Organometallic macrocyclic chemistry. 6. Chelate-assisted macrocyclization of 4,7,10-trithiatrideca-2,11-diyne

Article abstract of DOI:10.1021/om0305723

The diyne 4,7,10-trithiatrideca-2,11-diyne (TTDD) reacts smoothly at room temperature with [Ru(CO)₂(PPh₃)₃] to form [Ru(CO)(PPh₃) {η⁴-S(C₂H₄SCCMe)₂CO-κS}], a cyclopentadienone complex in which the unique sulfur atom is also coordinated to the metal but may be displaced by dppe to provide [Ru(CO)(dppe){η⁴-S(C₂H₄SCCMe)₂CO }]. In contrast, 2,8-decadiyne fails to cyclize even at elevated temperatures, implicating thioether coordination in the mechanism of TTDD macrocyclization.

Full text of DOI:10.1021/om0305723

Organometallics 2004, 23, 81-85
81
Or ga n om eta llic Ma cr ocyclic Ch em istr y. 6.1
Ch ela te-Assisted Ma cr ocycliza tion of
4,7,10-Tr ith ia tr id eca -2,11-d iyn e
Anthony F. Hill,* A. David Rae,† Madeleine Schultz, and Anthony C. Willis
Research School of Chemistry, Institute of Advanced Studies, Australian National University,
Canberra, Australian Capital Territory 0200, Australia
Received August 11, 2003
The diyne 4,7,10-trithiatrideca-2,11-diyne (TTDD) reacts smoothly at room temperature
with [Ru(CO)2(PPh3)3] to form [Ru(CO)(PPh3){η4-S(C2H4SCCMe)2CO-κS}], a cyclopentadi-
enone complex in which the unique sulfur atom is also coordinated to the metal but may be
displaced by dppe to provide [Ru(CO)(dppe){η4-S(C2H4SCCMe)2CO}]. In contrast, 2,8-
decadiyne fails to cyclize even at elevated temperatures, implicating thioether coordination
in the mechanism of TTDD macrocyclization.
In tr od u ction
ognized intermediates in the alkyne coupling reactions
mediated by [Ru(CO)3(PPh3)2] in refluxing toluene,
curiously under an atmosphere of CO2.9 Herein we
report the reaction of TTDD with [Ru(CO)2(PPh3)3],
which does indeed provide access to a novel polythia-
macrocycle via [2 + 2 + 1] macrocyclization of the R,ω-
diyne with coordinated CO.
A range of ruthenium complexes have been shown to
couple alkynes.2 The various products include examples
of ruthenacyclopentadienes,3 cyclobutadiene complexes,4
enynes in the case of terminal alkynes,5 and either free
arenes or their complexes.6 For substrates bearing
carbonyl ligands, the possibility of CO incorporation
arises, leading to cyclopentadienone or quinone for-
mation,7-9 including polymetallic examples.10 With this
plethora of possibilities in mind, we are investigating
the organometallic chemistry of 4,7,10-trithiatrideca-
2,11-diyne (TTDD) with ruthenium complexes, in the
hope that new routes to functionalized thioether mac-
rocycles might be developed.
The complex [Ru(CO)2(PPh3)3] has been shown to
react cleanly with diphenylacetylene or diphenylbuta-
diyne to provide the simple adducts [Ru(η2-PhCtCR)-
(CO)2(PPh3)2] (R ) Ph (1a ),11 CtCPh (1b)12). In these
reactions, which proceed under ambient conditions, no
further coordination or coupling of the alkynes ensues,
although complexes 1 appear plausible through unrec-
Resu lts a n d Discu ssion
Syn th esis. Addition of benzene or toluene to an
equimolar mixture of TTDD and [Ru(CO)2(PPh3)3] at
room temperature results in the precipitation of a
crystalline product. The complex is a bright yellow, air-
stable solid, poorly soluble in aliphatic and aromatic
solvents but with reasonable solubility in halogenated
solvents and ethanol. It is formulated as [Ru(CO)(PPh3)-
{η4-S(C2H4SCCMe)2CO-κS}] (2) on the basis of spectro-
scopic data and X-ray crystallography. The triclinic
crystal chosen for study was twinned, and the new
refinement procedures are described later in this paper.
