C-C Coupling Reactions of (Sulfene)ruthenium Complexes with Enolates

Article abstract of DOI:10.1002/(SICI)1099-0682(199805)1998:5<605::AID-EJIC605>3.0.CO;2-H

Sulfene complexes [CpRu(PR′₃)₂(RHC=SO₂)]PF6 (2a-d) are obtained from the corresponding sulfur dioxide complexes 1a-c and diazomethane or -ethane. Reaction of [CpRu(dppm)(SO₂)]Cl (1d) and phenyldiazomethane gives

Full text of DOI:10.1002/(SICI)1099-0682(199805)1998:5<605::AID-EJIC605>3.0.CO;2-H

FULL PAPER
Sulfur(IV) Compounds as Ligands, 23[᭛]
C؊C Coupling Reactions of (Sulfene)ruthenium Complexes with Enolates
Wolfdieter A. Schenk* and Jürgen Bezler
Institut für Anorganische Chemie der Universität Würzburg,
Am Hubland, D-97074 Würzburg, Germany
Fax: (internat.) ϩ 49(0)931/888-4605
E-mail: wolfdieter.schenk@mail.uni-wuerzburg.de
Received December 2, 1997
Keywords: Enolates / Nucleophilic additions / Ruthenium / S ligands / Sulfenes
Sulfene complexes [CpRu(PRЈ3)2(RHC=SO2)]PF6 (2aϪd) are
obtained from the corresponding sulfur dioxide complexes
1aϪc and diazomethane or -ethane. Reaction of
[CpRu(dppm)(SO2)]Cl (1d) and phenyldiazomethane gives
the chlorobenzylsulfinato complex [CpRu(dppm)(SO2-
CHPhCl)] (3). Alternatively, 2a may be synthesized by sulfur
dioxide addition to the carbene complex [CpRu(dppm)-
Treatment of 2aϪd or 3 with the enolates of cyclic 2-methyl-
1,3-diketones, methyl malonates, open-chain cyano or β-oxo
esters, and cyclic β-oxo esters gives the CϪC coupling pro-
ducts 6a, b, 7a؊e, 8a؊c, 9aϪc in high yields and, in one case,
with high diastereoselectivity as well. The functionalized sul-
finate ligands thus formed may be alkylated and subsequ-
ently removed from the metal center by ligand substitution
(CH2)]PF6 (5) which, in turn, is obtained from the correspon- with acetonitrile. After MeCN/SO2 exchange, the ruthenium
ding methyl complex [CpRu(dppm)(CH3)] and [Ph3C]PF6. complex can be recycled.
Highly reactive and unstable molecules can often be sta-
bilized by coordination to a transition metal Ϫ this prin-
ciple is certainly one of the most fascinating aspects of or-
ganic transition-metal chemistry.[1] In an ideal case, the
species under consideration is not only “tamed”, but is suf-
ficiently modified such that it undergoes novel types of re-
actions. Sulfenes R1R2CϭSO2 are short-lived intermediates
that may be generated for example by 1,2-elimination or [2
ϩ 4]-cycloreversion reactions.[2] Their typical transform-
ations include 1,2-additions across the CϭS double bond,
nucleophilic
addition
at
sulfur,
and
cycload-
ditions.[2][3][4][5][6][7] Recently, we have synthesized η2(C,S)-
sulfene complexes of the type [CpRu(PR3)2(CH2ϭSO2)]ϩ
by methylene addition to the corresponding sulfur dioxide
complexes.[8][9] In these species, the formal polarity of the
sulfene is reversed. Nucleophiles such as halide or pseudo-
halide ions, amines and phosphanes are added at the carbon
atom. With enamines, CϪC coupling occurs with high yield
and chemoselectivity.[9] We now report on the addition of
enolates to sulfene complexes.
acid esters were unsuccessful. However, when we treated the
chloride salt 1d with phenyldiazomethane, we obtained the
chlorobenzylsulfinate complex 3 in high yield (eq. 2). Com-
plex 3 represents a synthetic equivalent for the correspond-
ing phenylsulfene complex (see below).
Results
Synthesis of Sulfene Complexes
The reaction of the sulfur dioxide complex 1a with diazo-
methane or -ethane to give the sulfene complexes 2a,d has
been described previously.[9] Similarly, 1b, c give the sulfene
complexes 2b, c (eq. 1).
Attempts to perform analogous reactions of 1a with
phenyldiazomethane, diphenyldiazomethane, or diazoacetic
An alternative synthetic access to sulfene complexes is
provided by the addition of SO2 to carbene com-
plexes.[10][11] Thus, when the methyl complex 4 is treated at
low temperature with triphenylmethyl hexafluorophos-
phate, a red solution of the carbene complex 5 is ob-
tained,[12] which, upon addition of SO2, undergoes immedi-
ate discoloration to yield 2a (eq. 3). However, in spite of
[᭛]
Part 22: Ref.[15]
.
Eur. J. Inorg. Chem. 1998, 605Ϫ611
WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1998
1434Ϫ1948/98/0505Ϫ0605 $ 17.50ϩ.50/0
605

W. A. Schenk, J. Bezler
FULL PAPER
numerous attempts, we have not been able to extend this
reaction to complexes of substituted sulfenes.
the analogous phenyl derivative 7e was obtained from the
chlorobenzylsulfinate complex 3 (eq. 5).
2b, c are slightly yellow crystalline compounds which,
even at Ϫ20°C, decompose within a few days. 2c has spec-
troscopic properties very similar to those of 2a and the crys-
tallographically characterized complex [Cp*Ru(PMe3)2(η2-
CH2ϭSO2)]PF6.[9] 2b, on the other hand, is unusual in that
it is fluxional on the NMR timescale due to a rapid rotation
of the sulfene ligand. Standard treatment[13] of the tempera-
ture-dependent 31P-NMR spectra using a two-site exchange
model[14] yields an activation barrier of ∆G϶ ϭ 60 kJ
molϪ1. A similar ligand rotation has been found for the
analogous sulfur trioxide complex [Cp*Ru(PMe3)2(η2-Oϭ
Products 6 and 7 were obtained as light-yellow crystalline
solids. Due to their symmetrical structure they have fairly
simple NMR spectra, which are in full accord with the con-
stitutions shown in eqs. 4 and 5. Of note is the significant
downfield shift (> 90 ppm) of the resonance of the former
sulfene carbon atom that accompanies its release from the
ruthenium atom. In similar experiments, the sulfene com-
plexes 2a, b were treated with the ester enolates of 2-methyl-
3-oxobutyric acid and 2-cyanopropionic acid (eq. 6), while
2a, d were allowed to react with the deprotonated esters of
2-oxocyclopentane- and 2-oxocyclohexane-1-carboxylic ac-
ids (eq. 7).
1
SO2)]PF6.[15] In the H-NMR spectra, the two non-equiva-
lent protons of the methylene groups give rise to two widely
separated signals with the typical geminal coupling of ca. 4
Hz. The high-field signals show additional splitting due to
strong coupling with one of the two phosphorus atoms. The
13C resonance of the sulfene carbon atom appears as a
doublet at δ ϭ Ϫ20. Finally, two fairly strong absorptions
in the infrared spectrum at ν˜ ഠ 1230 and 1100 cmϪ1 are
typical for the η2(C,S)-coordinated sulfene ligand.[9]
The chlorobenzylsulfinato complex 3 is a yellow, crystal-
line, air-stable compound. The two diastereotopic phos-
phorus atoms give rise to a narrow AB system in the 31P-
NMR spectrum, while the resonance of the α-carbon nu-
cleus at the sulfur atom is split into a narrow doublet of
doublets due to coupling with the two non-equivalent phos-
phorus nuclei. Here, the ν(SO) absorptions fall in the typi-
cal range of S-sulfinato complexes.[16]
Reactions with Enolates
Reactions of 2a in THF with the sodium enolates of 2-
methylcyclopentane-1,3-dione and 2,5,5-trimethylcyclohex-
ane-1,3-dione gave the expected addition compounds 6a, b
in good yields (eq. 4).
Similarly, treatment of 2a, b and d with the lithium eno-
lates of the diethyl or isopropylidene esters of methylma-
Again, the expected coupling products were obtained in
lonic acid yielded the CϪC coupling products 7aϪd, while good yields as light-yellow, air-stable, crystalline materials.
606
Eur. J. Inorg. Chem. 1998, 605Ϫ611

Sulfur(IV) Compounds as Ligands, 23
FULL PAPER
Since a stereocenter adjacent to the sulfene carbon atom is dioxide and allowing it to react for a few days at 20°C
formed in this reaction, the methylene protons as well as (eq. 10).
the phosphorus nuclei become diastereotopic. 9c was iso-
lated in 71% yield as a single diastereoisomer. NMR-spec-
troscopic analysis of the crude reaction mixture revealed an
almost quantitative formation of 9c and none of the op-
posite diastereomer. Unfortunately, this compound crys-
tallized only as stacks of very thin platelets, which were un-
suitable for X-ray structure determination.
Release of the Sulfinate Ligands
The reactions of 7a and 8c with oxonium salts in di- Discussion
chloromethane (eq. 8) gave the expected O-alkylation[17]
products 10aϪc, which were isolated in almost quantitative
yield as yellow, crystalline, highly moisture-sensitive materi-
The methylene transfer outlined in eq. 1 is initiated by
nucleophilic attack of the diazo compound on the coordi-
nated sulfur dioxide.[9] This explains why less nucleophilic
als. Alkylation of one of the SϭO functions introduces a
diazo compounds do not react Ϫ phenyldiazomethane
new stereocenter at the sulfur atom and renders the methyl-
seems to represent the limiting case. The expected phenyl-
ene protons as well as the phosphorus nuclei diastereotopic.
sulfene complex was too unstable to be isolated but, due to
Only negligible diastereoselectivity (2%) is observed in the
its high electrophilicity,[9] could be trapped by the addition
formation of 10c.
of chloride ions. The “inverse synthesis” of the sulfene com-
plex 2a as outlined in eq. 3 indicates that low-valent cationic
carbene complexes such as 5, which are normally seen as
role models of electrophilic carbenes,[21] may also exhibit
some nucleophilic character. A further extension of this
synthesis to complexes of substituted sulfenes, however, was
thwarted by the inaccessibility of the corresponding car-
bene complexes.
The rapid rotation of the sulfene ligand in 2b deserves
some comment. On the basis of steric considerations alone,
it might be tempting to assume that the sulfene ligand can
rotate more freely in the less congested dppm complex 2a.
The rotational barrier of a single-faced π-acceptor ligand,
however, depends to a large extent on the spatial extension
The role of sulfinic acid esters as ligands in coordination
and energy difference of the occupied aЈ and aЈЈ frontier
compounds has received very little attention.[17][18] Com-
orbitals of the [CpML2] fragment.[22] The antisymmetric aЈЈ
pared to sulfoxides, they are expected to be quite weak do-
nors. Indeed, when 10a, b are heated in acetonitrile a slow
ligand substitution takes place yielding the known aceto-
is the HOMO which is also MϪL antibonding. With in-
creasing pyramidalization of the [CpML2] fragment, that is
with decreasing LϪMϪL angle, the energy of this orbital
nitrile complex 11[19] along with the free esters 12a, b (eq.
is increased,[23] leading to a stronger fixation of the π-ac-
9).
ceptor ligand perpendicular to the symmetry plane of the
[CpML2] complex.
Even in the early stages of this project, it soon became
apparent that cationic sulfene complexes are highly reactive
electrophiles.[8] Compared to uncoordinated sulfene, which
adds nucleophiles at the sulfur atom,[2][3] the sulfene com-
plexes studied here exhibit a reversed polarity;[9] only hard
nucleophiles such as alkoxides are added at the sulfur
atom.[8] Initial attempts to treat 2a with Na[acac] gave in-
tractable product mixtures, the spectral analyses of which
indeed indicated competing CϪC and CϪO coupling, as
well as further reactions initiated by deprotonation of the
Despite the long reaction time, we observed no re- products. All these problems could readily be overcome by
arrangement[20] to the corresponding sulfones. The mix- employing salts of tertiary CϪH acidic compounds. In
tures could be readily separated by extraction with diethyl these cases, the reactions are clean and give the desired ad-
ether, leaving 12a, b in quantitative yields as colorless oils. dition products in high yields. Particularly noteworthy is the
11 may be converted back into the starting SO2 complex 1a high diastereoselectivity of the formation of 9c (eq. 7). This
Ϫ
or its BF4 salt 1e simply by dissolving it in liquid sulfur is certainly a result of the rigid fixation of the methylsulfene
Eur. J. Inorg. Chem. 1998, 605Ϫ611
607

W. A. Schenk, J. Bezler
FULL PAPER
Bruker AMX 400, δ values relative to 85% H3PO4. The 1H- and
ligand in a sterically congested environment, which allows
the prochiral enolate to approach in one orientation only.
