Preparation and reactivity of organometallic complexes bearing the fragment Cp*Ru(CO)(PR3) (PR3 = PMeiPr2, PEt3): (see abstract)

Article abstract of DOI:10.1021/om034186x

The reactions of [Cp*RuCl(CO)(PMeⁱPr₂)] (1) and [Cp*RuCl(CO)(PEt₃)] (2) with NaBAr′₄ in fluorobenzene both under argon and under dinitrogen generate the binuclear compounds [{Cp*Ru(CO)(PMeⁱPr₂)}₂(μ-Cl)] [BAr′₄] (3) and [{Cp*Ru(CO)(PEt₃)}₂(μ-CL)] [BAr′₄] (4), respectively, which were fully characterized. The crystal structure of compound 4 is reported, showing for the first time two chiral Cp*Ru fragments bonded through only one bridging chloride ligand. No dinitrogen complexes or 16-electron species could be isolated. Halide abstraction from 1 using dry acetone as solvent yields the compound [Cp*Ru(CO){η¹-OC-(CH₃)₂} (PMeⁱPr₂)][BAr′₄] (5). A range of olefins react with [Cp*RuCl(CO)(PMeⁱPr₂)] and NaBAr′₄ furnishing the corresponding cationic η²-alkene complexes [Cp*Ru(CO)(L)(PMeⁱ-Pr₂)][BAr′₄] (L = C₂H₄, 6; H₂C=CHPh, 7; and H₂C=CHCOOCH₃, 8), which are stable under argon atmosphere in solution. The crystal structure of compound 6 is also reported. Both 1 and 2 react with SnCl₂ in CH₂Cl₂ to yield the insertion derivatives [Cp*Ru(CO)(SnCl₃)-(PR₃)] (PR₃ = PMeⁱPr₂, 9; PEt₃, 10), which have also been characterized.

Full text of DOI:10.1021/om034186x

504
Organometallics 2004, 23, 504-510
P r ep a r a tion a n d Rea ctivity of Or ga n om eta llic
Com p lexes Bea r in g th e F r a gm en t “Cp *Ru (CO)(P R3)”
(P R3 ) P MeiP r 2, P Et3): Din u clea r Com p lexes
[{Cp *Ru (CO)(P R3)}2(µ-Cl)]+ Con ta in in g Tw o Ch ir a l
Cen ter s, η2-Alk en e, a n d Oth er Mon on u clea r Com p lexes
Manuel J ime´nez-Tenorio, M. Dolores Palacios, M. Carmen Puerta, and
Pedro Valerga*
Departamento de Ciencia de los Materiales e Ingenier´ıa Metalu´rgica y Qu´ımica Inorga´nica,
Facultad de Ciencias, Universidad de Ca´diz, 11510 Puerto Real, Ca´diz, Spain
Received September 23, 2003
The reactions of [Cp*RuCl(CO)(PMeiPr2)] (1) and [Cp*RuCl(CO)(PEt3)] (2) with NaBAr′4
in fluorobenzene both under argon and under dinitrogen generate the binuclear compounds
[{Cp*Ru(CO)(PMeiPr2)}2(µ-Cl)][BAr′4] (3) and [{Cp*Ru(CO)(PEt3)}2(µ-Cl)][BAr′4] (4), respec-
tively, which were fully characterized. The crystal structure of compound 4 is reported,
showing for the first time two chiral “Cp*Ru” fragments bonded through only one bridging
chloride ligand. No dinitrogen complexes or 16-electron species could be isolated. Halide
abstraction from 1 using dry acetone as solvent yields the compound [Cp*Ru(CO){η1-OC-
(CH3)2}(PMeiPr2)][BAr′4] (5). A range of olefins react with [Cp*RuCl(CO)(PMeiPr2)] and
NaBAr′4 furnishing the corresponding cationic η2-alkene complexes [Cp*Ru(CO)(L)(PMei-
Pr2)][BAr′4] (L ) C2H4, 6; H2CdCHPh, 7; and H2CdCHCOOCH3, 8), which are stable under
argon atmosphere in solution. The crystal structure of compound 6 is also reported. Both 1
and 2 react with SnCl2 in CH2Cl2 to yield the insertion derivatives [Cp*Ru(CO)(SnCl3)-
(PR3)] (PR3 ) PMeiPr2, 9; PEt3, 10), which have also been characterized.
In tr od u ction
(PEt3)2, (PPhiPr2)2, (PPh3)2),3,4 as well as some others
containing hard nitrogen donor ligands.5-7 However, the
reaction of [Cp*RuCl(dppm)] (dppm ) bis(diphenylphos-
phino)methane) with NaBAr′4 in fluorobenzene under
argon generates the binuclear complex [{Cp*Ru}2(µ-Cl)-
(µ-dppm)2][BAr′4].8 No complex was isolated from a
similar reaction using [Cp*RuCl(dppe)] (dppe ) 1,2-bis-
(diphenylphosphino)ethane) under argon, although ha-
lide abstraction from [Cp*RuCl(PP)] (PP ) dppm, dppe)
under dinitrogen yielded the corresponding cationic
terminal dinitrogen complexes [Cp*Ru(N2)(PP)][BAr′4].8
Attempts to isolate species [Cp*Ru(PP)]+, analogous to
those containing other phosphine ligands such as PiPr3,
PCy3, or PMe3, led to the sandwich derivative [Cp*Ru-
(η6-FPh)][BAr′4]. Both [Cp*Ru(PPh3)2][BAr′4] and [Cp*Ru-
(PPhiPr2)2][BAr′4] are unstable and rearrange to the 18-
electron sandwich species [Cp*Ru(η6-C6H5PR2)][BAr′4],
Half-sandwich compounds [Cp*RuCl(PP)] (PP ) two
monodentate or one bidentate phosphine ligand) have
been well studied over the past years.1 However, there
is only a small group of well-known related compounds
[Cp*RuCl(CO)P] in which a carbonyl ligand substitutes
one phosphine.2 This change modifies properties and
reactivity of the metal center. They should also be
obtained by different synthetic methods.
On the other hand, the introduction of the noncoor-
dinating anion [BAr′4]- (BAr′4 ) tetrakis(3,5-bis(tri-
fluoromethyl)phenyl)borate) as halide scavenger has
recently allowed the isolation of coordinatively unsatur-
ated cationic complexes [Cp*Ru(PP)][BAr′4] (PP ) 1,2-
bis(diisopropylphosphino)ethane (dippe), (PMeiPr2)2,
i
and [Cp*Ru(η6-C6H5-POR2)][BAr′4] (R ) Ph, Pr) in the
* Corresponding author. Phone: +34 956016340. Fax: +34 95601-
6288. E-mail: pedro.valerga@uca.es.
presence of trace amounts of oxygen.4
(1) (a) Lomprey J . R.; Selegue, J . P. J . Am. Chem. Soc. 1989, 114,
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Smallridge, A. J . Adv. Organomet. 1990, 30, 1.
The 16-electron species can provide binding sites for
a range of molecules such as dihydrogen, dinitrogen, and
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Am. Chem. Soc. 2000, 122, 11230.
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10.1021/om034186x CCC: $27.50 © 2004 American Chemical Society
Publication on Web 12/24/2003

Dinuclear Complexes [{Cp*Ru(CO)(PR3)}2(µ-Cl)]+
Organometallics, Vol. 23, No. 3, 2004 505
alkenes. Dihapto-alkene complexes have been used as
intermediates in a large number of organic processes
such as hydrogenation, isomerization, and hydroformyl-
ation.9 After the first described ruthenium-η2-alkene
complex [RuCl2(CO)(H2CdCH2)(PMePh)2],10 other cat-
ionic half-sandwich complexes [CpRu(L)(PMe3)2]+ (L )
ethylene, styrene, propylene, and COD)11,12 have been
reported. We have carried out the syntheses of [(C5R5)-
Ru(H2CdCH2)(dippe)]+ (R ) H, Me)13 and [(C5R5)Ru-
(H2CdCH2)(PP′)]+ (R ) H, Me, P ) P′ ) PEt3; R ) H,
P ) PPh3, P′ ) PMeiPr2). Similarly, some other com-
plexes with styrene, [CpRu(H2CdCHPh)(PEt3)2]+, and
methyl-acrylate, [(C5R5)Ru(H2CdCHCOOMe)(PEt3)2]+
(R ) H, Me), have been obtained.14 Our synthetic
method was the abstraction of chloride ligand from the
starting compound [Cp*RuCl(PMeiPr2)] in the presence
of the corresponding alkene.
those systems containing the “Cp*RuCl(PP)” fragment
which we have previously reported. Related reactions
with alkenes, and SnCl2 insertion reactions into the
Ru-Cl bond, complete our work on this subject.
Resu lts a n d Discu ssion
20
The reduction of {Cp*RuCl2}2 with Zn in thf in the
presence of 1 equiv of diisopropylmethylphosphine
produces the 16-electron complex [Cp*RuCl(PMeiPr2)],
in dynamic equilibrium in solution with the correspond-
ing compound containing two phosphine ligands.21 The
treatment of these solutions with CO affords the com-
plex [Cp*RuCl(CO)(PMeiPr2)] (1). The presence of the
carbonyl ligand is confirmed by the IR spectrum of 1
showing the characteristic ν(CO) band as a sharp peak
at 1940 cm-1. In the 31P{1H } NMR spectrum 1 exhibits
1
The insertion of SnX2 in a M-X bond yielding
M-SnX3 is a well-known process. This reaction is
stereospecific, and when carried out with compounds
with catalytical activity, it produces a better selectivity
of the catalyst.15,16 Some products derived from these
reactions are very interesting to industry and pharma-
cology. The ruthenium chemistry involving SnCl3- as a
ligand is poorly developed, despite being promising; for
example, [Ru(SnCl3)5(PPh3)]3- catalyzes the formation
of acetic acid from methanol.17 In this way, we have
previously reported the reactions of [CpRuCl(dippe)] and
[Cp*RuCl(dippe)] with SnCl2 in CH2Cl2, which give
insertion derivatives of SnCl2 in the Ru-Cl bond,
namely, the orange compounds [CpRu(SnCl3)(dippe)]
and [Cp*Ru(SnCl3)(dippe)].18 The formation of these
derivatives is consistent with the lability of the chloride
ligand in the starting complexes. However, it has been
found that the dissociation of either chloride or phos-
phines is not really necessary for the formation of
insertion derivatives. The fact that the reaction of the
chiral complex [CpRuCl(dppp)] with SnCl2 proceeds
with net retention of configuration at the metal center
is consistent with the associative mechanism for this
reaction.19
a singlet at 42 ppm, and its H NMR spectrum displays
a characteristic doublet at 1.74, which corresponds to
Cp* hydrogens coupled to one phosphorus. A doublet
in the 13C{1H } NMR spectrum corresponds to the
carbonyl ligand carbon atom coupled with one phospho-
rus (J ) 20 Hz).
However, the same method was unsuccessful for the
synthesis of [Cp*RuCl(CO)(PEt3)] (2), which was alter-
natively prepared by displacement of one phosphine in
the direct reaction of [Cp*RuCl(PEt3)2]22 with CO. This
method has been already used to obtain analogous
complexes,23 although it often affords mixtures with
other undesirable products, consequently lowering the
yields. The spectral data for complexes 1 and 2 are very
similar. 2 also shows in the IR spectrum an intense ν-
(CO) peak at 1940 cm-1 as well as the doublet signal
1
corresponding to a Cp* proton resonance in the H NMR
spectrum and the doublet for the carbonylic carbon in
the 13C{1H } NMR spectrum.
Complexes 1 and 2 do not undergo chloride ion
dissociation in alcohol solution, this behavior being
different from that exhibited by the analogous [Cp*RuCl-
(P)2] systems. The carbonyl ligand is a stronger π-ac-
ceptor ligand compared to phosphines, and, therefore,
the ruthenium center is less electron rich in complexes
1 and 2. This accounts for their comparatively lower
tendency to dissociate chloride ions. The salt NaBAr′4
in fluorobenzene was used for chloride abstraction in
the same way as it was already used to isolate the 16-
electron complex [Cp*Ru(dippe)]+.3 Fluorobenzene was
chosen as solvent for its high polarity and weak coor-
dinative character in order to favor dissociation of the
sodium salt and the ruthenium complex. The anion
[BAr′4]- shows very weak or no tendency to coordinate,
contributing to the formation of unsaturated species.
When complex 1 reacts with NaBAr′4 in fluorobenzene,
the color changes from yellow-orange to red, character-
istic of the compound [{Cp*Ru(CO)(PMeiPr2)}2(µ-Cl)]-
[BAr′4] (3). In a similar way [{Cp*Ru(CO)(PEt3)}2(µ-
Cl)][BAr′4] (4) has also been obtained. The half-sandwich
In this work we describe the synthesis of [Cp*RuCl-
(CO)(PR3)] (PR3 ) PMeiPr2, PEt3) and halide abstraction
reactions with Na[BAr′4] in fluorobenzene and dry
acetone as solvents. The results are compared with
(9) Bennett, M. A.; Matheson, T. W. Comprehensive Organometallic
Chemistry; Pergamon: Oxford, 1982; Vol. 4, p 273.
(10) Brown, L. D.; Barnard, C. F. J .; Daniels, J . A.; Mawby, R. J .;
Ibers, J . A. Inorg. Chem. 1978, 17, 2932.
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(12) Treichel, P. M.; Komar, D. A. Inorg. Chim. Acta 1980, 42, 277.
(13) de los R´ıos, I.; J ime´nez Tenorio, M.; Padilla, J .; Puerta, M. C.;
Valerga, P. Organometallics 1996, 15, 4565.
(14) J ime´nez-Tenorio, M.; Padilla, J .; Puerta, M. C.; Valerga, P.
Unpublished work.
(15) (a) Consiglio, G.; Morandini, F.; Ciani, G.; Sironi, A.; Kretschmer,
M. J . Am. Chem. Soc. 1983, 105, 1391. (b) Morandini, F.; Consiglio,
G.; Straub, B.; Ciani, G.; Sironi, A. J . Chem. Soc., Dalton Trans. 1983,
1398.
(16) (a) Ferna´ndez, D.; Garc´ıa-Seijo, M. I.; Ke´gl, T.; Petocz, G.;
Kollar, L.; Garc´ıa-Ferna´ndez, M. E. Inorg. Chem. 2002, 41, 4435. (b)
Yamakawa, T.; Fujita T.; Shinoda, S. Chem. Lett. 1992, 905.
(17) (a) Shinoda, S.; Yamakawa, T. J . Chem Soc., Chem. Comun.
1990, 1511. (b) Ohnishi, T.; Suzuki, T.; Yamakawa, T.; Shinoda, S. J .
Mol. Catal. 1993, 84, 51.
(20) Tilley, T. D.; Grubbs, R. H.; Bercaw, J . E. Organometallics 1984,
3, 274.
(21) J ime´nez Tenorio, M.; Puerta, M. C.; Valerga, P. J . Organomet.
Chem. 2000, 609, 161.
(18) de los R´ıos, I.; J ime´nez Tenorio, M.; Padilla, J .; Puerta, M. C.;
Valerga, P. J . