.1,
131.7 (2 d, J CP ) 9, Ph), 130.0, 129.9, 129.2 (3 d, J CP ) 2, Ph),
127.6, 127.4 (2 d, J CP ) 6, Ph), 152.4, 145.6 (2 s, 2 dCCH3),
111.6, 111.0 (2 s, 2 dCH2), 82.4 (s, C5H5), 51.1 (br d, J CP ) 6,
SCH), 49.7 (s, SCHCH2), 38.3, 37.8 (2 dd, J CP ) 39/27, 19/17;
2 PCH), 22.8, 18.3 (2 s, 2 dCCH3), 17.8, 16.4 (2 dd, J CP ) 16/
15, 2/4; 2 PCHCH3), other Ph signals obscured; 31P{1H} 87.5,
76.2 (2 d, J PP ) 34). NMR for (SSR)-8b (C6D6):26 1H 8.19, 7.70,
7.63, 7.30, 7.29-6.89 (5 m, 4 Ph), 4.77, 4.72, 4.66, 4.57 (4 m,
2 dCHH′), 4.61 (s, C5H5), 2.72, 2.15 (2 m, 2 PCH), 2.63 (dd,
Meth od B. A flame-dried Schlenk flask was charged with
-
5a +PF6 (0.100 g, 0.117 mmol) and THF (10 mL) and cooled
to -80 °C. Then t-BuOK (1.0 M in THF; 0.18 mL, 0.18 mmol)
was slowly added with stirring. The cold bath was removed.
After 1 h, volatiles were removed by rotary evaporation. The
residue was dissolved in a minimum of toluene and flash
chromatographed on a silica gel column (230-400 mesh, 30
× 1.0 cm) with hexanes/ether (4:1 v/v) and N2 pressure. Two
orange bands were collected. Volatiles were removed by rotary
(31) These 1H NMR assignments were confirmed by COSY experi-
ments.
(30) Dewey, M. A.; Gladysz, J . A. Organometallics 1993, 12, 2390.

Diallyl Sulfide Complexes of Fe and Ru
Organometallics, Vol. 15, No. 22, 1996 4701
J HH ) 10, 5, SCH), 2.42 (m, SCHCHH′), 0.81, 0.61 (2 dd, J HP
) 11, J HH ) 7; 2 PCHCH3); 13C{1H} 135.4, 133.4 (2 d, J CP ) 9,
Ph), 134.4 (d, J CP ) 10, Ph), 129.5, 129.1 (2 br s, Ph), 152.3,
145.7 (2 s, 2 dCCH3), 111.2, 110.5 (2 s, 2 dCH2), 83.9 (s, C5H5),
52.2 (dd, J CP ) 6, 4, SCH), 48.5 (s, SCHCH2), 42.2, 36.6 (2 dd,
J CP ) 31/30, 21/19; 2 PCH), 22.2, 18.2 (2 s, 2 dCCH3), 16.6,
15.9 (2 dd, J CP ) 17/18, 5/3; 2 PCHCH3), other Ph signals
obscured; 31P{1H} 92.3, 72.1 (2 d, J PP ) 42).
solved in a minimum of CH2Cl2 and flash chromatographed
on a silica gel column (230-400 mesh, 30 × 2.5 cm) with
pentane/CH2Cl2 (9:1 v/v) and N2 pressure. Volatiles from the
first fraction were removed by rotary evaporation to give
previously characterized3b 10a as a faint yellow liquid (0.0993g,
0.486 mmol, >99%). The column was eluted with 6:94 acetone/
CH2Cl2 (v/v) to give a red-orange fraction. Solvent was
removed by rotary evaporation to give 6 (0.3507 g, 0.4874
mmol, >99%) as an orange syrup. NMR data were identical
with those above.
NMR for 10a (acetone-d6):26 1H 7.59-7.31 (m, Ph), 5.97-
5.74 (m, 2 CHd), 5.28-5.10 (m, 2 dCH2), 3.85 (d, J ) 14,
CHH′Ph), 3.77 (d, J ) 14, CHH′Ph), 3.31 (m, SCH), 2.46
(SCHCHH′). These data matched literature values.3b
CH 3SCH (C(CH 3)dCH 2)CH 2C(CH 3)dCH 2 (9b ) a n d 6.
Complex 8b (0.0291 g, 0.0397 mmol), CH3I (3 µL, 0.05 mmol),
acetone (10 mL), and NaI (0.119 g, 0.793 mmol) were combined
in a procedure analogous to that for 9a . An identical workup
gave 9b as a faint yellow liquid (0.0044 g, 0.028 mmol, 71%)
and 6 (0.0257 g, 0.0357 mmol, 90%) as an orange syrup.
NMR for 9b (CDCl3):26 1H 4.88-4.75 (m, 2 dCH2), 3.31 (t,
J HH ) 8, SCH), 2.34 (d, J HH ) 8, SCHCHH′), 1.95 (d, J HH ) 1,
SCH3), 1.76 (s, 2 CH3). These data matched literature values.3b
P h CH2SCH(C(CH3)dCH2)CH2C(CH3)dCH2 (10b) a n d 6.
Complex 8b (0.0787 g, 0.107 mmol), PhCH2I (0.0282 g, 0.129
mmol), acetone (20 mL), and NaI (0.321 g, 2.14 mmol) were
combined in a procedure analogous to that for 10a . An
identical workup gave 10b as a light yellow liquid (0.0248 g,
0.107 mmol, >99%; 88:12 S/R, Ag(fod)/Eu(hfc)3 analysis10,20 of
112.6 ppm 13C NMR signal) and 6 (0.0749 g, 0.104 mmol, 97%)
as an orange syrup.
CH3SCH(CHdCH2)CH2CHdCH2 (9a ) a n d (η5-C5H5)Ru -
(S,S-ch ir a p h os)(I) (6). A flask was charged with 8a (0.8298
g, 1.175 mmol; 75:25 SSS/SSR), acetone (50 mL), and CH3I
(81 µL, 1.3 mmol) and fitted with a condenser. The orange
solution turned yellow within 2 min and was refluxed for 1 h.
Then NaI (3.5 g, 23 mmol) was added, and the mixture
refluxed for 5 h. The sample was concentrated by rotary
evaporation, and the volatiles were transferred (25-50 °C, oil
pump vacuum) into a liquid N2-cooled receiver. Residual
solvent was removed by rotary evaporation to give previously
characterized3b (S)-9a as a pale green-yellow liquid (0.1125 g,
0.8773 mmol, 75%; 71:29 S/R, Ag(fod)/Eu(hfc)3 analysis10,20 of
the 117.0 ppm 13C NMR signal). The residue from the vacuum
transfer was dissolved in CH2Cl2 and flash chromatographed
on a silica gel column (230-400 mesh, 30 × 1.0 cm) with
CH2Cl2 and N2 pressure. Volatiles were removed by rotary
evaporation to give 6 (0.829 g, 1.15 mmol, 98%) as an orange
syrup.18
NMR for 9a (CDCl3):26 1H 5.82 (ddt, J HH ) 17, 10, 7,
CH2CHd), 5.61 (ddd, J HH ) 17, 10, 9, CHCHd), 5.14-4.96
(m, 2 dCH2), 3.11 (m, SCH), 2.38 (apparent tq, J HH ) 7, 1,
SCHCHH′), 2.00 (s, SCH3); 13C{1H} 138.4, 135.4 (2 s, 2 CHd),
117.0, 115.6 (2 s, 2 dCH2), 50.1 (s, SCH), 38.6 (s, SCHCH2),
13.9 (s, SCH3). These data matched literature values.3b NMR
for 6 (CDCl3):26 1H 7.93, 7.58-7.17, 7.01 (3 m, 4 Ph), 4.45 (s,
C5H5), 3.03, 2.14 (2 m, 2 PCH), 1.13, 1.04 (2 dd, J HP ) 11/11,
J HH ) 7/7; 2 PCHCH3); 31P{1H} 82.6, 74.0 (2 d, J PP ) 34).
These data matched literature values.18
NMR for 10b (CDCl3):26 1H 7.31-7.20 (m, Ph), 4.93-4.69
(m, 2 dCH2), 3.60 (d, J HH ) 13, CHH′Ph), 3.56 (d, J HH ) 13,
CHH′Ph), 3.42 (t, J HH ) 8, SCH), 2.31 (d, J HH ) 8, SCHCHH′),
1.80, 1.65 (2 s, 2 CH3). These data matched literature values.3b
P h CH2SCH(CHdCH2)CH2CHdCH2 (10a ) a n d 6. Com-
plex 8a (0.3429 g, 0.4858 mmol), PhCH2I (0.1170 g, 0.5340
mmol), acetone (20 mL), and NaI (0.154 g, 1.03 mmol) were
combined in a procedure analogous to that for 9a . Volatiles
were removed by rotary evaporation. The residue was dis-
Ack n ow led gm en t. We thank the NSF for financial
support. Postdoctoral fellowships were generously pro-
vided by the NIH (P.T.B., P.C.C) and NATO (D.V.).
OM960541Q