The alkylation of the sulfinate function to give complexes
of sulfinic acid esters provides a means of removing the
metal complex from the organic moiety under mild con-
ditions. Furthermore, the ionic acetonitrile complex thus
obtained is easily separated from the organic component
and can be converted back to the sulfur dioxide complex.
A closed cycle is thus created, which allows the assembly
13C-NMR signals of the phosphane ligands and the 31P-NMR sig-
Ϫ
nals of the PF6 ion are very similar for all compounds and have
therefore been omitted from the lists of spectral data. Ϫ Elemental
analyses: Analytical Laboratory of the Institut für Anorganische
Chemie. Ϫ The following starting materials were obtained as de-
scribed in the literature: [CpRu(PR3)2(SO2)]X (1a؊d),[25]
[CpRu(dppm)Cl],[19] [CpRu(dppm)(RHCϭSO2)]PF6 (2a, d),[9] di-
azomethane, diazoethane,[26] phenyldiazomethane.[27] Enolates
were obtained from the corresponding 1,3-dicarbonyl compounds
of chain-extended sulfinic acid esters from sulfur dioxide, by deprotonation using lithium diisopropylamide or sodium bis(tri-
methylsilyl)amide. All other reagents were used as purchased.
diazomethane or -ethane, and enolates (Scheme 1). Perti-
nent literature reports sulfinic acid esters to be prone to
rearrangement to the corresponding sulfones.[20] Under our
conditions, no such rearrangement could be detected, but
we have at present no clear explanation as to the unexpec-
ted stability of 12a, b.
[CpRu(dppe)(H2CϭSO2)]PF6 (2b): To a solution of 1b (177
mg, 0.23 mmol) in dichloromethane (20 ml) a solution of diazo-
methane in diethyl ether (1 ml, 0.30 mmol) was added at Ϫ70°C.
Gas evolution and a rapid color change to light-yellow were ob-
served. The mixture was allowed to warm to 0°C, and all volatiles
were removed in vacuo. After recrystallization from dichlorometh-
ane/pentane, a tan-colored microcrystalline powder was obtained.
Yield 160 mg (89%), m.p. 156°C (dec.). Ϫ 1H NMR (400 MHz,
Scheme 1
2
3
CD2Cl2, Ϫ70°C): δ ϭ 0.02 [dd, J(H,H) ϭ 4.4 Hz, J(P,H) ϭ 16.8
Hz, 1 H, HCϭSO2], 3.30 (br. m, 1 H, HCϭSO2), 5.68 (s, 5 H,
C5H5). Ϫ 13C NMR (100 MHz, CD2Cl2, Ϫ70°C): δ ϭ Ϫ20.2 [d,
2J(P,C) ϭ 6 Hz, H2CϭSO2], 85.6 (s, C5H5). Ϫ 31P NMR (162 MHz,
CD2Cl2, Ϫ70°C): δ ϭ 73.8 [d, 2J(P,P) ϭ 20 Hz], 78.7 [d, 2J(P,P) ϭ
20 Hz].
Ϫ IR (Nujol): ν˜ ϭ Ϫ
1236, 1093 cmϪ1 (SϭO).
C32H31F6O2P3RuS (787.6): calcd. C 48.80, H 3.97, S 4.07; found C
48.88, H 4.14, S 4.01.
[CpRu(PMe3)2(H2CϭSO2)]PF6 (2c): This compound was pre-
pared analogously from 1c (120 mg, 0.23 mmol) and diazomethane
1
(0.45 mmol). Yield 109 mg (89%), m.p. 91°C (dec.). Ϫ H NMR
(400 MHz, [D6]acetone, 20°C): δ ϭ 0.71 [dd, 2J(H,H) ϭ 3.9 Hz,
3J(P,H) ϭ 17.6 Hz, 1 H, HCϭSO2], 2.57 (br. m, 1 H, HCϭSO2),
5.92 (s, 5 H, C5H5). Ϫ 13C NMR (100 MHz, [D6]acetone, 20°C):
2
δ ϭ Ϫ22.3 [d, J(P,C) ϭ 5 Hz, H2CϭSO2], 96.0 (s, C5H5). Ϫ 31P
NMR (162 MHz, [D6]acetone, 20°C): δ ϭ 7.7 [d, 2J(P,P) ϭ 43 Hz],
2
9.7 [d, J(P,P) ϭ 43 Hz]. Ϫ IR (Nujol): ν˜ ϭ 1220, 1104 cmϪ1 (Sϭ
Esters of sulfinic acids have a number of important appli-
cations in organic synthesis.[24] Most pertinent work has
been carried out on arenesulfinic acid esters, which seem to
be much more readily accessible than their alkane counter-
parts. It is thus particularly gratifying that the reaction se-
quence outlined here not only provides esters of aliphatic
sulfinic acids, but also tolerates a number of different func-
tional groups.
O). Ϫ C12H25F6O2P3RuS (541.4): calcd. C 26.62, H 4.65; found C
26.95, H 4.72.
[CpRu(dppm)(SO2CHClPh)] (3): This compound was pre-
pared analogously from 1d (85 mg, 0.13 mmol) and phenyldiazo-
methane (0.25 mmol). The crude product was purified by chroma-
tography on a short silica gel column using acetone/dichlorometh-
ane (2:1) as eluent. Yield 68 mg (71%), m.p. 171°C (dec.). Ϫ 1H
NMR (400 MHz, C6D6, 20°C): δ ϭ 4.50 (s, 1 H, CHClPh), 4.89
(s, 5 H, C5H5). Ϫ 13C NMR (100 MHz, C6D6, 20°C): δ ϭ 83.2 [t,
This work has been supported by the Deutsche Forschungsge-
meinschaft (SFB 347 “Selektive Reaktionen Metall-aktivierter Mo-
leküle”).
2J(P,C) ϭ 2 Hz, C5H5], 83.3 [dd, J(P,C) ϭ 2 Hz, J(P,C) ϭ 1 Hz,
CHClPh]. Ϫ 31P NMR (162 MHz, C6D6, 20°C): δ ϭ 11.0 [d,
2J(P,P) ϭ 90 Hz], 12.2 [d, 2J(P,P) ϭ 90 Hz]. Ϫ IR (Nujol): ν˜ ϭ
1184, 1032 cmϪ1 (SϭO). Ϫ C37H33ClO2P2RuS (740.2): calcd. C
60.04, H 4.49; found C 60.65, H 4.57.
2
2
Experimental Section
All experiments were carried out in Schlenk tubes under nitrogen
using suitably purified solvents. The crystallization of oily products
[CpRu(dppm)(CH3)] (4): A solution of [CpRu(dppm)Cl] (300
was often conveniently induced by immersing the Schlenk tube in mg, 0.51 mmol) in toluene (10 ml) was treated at 20°C with methyl-
a small ultrasonic cleaning bath. Ϫ IR: Perkin-Elmer 283, Bruker magnesium chloride in THF (1.54 mmol). After 20 h, the excess
1
IFS 25. Ϫ H NMR: Bruker AMX 400, δ values relative to TMS;
Grignard reagent was quenched by adding methanol (5 ml). All
diastereotopic methylene protons of ethoxy groups invariably gave volatile material was then removed in vacuo and the solid residue
well-resolved ABX3 spectra with 2J(H,H)
10.5 Hz and was redissolved in toluene (20 ml). The resulting solution was fil-
3J(H,H) ϭ 7.1 Hz; for the sake of simplicity they are denoted in tered through Celite, and the filtrate was concentrated to a volume
the following as “res. m” (resolved multiplet). Ϫ 13C NMR: Bruker
of 2 ml. Addition of pentane resulted in the deposition of the prod-
ϭ
AMX 400, δ values relative to TMS; assignments were routinely uct as yellow crystals. Yield 185 mg (64%), m.p. 176°C (dec.). Ϫ
3
checked by DEPT; in some cases the 13C-NMR signals of quater-
1H NMR (400 MHz, C6D6, 20°C): δ ϭ 0.20 [t, J(P,H) ϭ 7.1 Hz,
nary carbon atoms were too weak to be detected. Ϫ 31P NMR:
3 H, RuCH3], 4.87 (s, 5 H, C5H5). Ϫ 13C NMR (100 MHz, C6D6,
608
Eur. J. Inorg. Chem. 1998, 605Ϫ611

Sulfur(IV) Compounds as Ligands, 23
FULL PAPER
2
2
20°C): δ ϭ Ϫ23.1 [t, J(P,C) ϭ 13 Hz, RuCH3], 80.3 [t, J(P,C) ϭ 1.36 (s, 3 H, CH3), 2.57 (s, 2 H, SO2CH2), 4.07 (res. m, 4 H, OCH2),
2 Hz, C5H5]. Ϫ 31P NMR (162 MHz, C6D6, 20°C): δ ϭ 22.8 (s). Ϫ 4.85 (s, 5 H, C5H5). Ϫ 13C NMR (100 MHz, CDCl3, 20°C): δ ϭ
C31H30P2Ru (565.6): calcd. C 65.83, H 5.35; found C 65.52, H 5.42. 14.0 (s, CH3), 19.2 (s, CH3), 53.2 (s, Cquat), 61.0 (s, OCH2), 72.3 (s,
CH2SO2), 85.6 (s, C5H5), 171.4 (s, CO). Ϫ 31P NMR (162 MHz,
[CpRu(dppm)(H2CϭSO2)]PF6 (2a). Ϫ From 4: To a solution
CDCl3, 20°C): δ ϭ 83.0 (s). Ϫ IR (Nujol): ν˜ ϭ 1741, 1725 (CϭO),
of 4 (185 mg, 0.33 mmol) in dichloromethane (20 ml), a solution
1142, 1024 cmϪ1 (SϭO). Ϫ C40H44O6P2RuS (815.9): calcd. C 58.89,
of [Ph3C]PF6 (130 mg, 0.34 mmol) in the same solvent (2 ml) was
added at Ϫ70°C. Sulfur dioxide was then introduced into the deep-
red solution, and the mixture allowed to warm to 0°C. After con-
centration to a volume of 2 ml, the product was precipitated by
adding pentane. Yield 218 mg (86%), colorless crystalline powder,
identical (NMR, IR) with the known 2a.[9]
H 5.44; found C 58.18, H 5.22.
7d: Yield 117 mg (72%), m.p. 207°C (dec.). Ϫ 1H NMR (400
3
MHz, CDCl3, 20°C): δ ϭ 0.41 [t, J(H,H) ϭ 7.3 Hz, 3 H, CH3],
3
3
1.15 [t, J(H,H) ϭ 7.1 Hz, 3 H, CH3], 1.21 [t, J(H,H) ϭ 7.1 Hz,
3 H, CH3], 1.43 (s, 3 H, CH3), 3.66 [q, 3J(H,H) ϭ 7.3 Hz, 1 H,
SO2CHMe], 4.02 (res. m, 2 H, OCH2), 4.17 (res. m, 2 H, OCH2),
5.02 (s, 5 H, C5H5). Ϫ 13C NMR (100 MHz, CDCl3, 20°C): δ ϭ
11.2 (s, CH3), 14.2 (s, CH3), 15.6 (s, CH3), 57,5 (s, Cquat), 61.0 (s,
OCH2), 61.1 (s, OCH2), 74.5 (s, SO2CHMe), 82.7 (s, C5H5), 171.3
(s, CO), 171.4 (s, CO). Ϫ 31P NMR (162 MHz, CDCl3, 20°C): δ ϭ
Addition of Enolates: To a solution of Li[N(iPr)2] (25 mg, 0.22
mmol) or Na[N(SiMe3)2] (40 mg, 0.22 mmol) in THF (5 ml), an
equimolar amount of the respective CϪH acidic compound was
added at Ϫ70°C. The resulting slurry was then added to a solution
of 0.20 mmol of the sulfene complex in THF (10 ml). The mixture
was allowed to warm to 20°C and stirred for 2 h. The solvent was
then removed in vacuo, the oily residue was taken up in dichloro-
methane and chromatographed (neutral alumina, activity grade I,
acetone/dichloromethane, 2:1). A broad, light-yellow band contain-
ing the product was collected. The solvent was evaporated and the
product was recrystallized from benzene/pentane.
6a: Yield 76 mg (51%), m.p. 232°C (dec.). Ϫ 1H NMR (400
MHz, CD2Cl2, 20°C): δ ϭ 0.58 (s, 3 H, CH3), 2.34Ϫ2.48,
2.87Ϫ2.92 (m, 4 H, CH2CH2), 2.89 (s, 2 H, SO2CH2), 4.95 (s, 5 H,
C5H5). Ϫ 13C NMR (100 MHz, CD2Cl2, 20°C): δ ϭ 20.2 (s, CH3),
35.2 (s, CH2CH2), 52.9 (s, Cquat), 82.3 (s, CH2SO2), 84.0 [t,
2J(P,C) ϭ 2 Hz, C5H5], 216.2 (s, CO). Ϫ 31P NMR (162 MHz,
CD2Cl2, 20°C): δ ϭ 12.9 (s). Ϫ IR (Nujol): ν˜ ϭ 1715 (CϭO), 1144,
1024 cmϪ1 (SϭO). Ϫ C37H36O4P2RuS (739.8): calcd. C 60.07, H
4.91; found C 60.54, H 5.30.
2
2
8.8 [d, J(P,P) ϭ 86 Hz], 11.1 [d, J(P,P) ϭ 86 Hz]. Ϫ IR (Nujol):
ν
ϭ
1744, 1704 (CϭO), 1156, 1024 cmϪ1 (SϭO).
Ϫ
˜
C40H44O6P2RuS (815.9): calcd. C 58.89, H 5.44; found C 57.99,
H 5.07.
7e: This compound was obtained from 3. To ensure complete
reaction the mixture was refluxed for 2 h. Yield 142 mg (81%), m.p.
156°C (dec.). Ϫ 1H NMR (400 MHz, C6D6, 20°C): δ ϭ 0.75 [t,
3J(H,H) ϭ 7.1 Hz, 3 H, CH3], 0.94 [t, 3J(H,H) ϭ 7.1 Hz, 3 H,
CH3], 2.33 (s, 3 H, CH3), 3.64 (res. m, 2 H, OCH2), 3.95 (res. m, 1
H, OCH2), 4.13 (res. m, 1 H, OCH2), 4.35 (s, 5 H, C5H5), 4.55 (s,
1 H, SO2CHPh). Ϫ 13C NMR (100 MHz, C6D6, 20°C): δ ϭ 13.8
(s, CH3), 14.0 (s, CH3), 18.2 (s, CH3), 58,4 (s, Cquat), 60.5 (s, OCH2),
60.8 (s, OCH2), 78.4 (s, CHPhSO2), 82.6 (s, C5H5), 170.3 (s, CO),
170.5 (s, CO). Ϫ 31P NMR (162 MHz, C6D6, 20°C): δ ϭ 9.9 [d,
2J(P,P) ϭ 90 Hz], 14.0 [d, 2J(P,P) ϭ 90 Hz]. Ϫ IR (Nujol): ν ϭ
˜
1725, 1713 (CϭO), 1141, 1022 cmϪ1 (SϭO). Ϫ C45H46O6P2RuS
6b: Yield 124 mg (79%), m.p. 221°C (dec.). Ϫ 1H NMR (400
MHz, CD2Cl2, 20°C): δ ϭ 0.64 (s, 3 H, CH3), 0.91 (s, 3 H, CH3),
(877.9): calcd. C 61.56, H 5.28; found C 61.72, H 5.19.
2
8a: Yield 114 mg (74%), m.p. 221°C (dec.). Ϫ 1H NMR (400
1.00 (s, 3 H, CH3), 2.07 [d, J(H,H) ϭ 14.3 Hz, 2 H, CH2], 2.82
2
3
[d, J(H,H) ϭ 14.3 Hz, 2 H, CH2], 2.78 (s, 2 H, SO2CH2), 4.97 (s,
MHz, CDCl3, 20°C): δ ϭ 1.19 [t, J(H,H) ϭ 7.1 Hz, 3 H, CH3],
5 H, C5H5). Ϫ 13C NMR (100 MHz, CD2Cl2, 20°C): δ ϭ 19.1 (s,
CH3), 27.1 (s, CH3), 30.6 (s, CH3), 30.9 (s, CMe2), 52.4(s, CH2),
62.4 (s, Cquat), 78.2 (s, CH2SO2), 83.8 (s, C5H5), 209.0 (s, CO). Ϫ
31P NMR (162 MHz, CD2Cl2, 20°C): δ ϭ 13.5 (s). Ϫ IR (Nujol):
1.37 (s, 3 H, CH3), 1.98 [s, 3 H, C(O)CH3], 2.85 [d, 2J(H,H) ϭ 13.7
Hz, 1 H, SO2CH2], 2.94 [d, 2J(H,H) ϭ 13.7 Hz, 1 H, SO2CH2],
4.10 [q, 3J(H,H) ϭ 7.1 Hz, 2 H, OCH2], 4.94 (s, 5 H, C5H5). Ϫ 13C
NMR (100 MHz, CDCl3, 20°C): δ ϭ 14.0 (s, CH3), 19.3 (s, CH3),
26.3 (s, CH3), 58.8 (s, Cquat), 61.0 (s, OCH2), 74.2 (s, CH2SO2), 83.7
(s, C5H5), 172.2 (s, CO), 205.8 (s, CO). Ϫ 31P NMR (162 MHz,
ν˜
ϭ
1716, 1688 (CϭO), 1144, 1032 cmϪ1 (SϭO).
Ϫ
C40H42O4P2RuS (781.9): calcd. C 61.44, H 5.41; found C 60.96,
H 5.26.
2
CDCl3, 20°C): δ ϭ 12.6 [d, 2J(P,P) ϭ 90 Hz], 12.9 [d, J(P,P) ϭ 90
Hz]. Ϫ IR (Nujol): ν˜ ϭ 1728, 1708 (CϭO), 1148, 1036 cmϪ1 (Sϭ
O). Ϫ C38H40O5P2RuS (771.8): calcd. C 59.14, H 5.22; found C
58.90, H 5.08.
7a: Yield 125 mg (78%), m.p. 183°C (dec.). Ϫ 1H NMR (400
3
MHz, CDCl3, 20°C): δ ϭ 1.19 [t, J(H,H) ϭ 7.1 Hz, 6 H, CH3],
1.36 (s, 3 H, CH3), 2.86 (s, 2 H, SO2CH2), 4.10 (res. m, 4 H, OCH2),
4.93 (s, 5 H, C5H5). Ϫ 13C NMR (100 MHz, CDCl3, 20°C): δ ϭ
14.0 (s, CH3), 19.4 (s, CH3), 53.2 (s, Cquat), 61.0 (s, OCH2), 73.3 (s,
CH2SO2), 83.6 (s, C5H5), 171.5 (s, CO). Ϫ 31P NMR (162 MHz,
CDCl3, 20°C): δ ϭ 12.6 (s). Ϫ IR (Nujol): ν˜ ϭ 1740, 1712 (CϭO),
1152, 1028 cmϪ1 (SϭO). Ϫ C39H42O6P2RuS (801.8): calcd. C 58.42,
H 5.28; found C 57.96, H 5.59.
7b: Yield 129 mg (82%), m.p. 207°C (dec.). Ϫ 1H NMR (400
MHz, CD2Cl2, 20°C): δ ϭ 1.48 (s, 3 H, CH3), 1.56 (s, 3 H, CH3),
1.74 (s, 3 H, CH3), 2.94 (s, 2 H, SO2CH2), 4.95 (s, 5 H, C5H5). Ϫ
13C NMR (100 MHz, CDCl3, 20°C): δ ϭ 27.0 (s, CH3), 27.6 (s,
CH3), 30.2 (s, CH3), 43.4 (s, Cquat), 75.3 (s, CH2SO2), 83.6 (s,
C5H5), 106.5 (s, O2CMe2), 168.5 (s, CO). Ϫ 31P NMR (162 MHz,
CDCl3, 20°C): δ ϭ 13.1 (s). Ϫ IR (Nujol): ν˜ ϭ 1744, 1732 (CϭO),
1160, 1028 cmϪ1 (SϭO). Ϫ C38H38O6P2RuS (785.8): calcd. C 58.08,
H 4.87; found C 58.17, H 4.87.
8b: Yield 47 mg (31%), m.p. 211°C (dec.). Ϫ 1H NMR (400
3
MHz, CDCl3, 20°C): δ ϭ 1.28 [t, J(H,H) ϭ 7.1 Hz, 3 H, CH3],
1.37 (s, 3 H, CH3), 2.51 [d, 2J(H,H) ϭ 13.2 Hz, 1 H, SO2CH2],
2.75 [d, 2J(H,H) ϭ 13.2 Hz, 1 H, SO2CH2], 4.22 (res. m, 1 H,
OCH2), 4.23 (res. m, 1 H, OCH2), 4.95 (s, 5 H, C5H5). Ϫ 13C NMR
(100 MHz, CDCl3, 20°C): δ ϭ 13.9 (s, CH3), 22.2 (s, CH3), 40.6
(s, Cquat), 62.5 (s, OCH2), 73.0 (s, CH2SO2), 83.6 (s, C5H5), 119.7
(s, CN), 168.6 (s, CO). Ϫ 31P NMR (162 MHz, CDCl3, 20°C): δ ϭ
12.5 [d, 2J(P,P) ϭ 90 Hz], 13.0 [d, 2J(P,P) ϭ 90 Hz]. Ϫ IR (Nujol):
ν˜ ϭ 1744 (CϭO), 1168, 1032 cmϪ1 (SϭO). Ϫ C37H37NO4P2RuS
(754.8): calcd. C 58.88, H 4.94, N 1.86; found C 59.09, H 4.45,
N 1.23.
8c: Yield 127 mg (78%), m.p. 216°C (dec.). Ϫ 1H NMR (400
MHz, CDCl3, 20°C): δ ϭ 1.35 (s, 12 H, tBu and CH3), 2.04 [s, 3
2
H, C(O)CH3], 2.32 [d, J(H,H) ϭ 14.0 Hz, 1 H, SO2CH2], 2.87 [d,
7c: Yield 124 mg (76%), m.p. 209°C (dec.). Ϫ 1H NMR (400 2J(H,H) ϭ 14.0 Hz, 1 H, SO2CH2], 4.84 (s, 5 H, C5H5). Ϫ 13C
3
MHz, CDCl3, 20°C): δ ϭ 1.18 [t, J(H,H) ϭ 7.1 Hz, 6 H, CH3], NMR (100 MHz, CDCl3, 20°C): δ ϭ 19.5 (s, CH3), 26.9 (s, CH3),
Eur. J. Inorg. Chem. 1998, 605Ϫ611
609

W. A. Schenk, J. Bezler
FULL PAPER
2
27,7 (s, tBu), 59.1 (s, Cquat), 73.5 (s, CH2SO2), 80.7 (s, CMe3), 85.6 86 Hz], 5.8 [d, J(P,P) ϭ 86 Hz]. Ϫ IR (Nujol): ν˜ ϭ 1726 (CϭO)
(s, C5H5), 170.7 (s, CO), 206.1 (s, CO). Ϫ 31P NMR (162 MHz, cmϪ1. Ϫ C40H45BF4O6P2RuS (903.7): calcd. C 53.16, H 5.02; found
2
CDCl3, 20°C): δ ϭ 82.1 [d, 2J(P,P) ϭ 19 Hz], 84.2 [d, J(P,P) ϭ 19 C 52.69, H 5.35.
Hz]. Ϫ IR (Nujol): ν˜ ϭ 1725, 1702 (CϭO), 1140, 1022 cmϪ1 (Sϭ
10b: Yield 91 mg (93%), m.p. 135°C (dec.). Ϫ 1H NMR (400
O). Ϫ C41H46O5P2RuS (813.9): calcd. C 60.51, H 5.70; found C
60.39, H 5.92.
MHz, [D6]acetone, 20°C): δ ϭ 1.10 [t, 3J(H,H) ϭ 7.1 Hz, 3 H,
CH3], 1.16 [t, 3J(H,H) ϭ 7.1 Hz, 3 H, CH3], 1.21 [t, 3J(H,H) ϭ 7.1
3
9a: Yield 111 mg (71%), m.p. 190°C (dec.). Ϫ 1H NMR (400
Hz, 3 H, SOCH3], 1.22 (s, 3 H, CH3), 2.95 [dq, J(H,H) ϭ 7.1 Hz,
2
2J(H,H) ϭ 9.6 Hz, 1 H, OCH2], 3.07 [d, J(H,H) ϭ 15.1 Hz, 1 H,
3
MHz, CDCl3, 20°C): δ ϭ 1.12 [t, J(H,H) ϭ 7.1 Hz, 3 H, CH3],
SO2CH2], 3.62 [dq, 3J(H,H) ϭ 7.1 Hz, 2J(H,H) ϭ 9.6 Hz, 1 H,
2
1.56 (m, 2 H, CH2), 1.99 (m, 2 H, CH2), 2.22 [d, J(H,H) ϭ 13.6
2
Hz, 1 H, SO2CH2], 2.50 (m, 2 H, CH2), 2.95 [d, 2J(H,H) ϭ 13.6
Hz, 1 H, SO2CH2], 4.02 (res. m, 1 H, OCH2), 4.03 (res. m, 1 H,
OCH2), 4.87 (s, 5 H, C5H5). Ϫ 13C NMR (100 MHz, CDCl3,
20°C): δ ϭ 14.1 (s, CH3), 19.4 (s, CH2), 30.4 (s, CH2), 37.4 (s, CH2),
59.6 (s, Cquat), 61.1 (s, OCH2), 71.1 (s, CH2SO2), 83.8 (s, C5H5),
170.1 (s, CO), 214.6 (s, CO). Ϫ 31P NMR (162 MHz, CDCl3,
OCH2], 3.88 [d, J(H,H) ϭ 15.1 Hz, 1 H, SO2CH2], 4.10 (res. m, 4
H, OCH2), 5.55 (s, 5 H, C5H5). Ϫ 13C NMR (100 MHz, [D6]ace-
tone, 20°C): δ ϭ 13.9 (s, CH3), 14.0 (s, CH3), 14.1 (s, CH3), 19.2
(s, CH3), 54.1 (s, Cquat), 61.9 (s, OCH2), 62.4 (s, OCH2), 63.1 (s,
OCH2), 73.6 (s, CH2SO2), 85.6 (s, C5H5), 169.7 (s, CO), 170.0 (s,
CO). Ϫ 31P NMR (162 MHz, [D6]acetone, 20°C): δ ϭ 2.6 [d,
2J(P,P) ϭ 85 Hz], 5.5 [d, 2J(P,P) ϭ 85 Hz]. Ϫ IR (Nujol): ν˜ ϭ 1733
(CϭO), 1150 (SϭO) cmϪ1. Ϫ C41H47F6O6P3RuS (975.9): calcd. C
50.46, H 4.85; found C 50.82, H 4.99.
2
2
20°C): δ ϭ 12.4 [d, J(P,P) ϭ 90 Hz], 13.1 [d, J(P,P) ϭ 90 Hz]. Ϫ
IR (Nujol): ν ϭ 1745, 1716 (CϭO), 1149, 1022 cmϪ1 (SϭO). Ϫ
˜
C39H40O5P2RuS (783.8): calcd. C 59.76, H 5.14; found C 58.47,
H 5.02.
10c: Yield 90 mg (91%), m.p. 118°C (dec.). Ϫ 1H NMR (400
MHz, [D6]acetone, 20°C) (assignment to the two different dia-
9b: Yield 123 mg (77%), m.p. 172°C (dec.). Ϫ 1H NMR (400
3
3
stereomers was not possible): δ ϭ 0.75 [t, J(H,H) ϭ 7.0 Hz, 3 H,
MHz, CDCl3, 20°C): δ ϭ 1.14 [t, J(H,H) ϭ 7.0 Hz, 3 H, CH3],
2
CH3], 1.20 (s, 3 H, CH3), 1.40 (s, 9 H, tBu), 1.93, 2.04 [s, 3 H,
C(O)CH3], 2.71, 2.86, 3.30, 3.32 [d, 2J(H,H) ϭ 15.2 Hz, 2 H,
SO2CH2], 2.95 (m, 2 H, SOCH2), 5.41, 5.42 (s, 5 H, C5H5). Ϫ 13C
NMR (100 MHz, [D6]acetone, 20°C): δ ϭ 13.8, 14.6 (s, CH3), 18.9,
19.4 (s, CH3), 25.6, 26.2 (s, CH3), 27.6, 27.7 (s, tBu), 60.6, 60.7 (s,
Cquat), 62.4, 62.6 (s, SOCH2), 73.9, 74.2 (s, CH2SO2), 83.0, 83.1 (s,
CMe3), 87.4, 87.5 (s, C5H5), 169.6, 169.7 (s, CO), 202.3, 202.7 (s,
CO). Ϫ 31P NMR (162 MHz, [D6]acetone, 20°C), major (51%)
1.28Ϫ1.54 (m, 4 H, CH2), 2.05 (m, 4 H, CH2), 2.79 [d, J(H,H) ϭ
13.0 Hz, 1 H, SO2CH2], 2.90 [d, 2J(H,H) ϭ 13.0 Hz, 1 H, SO2CH2],
4.06 [q, 3J(H,H) ϭ 7.0 Hz, 2 H, OCH2], 4.88 (s, 5 H, C5H5). Ϫ 13C
NMR (100 MHz, CDCl3, 20°C): δ ϭ 14.1 (s, CH3), 21.2 (s, CH2),
26.4 (s, CH2), 32.4 (s, CH2), 39.6 (s, CH2), 60.9 (s, Cquat), 60.9 (s,
OCH2), 72.0 (s, CH2SO2), 83.7 (s, C5H5), 171.1 (s, CO), 207.7 (s,
CO). Ϫ 31P NMR (162 MHz, CDCl3, 20°C): δ ϭ 12.6 [d, 2J(P,P) ϭ
2
90 Hz], 12.8 [d, J(P,P) ϭ 90 Hz]. Ϫ IR (Nujol): ν ϭ 1731, 1701
˜
2
2
(CϭO), 1153, 1028 cmϪ1 (SϭO). Ϫ C40H42O5P2RuS (797.9): calcd.
diastereomer: δ ϭ 69.2 [d, J(P,P) ϭ 21 Hz], 73.3 [d, J(P,P) ϭ 21
Hz], minor (49%) diastereomer: δ ϭ 66.2 [d, 2J(P,P) ϭ 21 Hz], 72.8
C 60.22, H 5.31; found C 59.92, H 5.37.
[d, J(P,P) ϭ 21 Hz]. Ϫ IR (Nujol): ν˜ ϭ 1716 (CϭO), 1150 cmϪ1
2
9c: Yield 113 mg (71%), m.p. 191°C (dec.). Ϫ 1H NMR (400
(SϭO). Ϫ C43H51F6O5P3RuS (987.9): calcd. C 52.28, H 5.20, S
3.25; found C 51.99, H 5.33, S 3.15.
3
MHz, CDCl3, 20°C): δ ϭ 0.79 [t, J(H,H) ϭ 6.3 Hz, 3 H, CH3],
3
1.26 [t, J(H,H) ϭ 7.1 Hz, 3 H, CH3], 1.66Ϫ1.91 (m, 2 H, CH2),
Liberation of the Sulfinic Acid Esters: The respective ester com-
plexes 10a, b (0.2 mmol) were dissolved in acetonitrile (10 ml) and
heated under reflux (15 h). Thereafter, the mixtures were concen-
trated to dryness and the resulting residues were suspended in di-
ethyl ether. The acetonitrile complexes 11a, b separated as yellow
powders upon ultrasound treatment. In each case, the supernatant
was concentrated to dryness, leaving the esters 12a, b as colorless,
spectroscopically pure oils in almost quantitative yields.