An alternative and more expedient synthesis of 2 was
also developed via the reaction of [RuHCl(CO)2(PPh3)2]
with TTDD in the presence of DBU, avoiding the need
to isolate [Ru(CO)2(PPh3)3].13 The complex 2 is also
formed from the reaction of [Ru(CO)3(PPh3)2] with
TTDD, but only under forcing conditions (refluxing
toluene).
* To whom correspondence should be addressed. E-mail: a.hill@
rsc.anu.edu.au.
† To whom crystallographic enquiries should be addressed. E-mail:
david.rae@anu.edu.au.
(1) Part 5: Cannadine, J . C.; Hill, A. F.; White, A. J . P.; Williams,
D. J .; Wilton-Ely, J . D. E. T. Organometallics 1996, 15, 5409-5415.
(2) Bennett, M. A.; Khan, K.; Wenger, E. In Comprehensive Orga-
nometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G.,
Eds.; Pergamon: Oxford, U.K., 1995; Vol. 7.
(3) Albers, M. O.; De Waal, D. J . A.; Liles, D. C.; Robinson, D. J .;
Singleton, E.; Wiege, M. B. J . Chem. Soc., Chem. Commun. 1986,
1680-1682.
The molecular geometry of the chiral complex 2 is
depicted in Figure 1 and comprises a cyclopentadienone
coordinated to ruthenium(0), to which are also coordi-
nated one carbonyl ligand and one triphenylphosphine
ligand. The cyclopentadienone arises from the regiose-
lective [2 + 2 + 1] macrocyclization of the R,ω-diyne with
(4) Crocker, M.; Froom, S. F. T.; Green, M.; Nagle, K. R.; Orpen, A.
G.; Thomas, D. M. J . Chem. Soc., Dalton Trans. 1987, 2803-2814.
(5) Dobson, A.; Moore, D. S.; Robinson, S. D.; Hursthouse, M. B.;
New, L. Polyhedron 1985, 4, 1119-1130.
(6) Pertici, P.; Verrazzani, A.; Vitulli, G.; Baldwin, R.; Bennett, M.
A. J . Organomet. Chem. 1998, 551, 37-47.
(11) Cavit, B. E.; Grundy, K. R.; Roper, W. R. J . Chem. Soc., Chem.
Commun. 1972, 60-61.
(12) Alcock, N. W.; Hill, A. F.; Melling, R. P.; Thompsett, A. R.
Organometallics 1993, 12, 641-648.
(13) The dehydrochlorination of [RuHCl(CO)2(PPh3)2] by DBU in the
presence of CO or PPh3 provides [Ru(CO)2(PPh3)2(L)] (L ) CO, PPh3),
and that of [PtHCl(PPh3)2] in the presence of PhCtCPh provides [Pt-
(η-PhCtCPh)(PPh3)2]: Grundy, K. R. Inorg. Chim. Acta 1981, 53,
L225-L226.
(7) Bruce, M. I.; Knight, J . R. J . Organomet. Chem. 1968, 12, 411-
413.
(8) Washington, J .; McDonald, R.; Takats, J .; Menashe, N.; Reshef,
D.; Shvo, Y. Organometallics 1995, 14, 3996-4003.
(9) Yamazaki, H.; Taira, Z. J . Organomet. Chem. 1999, 578, 61-
67.
(10) Bruce, M. I.; Skelton, B. W.; White, A. H.; Zaitseva, N. N. J .
Organomet. Chem. 1998, 558, 197-207.
10.1021/om0305723 CCC: $27.50 © 2004 American Chemical Society
Publication on Web 12/02/2003

82 Organometallics, Vol. 23, No. 1, 2004
Hill et al.
Ta ble 1. Com p a r a tive Geom etr ic P a r a m eter s (Å)
for (P h C)4CO (3),17 [Ru 0{η4-(P h C)4CO}(CO)3] (4),18
[Ru II{η4-(HC)4CO}Br (η-C5H5)] (5),19 a n d 2a
3
4
5
2
a
b
c
d
e
f
1.211
1.502
1.350
1.521
1.224
1.488
1.447
1.437
2.228
2.213
1.22
1.49
1.42
1.46
2.263
2.167
1.250
1.462
1.427
1.459
2.282
2.191
a
The parameters b, c, e, and f are the average of two values.
ring significantly (4 vs 5). Consideration of these data
suggests that the inclusion of the cyclopentadienone of
2 within a chelated cyclic structure (involving two
π-dative thiolate substituents) does not lead to signifi-
cant changes in the geometry or indeed the orientation
(tilting) of the ring.
The 1H NMR spectrum of 2 (CD2Cl2) reflects the
chirality of the complex, with eight well-separated
multiplets being observed over the range δ 1.11-4.10,
corresponding to each of the eight chemically inequiva-
lent S(C2H2)2 proton environments (see the Supporting
Information for COSY (1H,1H) and HMQC (C-H cor-
relation) spectra). In the 13C{1H} NMR spectrum, the
metal carbonyl appears at δ 208.3 (br, cis-2J (PC) not
resolved), while the ketonic carbonyl is observed at δ
155.0. The two carbonyl environments are also reflected
in the infrared spectrum of 2, with νCO for the metal
carbonyl observed at 1929 cm-1 and the ketonic carbonyl
at 1561 cm-1 (CH2Cl2).
A mechanism for the formation of 2 is suggested in
Scheme 1. This involves initial loss of a phosphine
ligand, with coordination of one of the triple bonds of
TTDD, akin to the reactions of [Ru(CO)2(PPh3)3] with
PhCtCR (R ) Ph, CtCPh).11,12 Coupling of the coor-
dinated alkyne with carbon monoxide and dissociation
of either a phosphine or hemilabile thioether donor20-22
allows coordination of the second alkynyl group, and
insertion of this linkage into the vinylic bond of the
metallacycle with ultimate reductive elimination pro-
vides the cyclopentadienone. The specific order of events
remains conjecture; however, a similar process was
inferred from the reactions of [Os(CO)5] with alkynes.8
More definitive support comes from Roper’s observation
that [Os(CO)(CS)(PPh3)3] reacts with diphenylacetylene
or ethyne to provide an osmacyclobutenethione20 or an
osmacyclohexadienethione (“osmabenzene,” Scheme 2),
respectively.23
F igu r e 1. ORTEP diagram (50% probability ellipsoids) of
2 (hydrogen atoms and phenyl rings omitted). Selected
bond distances (Å) and angles (deg): Ru1-S2 ) 2.377(1),
Ru1-P1 ) 2.342(1), Ru1-C2 ) 2.239(6), Ru1-C3 ) 2.171-
(6), Ru1-C8 ) 2.210(6), Ru1-C9 ) 2.325(6), Ru1-C11 )
2.492(6), Ru1-C12 ) 1.854(7), C2-C3 ) 1.433(8), C2-C11
) 1.453(9), C3-C8 ) 1.459(8), C8-C9 ) 1.420(7), C9-C11
) 1.471(9), C11-O1 ) 1.250(7), C12-O2 ) 1.159(7); P1-
Ru1-S2 ) 91.5(1), P1-Ru1-C12 ) 88.5(2), S2-Ru1-C12
) 96.2(2).
carbon monoxide, such that a nine-membered trithia-
macrocycle is annulated to the cyclopentadienone. Mono-
nuclear ruthenium(0) thioether complexes have yet to
be structurally characterized; however, polynuclear
ruthenium(0) carbonyl adducts of cyclic thioethers typi-
cally display Ru-S separations of 2.306-2.409 Å.14-16
Thus, the bond between ruthenium and the unique
sulfur of the macrocycle (Ru1-S2 at 2.377(1) Å) appears
unremarkable, as do the bond lengths between ruthe-
nium and the carbonyl and phosphine ligands. The
geometric parameters of interest are associated with the
η4-cyclopentadienone ligand. However, to date there do
not appear to exist any structural data for either free
or complexed chalcogen-substituted cyclopentadienones.
A wealth of data exists for nonfunctionalized cyclopen-
tadienone complexes of both ruthenium(0) and ruthe-
nium(II). From these, the general pattern emerges that
η4 coordination results in a loss of the localized single
and double bonding apparent in free cyclopentadi-
enones, while the geometric parameters associated with
the (noncoordinated) ketone remain essentially un-
changed. This is illustrated in Table 1 with reference
to the crystal structures of (PhC)4CO (3),17 [Ru0{η4-
(PhC)4CO}(CO)3] (4),18 [RuII{η4-(HC)4CO}Br(η-C5H5)]
(5),19 and 2. The oxidation state of the ruthenium
appears not to affect geometric parameters within the
To investigate the assertion that thioether coordina-
tion plays a role, 2,8-decadiyne was treated with [Ru-
(14) Adams, R. D.; Falloon, S. B.; McBride, K. T. Organometallics
1994, 13, 4870-4874.
(15) Adams, R. D.; Falloon, S. B.; McBride, K. T.; Yamamoto, J . H.
Organometallics 1995, 14, 1729-1747.
(20) The labilization of coligands by alkynes bound to zerovalent
group 8 metal complexes may be traced to the ability of alkynes to
serve as four-electron donors:21,22 Elliot, G. P.; Roper, W. R. J .
Organomet. Chem. 1983, 250, C5-C8.
(21) Espuelas, J .; Esteruelas, F. J . L.; Lo´pez, A. M.; Oro, L. A.;
Valero, C. J . Organomet. Chem. 1994, 468, 223-228.
(22) Ogasawara, M.; Maseras, F.; Gallego-Planas, N.; Kawamura,
K.; Ito, K.; Toyota, K.; Streib, W. E.; Komiya, S.; Eisenstein, O.;
Caulton, K. G. Organometallics 1997, 16, 1979-1993.
(23) Elliot, G. P.; Roper, W. R.; Waters, J . M. J . Chem. Soc., Chem.
Commun. 1982, 811-813.
(16) Adams, R. D.; Yamamoto, J . H. Organometallics 1995, 14,
3704-3711.
(17) Alvarez-Toledano, C.; Baldovino, O.; Espinoza, G.; Toscano, R.
A.; Gutie´rrez-Pe´rez, R.; Garc´ıa-Mellado, O. J . Organomet. Chem. 1997,
540, 41-49.
(18) Blum, Y.; Shvo, Y.; Chodosh, D. F. Inorg. Chim. Acta 1985, 97,
L25-L26.
(19) Smith, T. P.; Kwan, K. S.; Taube, H.; Bino, A.; Cohen, S. Inorg.
Chem. 1984, 23, 1943-1945.

Organometallics Macrocyclic Chemistry
Organometallics, Vol. 23, No. 1, 2004 83
Sch em e 1. Syn th esis a n d Su ggested Mech a n ism
the starting ethylene complex. Heating the mixture led
to the disappearance of this resonance and the produc-
tion of a variety of products, including [Ru(CO)2(PPh3)3],
[Ru(CO)3(PPh3)2], and PPh3 as well as unreacted start-
ing material and several uncharacterized products.
Similar results were obtained when the reaction was
carried out in the presence of tetrahydrothiophene.
Thus, the inclusion of intramolecular thioether donors
clearly plays a crucial role in the macrocyclization
leading to 2.
for th e F or m a tion of 2 (L ) P P h 3)
Thioether coordination to ruthenium(0) might be
expected to be weak. Accordingly, 2 was treated with
1,2-bis(diphenylphosphino)ethane (dppe) in refluxing
toluene. This led to gradual dissolution of 2 concomitant
with the formation of [Ru{η4-S(C2H4SCCMe)2CO}(CO)-
(dppe)] (6) as a pale yellow solid (Scheme 1). The
comparative simplicity and chemical shift range of the
1
S(C2H4)2 component of the H NMR spectrum relative
to 2 suggests that the unique sulfur atom is no longer
coordinated to the ruthenium center. Thus, the pendant
macrocycle and the bidentate dppe ligand straddle a
molecular plane of symmetry, a premise further sup-
ported by the appearance of a single resonance (δ 60.5)
in the 31P{1H} NMR spectrum of 6 and a single methyl
1
resonance in both the H and 13C{1H} NMR spectra (δ
1.62 and 9.2, respectively). Notably, the formation of
[Ru(CO)(dppe)2]24 was not observed in this reaction,
indicating that the cyclopentadienone coordination was
not labile.
The reactions of 2 with a variety of other small
molecules were investigated. At room temperature in
CH2Cl2, 2 does not react with NEt3, TTDD, or CO; it
also does not react with CNC6H3Me2-2,6 in refluxing
toluene or with MeLi in diethyl ether at room temper-
ature. With bromine or AgPF6, reactions occur at room
temperature (CH2Cl2), providing, however, thus far
intractable mixtures. Unfortunately, for the present
system the prospect of including this [2 + 2 + 1]
macrocyclization within a catalytic synthesis is unten-
able due to (i) the rapid and irreversible reaction of
[Ru(CO)2(PPh3)3] with CO to provide substitution-inert
[Ru(CO)3(PPh3)2] and (ii) the failure of the product 2 to
react with CO or TTDD to liberate the desired macro-
cycle. However, these are factors peculiar to this par-
ticular zerovalent ruthenium system and it may be
hoped that the key steps demonstrated here may be
extendable to other, more potentially labile, metal
centers.
Sch em e 2. Mod el Com p ou n d s Releva n t to
Cyclop en ta d ien on e F or m a tion (L ) P P h 3)20,23
Cr ysta l Str u ctu r e Solu tion . The constrained least-
squares refinement program RAELS2000 was used for
refinement.25 As detailed elsewhere,26 this program
2
allows twin parameters ai in the model Y(h i) ) ∑iai|F(h i)|
to be modified to become aipj, where pj is a refinable
parameter and j is an integer included on the reflection
file (pj ) 1.0 if j ) 0). In an undistorted reciprocal space,
the spacing between twin-related spots is in the direc-
tion of c*. Procedures for the optimization of data
collection select a strategy that tends to have c* roughly
parallel to the plane of the CCD plate. This had the
(η-C2H4)(CO)2(PPh3)2].11 This complex serves as an
alternative synthetic equivalent of “Ru(CO)2(PPh3)2” but
offers two advantages. First, it is more soluble (for in
situ spectroscopic monitoring), but more importantly,
the reactions of [Ru(CO)2(PPh3)3] with simple aliphatic
alkynes do not proceed to completion, due to competition
between the alkyne and liberated PPh3. Under condi-
tions analogous to those used for the synthesis of 2,
addition of 2 equiv of 2,8-decadiyne to a C6D6 solution
of [Ru(η-C2H4)(CO)2(PPh3)2] led to a new resonance in
the 31P{1H} NMR spectrum at δ 48.2, corresponding to
the simple alkyne adduct, observed in a 1:2 ratio with
(24) Roper, W. R.; Wright, L. J . J . Organomet. Chem. 1982, 234,
C5-C8.
(25) Rae, A. D. RAELS2000; Australian National University, Can-
berra, Australia, 2000.
(26) Rae, A. D.; Edwards, A. J . Proceedings, 20th European Crystal-
lography Conference: Cracow, Poland, 2001; p 147.

84 Organometallics, Vol. 23, No. 1, 2004
Hill et al.
fortuitous consequence that, in the data collection, the
separation of reflections overlapped because of twinning
was reasonably constant for any particular separation
along c*. The twin plane is an n glide perpendicular to
parameter TLX model27 was used for the group of atoms
(C1-C3, C8-C11, O1). All other non-hydrogen atoms
were refined as individual anisotropic atoms. Hydrogen
atoms were reincluded after each refinement cycle in
sensible calculated positions and given atomic displace-
ment parameters determined by the atoms to which
they are attached. The methyl hydrogens were included
in two orientations of half-occupancy.
1
c* at z ) /2.
For a reflection H ) ha * + kb* + lc* of the first twin
component, the corresponding reflection for the second
twin component is located at H′ ) ha ′* + kb′* + lc′*,
where a ′* ) a * - 2|a*/c*|(cos â*)c* and b ′* ) b* -
2|b*/c*|(cos R*)c*. Note that a ′*‚c′* ) a *‚c*, b′*‚c′* )
b*‚c*, and c′* ) -c*. The nearest twin component for
the first component is then H′′ ) ha * + kb* + l′′c*,
where H′′ is the nearest reflection to H′ ) ha * + kb* -
(l + 2h|a*/c*|(cos â*) + 2k|b*/c*|(cos R*))c*; i.e., l′′ is the
integer nearest to -(l - 0.3965h - 0.4993k) and the
separation in reciprocal space is (l′′ + l - 0.3965h -
0.4993k)c*. When the mirror is repeated, the h,k,l"
reflection of the second component is the reflection
nearest to the h,k,l reflection of the first component with
the same separation in reciprocal space. For convenience
we will say l′′ is -(l - 0.3965h - 0.5k), allowing values
for the separation in reciprocal space of reflections from
different twin components to be simply a function of h
and whether k is odd or even. To a first approximation,
assuming 0.3965 is exactly 2/5, almost total overlap
exists for h ) 5n when k is even, partial overlap exists
for h ) 5n ( 1 when k is odd, and even less partial
overlap exists for h ) 5n ( 2 when k is even; i.e., these
are the instances when |l′′ + l - 0.3965h - 0.5k| < 0.25.
We thus set j ) 0 for the first twin component and pj )
|h| for the second component, which only exists for the
appropriate parity of k.
Con clu d in g Rem a r k s
The macrocyclization of TTDD by [Ru(CO)2(PPh3)3]
is remarkable for the facility with which it proceeds
under ambient conditions. This we attribute, in part,
to the labilization of coligands by alkynes coordinated
to 16-electron metal centers (2- vs 4-electron alkyne
coordination).20 However, the failure of [Ru(CO)2(PPh3)3]
to cyclize 2,8-decadiyne indicates that thioether coor-
dination also plays a crucial role. While the synthesis
of 2 is illustrative of a potential route to functionalized
macrocyclic thioethers, the tenacity with which buta-
diene linkages bind to d8-M0L3 fragments suggests that
processes catalytic in metal will require extension of the
principle to other metal centers.
Exp er im en ta l Section
Syn th esis of [Ru (CO)(P P h 3)({η4-S(C2H4SCCMe)2CO-K-
S)] (2). A mixture of [Ru(CO)2(PPh3)3]11 (2.00 g, 2.12 mmol)
and 4,7,10-trithiatrideca-2,11-diyne (TTDD; 0.49 g, 2.12 mmol)
was stirred in dry toluene under nitrogen at room temperature
overnight. The pale yellow supernatant was decanted, and the
yellow product was dried in vacuo. Yield: 1.00 g (75%). Mp:
226-228 °C. Anal. Calcd for C30H29O2PRuS3: C, 55.45; H, 4.50;
P, 4.77; S, 14.80. Found: C, 55.72; H, 4.23; P, 4.80; S, 14.71.
1H NMR (CD2Cl2, 298 K, 300 MHz): δ 7.25 (m, 15 H, C6H5),
4.10 (ddd, 1 H, J HH ) 13.7, 13.5, 2.5 Hz, on C δ 28.6), 3.14
(ddd, 1 H, J HH ) 14.8, 3.0, 3.0 Hz, on C δ 40.3), 2.81 (ddd, 1 H,
J HH ) 15, 4.4, 2.8 Hz, on C δ 28.6), 2.68 (ddd, 1 H, J HH ) 13.3,
2.8, 2.7 Hz, on C δ 27.3), 2.30 (ddd, 1 H, J HH ) 14.8, 4.4, 2.4
Hz, on C δ 20.7), 2.12 (ddd, 1 H, coupling not resolved, on C δ
40.3), 2.01 (d, 3 H, J HP ) 1.4 Hz, CH3 on C δ 9.9, pseudo-trans
to CO), 2.00 (ddd, 1 H, coupling not resolved, on C δ 27.3),
1.13 (ddd, 1 H, J HH ) 14.9, 12.1, 2.9 Hz, on C δ 20.7), 0.96 (d,
3 H, J HP ) 4.1 Hz, CH3 on C δ8.8, pseudo-trans to PPh3).
The procedure used works well and is assisted by the
following. (i) When the overlapping reflection is much
more intense than the reference reflection, the back-
ground error increases, increasing the standard error
of the resulting intensity and thus reducing the weight-
ing for such reflections in the refinement. Refinement
only includes those reflections with I > 3σ(I), and some
of the most troublesome reflections get excluded from
refinement. Reflections for which Icalcd < 2.5σ(I) were
also excluded from the refinement. (ii) It was found that
excluding reflections with (sin θ)/λ < 0.2 was beneficial.
The limited number of reflections in this range are
better resolved than higher angle reflections. Their
exclusion highlights this and allows the pj values to
decrease as a function of |l′′ + l - 0.3965h - 0.5k| in a
sensible fashion. The values for p1 to p12 were found to
be 0.775(15), 0.210(13), 0.298(14), 0.836(15), 0.947(15),
0.655(15), 0.152(19), 0.409(20), 0.822(25), 0.909(30),
0.469(47), and 0.066(85) with values for |l′′ + l -
0.3965h - 0.5k| of 0.1035, 0.2070, 0.1895, 0.0860,
0.0175, 0.1210, 0.2245, 0.1720, 0.0685, 0.0350, 0.1385,
and 0.2420.
13C{1H} NMR (CD2Cl2, 298 K, 75 MHz): δ 208.3 (br, RuCO),
1
155.0 (CCO), 134.6 (d, J CP ) 45, C1(C6H5)), 133.9 (d, J CP
)
)
12, C2,3,5,6(C6H5)), 130.5 (d, 4J CP ) 2, C4(C6H5)), 128.7 (d, J CP
10 Hz, C2,3,5,6(C6H5)), 97.8, 89.7, 80.8, 80.2 (CdC × 4), 40.3
(CH2, R to C δ 27.3), 28.6 (CH2, R to C δ 20.7), 27.3 (CH2, R to
C δ 40.3), 20.7 (CH2, R to C δ 28.6), 9.9 (CH3, pseudo-trans to
CO), 8.8 (CH3, pseudo-trans to P). 31P{1H} NMR (CD2Cl2, 298
K, 121 MHz): δ 48.5 (s). IR (Nujol): 1918 (νRuCO), 1587, 1576,
1565 (νCO) cm-1. IR (CH2Cl2): 1929 (νRuCO), 1561 (νCO) cm-1
.
MS (FAB, positive ion, nba matrix): m/z 651 [M + H]+, 623
[M - CO + H]+ (isotopic distributions confirmed by simula-
tion). Crystal data: C30H29O2PRuS3, Mr ) 649.78, triclinic, P1h
(No. 2), a ) 9.4529(2) Å, b ) 11.2806(3) Å, c ) 13.1159(3) Å,
R ) 77.595(1)°, â ) 81.762(1)°, γ ) 89.895(1)°, V ) 1351.25(6)
Å3, Z ) 2, Fcalcd ) 1.597 g cm-3, T ) 200 K, yellow plate, 6144
independent measured reflections, R1 ) 0.052, wR2 ) 0.063,
4147 absorption-corrected reflections (I > 3σ(I), 2θ e 55°), 185
parameters.
Syn th esis of [Ru (CO)(d p p e){η4-S(C2H4SCCMe)2CO}]
(6). A solution of 2 (0.13 g, 0.20 mmol) and dppe (0.076 g, 0.2
mmol) in toluene (30 mL) was heated under reflux for 2 h.
The resulting pale yellow solution was cooled, filtered, and
The anisotropic refinement used a number of con-
straints. The three phenyl rings were constrained to
have a common refinable planar geometry of mm2
symmetry relative to the P atom to which they are
attached. All other non-hydrogen atom positional pa-
rameters were unconstrained. The atomic displacement
parameters for the triphenylphosphine was modeled
using TL rigid body models, with the T common to all
atoms (6 parameters) and the librations (6 parameters
per phenyl group) centered on the P atom. A 15-
(27) Rae, A. D. Acta Crystallogr., Sect. A 1975, A31, 570-574.

Organometallics Macrocyclic Chemistry
Organometallics, Vol. 23, No. 1, 2004 85
then freed of volatiles. The pale yellow product was washed
with hexane and diethyl ether to remove PPh3 and unreacted
dppe. Yield: 0.092 g, 60%. Mp: 132-134 °C dec. 1H NMR (298
K, 300 MHz, C6D6): δ 7.81, 7.30-7.0 (m × 2, 20 H, C6H5), 2.7-
2.3 (m, 8 H, SCH2), 2.2-2.0 (m, 4 H, PCH2), 1.62 (d, 6 H,
3J HP ) 2 Hz, CH3). 1H NMR (298 K, 300 MHz, CD2Cl2): δ 7.7-
7.1 (m, 20 H, C6H5), 3.1-2.6 (m, 8 H, SCH2), 2.6-2.4 (m, 4 H,
PCH2), 1.24 (s, 6 H, CH3). 13C{1H} NMR (C6D6, 298 K, 75
IR (Nujol): 1936 (νRuCO), 1568 (νCCO) cm-1. IR (CH2Cl2): 1933
(νRuCO), 1565 (νCCO) cm-1. MS (APCI, positive ion, MeCN): m/z
824.8 [M + Na + O]+, 786.8 [M]+. Satisfactory elemental
analytical data were not obtained, due to difficulties encoun-
tered in separating the product from dppe and PPh3 (1H and
31P{1H} NMR spectra are provided in the Supporting Informa-
tion).
1
MHz): δ 203.5 (br, RuCO), 171.6 (CCO), 135.8 (d, J CP ) 41
Su p p or tin g In for m a tion Ava ila ble: Tables giving crys-
tallographic details for 2 and figures giving COSY (H-H) and
HMQC (C-H correlation) spectra of 2 in CD2Cl2 and 1H and
31P{1H} NMR spectra for 6. This material is available free of
charge via the Internet at http://pubs.acs.org.
1
Hz, C1(C6H5)), 135.3 (d, J CP ) 38 Hz, C1(C6H5)), 133.3 (d,
J CP ) 12 Hz, C2,3,5,6(C6H5)), 133.0 (d, J CP ) 11 Hz, C2,3,5,6(C6H5)),
130.1 (s × 2, C4(C6H5)), remaining C6H5 resonances obscured
by C6D6, 95.3, 82.6 (CdC × 2), 35.9, 32.6 (SCH2), 30.0 (m,
PCH2), 9.2 (CH3). 31P{1H} NMR (298 K, 121 MHz, C6D6): δ
60.5 (s). 31P{1H} NMR (298 K, 121 MHz, CD2Cl2): δ 63.0 (s).
OM0305723