2.08 (m, 1 H, CH2), 2.43 (m, 1 H, CH2), 2.52 (m, 2 H, CH2), 3.72
[q, 3J(H,H) ϭ 6.3 Hz, 1 H, SO2CH], 4.15 (res. m, 1 H, OCH2),
4.16 (res. m, 1 H, OCH2), 5.07 (s, 5 H, C5H5). Ϫ 13C NMR (100
MHz, CDCl3, 20°C): δ ϭ 13.7 (s, CH3), 14.6 (s, CH3), 19.1 (s,
CH2), 29.3 (s, CH2), 32.1 (s, CH2), 59.3 (s, OCH2), 82.4 (s, C5H5),
98.6 (s, CHSO2), 165.3 (s, CO), signals of Cquat and CO (ketone)
not detected due to low intensity. Ϫ 31P NMR (162 MHz, CDCl3,
20°C): δ ϭ 11.9 [d, J(P,P) ϭ 88 Hz], 10.0 [d, J(P,P) ϭ 88 Hz]. Ϫ
IR (Nujol): ν˜ ϭ 1672, 1613 (CϭO), 1153, 1028 cmϪ1 (SϭO). Ϫ
C40H42O5P2RuS (797.9): calcd. C 60.22, H 5.31; found C 59.99,
H 5.12.
2
2
12a: 1H NMR (400 MHz, CDCl3, 20°C): δ ϭ 1.24 [t, 3J(H,H) ϭ
7.1 Hz, 6 H, CH3], 1.58 (s, 3 H, CH3), 3.16 [d, 2J(H,H) ϭ 13.6 Hz,
2
1 H, SO2CH2], 3.34 [d, J(H,H) ϭ 13.6 Hz, 1 H, SO2CH2], 3.72 (s,
3 H, SOCH3), 4.19 [q, 3J(H,H) ϭ 7.1 Hz, 4 H, OCH2]. Ϫ 13C
NMR (100 MHz, CDCl3, 20°C): δ ϭ 13.9 (s, CH3), 20.5 (s, CH3),
51.4 (s, Cquat), 62.0 (s, OCH2), 62.1 (s, OCH2), 63.0 (s, CH2SO2),
170.1 (s, CO).
O-Alkylation of the Sulfinato Complexes: To a solution of the
sulfinato complex (0.1 mmol) in dichloromethane (10 ml), a solu-
tion of the oxonium salt in the same solvent was added at Ϫ70°C.
After being allowed to warm to 20°C, the mixture was concen-
trated to a volume of 1 ml and the product was precipitated by the
addition of pentane. In some instances, 10a separated as an oil. In
this event, it was found that crystallization could be induced by
ultrasound treatment under pentane.
12b: 1H NMR (400 MHz, CDCl3, 20°C): δ ϭ 1.25 [t, 3J(H,H) ϭ
3
7.1 Hz, 6 H, CH3], 1.32 [t, J(H,H) ϭ 7.1 Hz, 3 H, CH3], 1.58 (s,
3 H, CH3), 3.19 [d, 2J(H,H) ϭ 13.6 Hz, 1 H, SO2CH2], 3.36 [d,
2J(H,H) ϭ 13.6 Hz, 1 H, SO2CH2], 4.06 (res. m, 2 H, SOCH2),
4.19 (res. m, 2 H, OCH2), 4.20 (res. m, 2 H, OCH2). Ϫ 13C NMR
(100 MHz, CDCl3, 20°C): δ ϭ 13.9 (s, CH3), 15.8 (s, CH3), 20.4
(s, CH3), 51.5 (s, Cquat), 62.0 (s, OCH2), 62.1 (s, OCH2), 63.2 (s,
SOCH2), 65.0 (s, CH2SO2), 170.1 (s, CO), 170.2 (s, CO).
10a: Yield 85 mg (94%), m.p. 88°C (dec.). Ϫ 1H NMR (400
3
MHz, CD2Cl2, 20°C): δ ϭ 1.10 (s, 3 H, CH3), 1.20 [t, J(H,H) ϭ
2
7.2 Hz, 6 H, CH3], 2.82 (s, 3 H, SOCH3), 3.07 [d, J(H,H) ϭ 15.0
Hz, 1 H, SO2CH2], 3.63 [d, 2J(H,H) ϭ 15.0 Hz, 1 H, SO2CH2],
4.15 (res. m, 4 H, OCH2), 5.31 (s, 5 H, C5H5). Ϫ 13C NMR (100
Acetonitrile/SO2 Exchange: In a small pressure tube, equipped
MHz, CD2Cl2, 20°C): δ ϭ 14.1 (s, CH3), 14.2 (s, CH3), 19.3 (s, with a Teflon needle valve, liquid sulfur dioxide (5 ml) was con-
CH3), 52.0 (s, SOCH3), 55.7 (s, Cquat), 62.2 (s, OCH2), 62.6 (s, densed onto the acetonitrile complex 11a, b (0.1 mmol). After 7 d
OCH2), 74.4 (s, CH2SO2), 84.6 (s, C5H5), 169.7 (s, CO), 169.9 (s,
at 20°C, the tube was vented and the yellow residue was recrys-
CO). Ϫ 31P NMR (162 MHz, CD2Cl2, 20°C): δ ϭ 2.6 [d, 2J(P,P) ϭ tallized from dichloromethane/pentane.
610
Eur. J. Inorg. Chem. 1998, 605Ϫ611

Sulfur(IV) Compounds as Ligands, 23
FULL PAPER
[13]
[14]
[15]
[16]
[17]
[18]
G. Binsch, H. Kessler, Angew. Chem. 1980, 92, 445Ϫ463; An-
gew. Chem. Int. Ed. Engl. 1980, 19, 411.
1a: Yield 72 mg (95%), spectroscopically identical to authentic
material.[19]
M. L. H. Green, L. L. Wong, A. Sella, Organometallics 1992,
11, 2660Ϫ2668.
1e: Yield 67 mg (96%) m.p. 158°C. Ϫ 31P NMR (162 MHz,
[D6]acetone, 20°C): δ ϭ Ϫ3.2 (s). Ϫ IR (Nujol): ν˜ ϭ 1279, 1115
(SϭO) cmϪ1. Ϫ C30H27BF4O2P2RuS (701.4): calcd. C 51.37, H
3.88, S 4.57; found C 50.94, H 3.88, S 4.50.
E. Dombrowski, W. A. Schenk, Angew. Chem. 1995, 107,
1098Ϫ1099; Angew. Chem. Int. Ed. Engl. 1995, 34, 1008Ϫ1009.
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gew. Chem. Int. Ed. Engl. 1971, 10, 315.
C. A. Poffenberger, A. Wojcicki, Inorg. Chem. 1980, 19,
3795Ϫ3803.
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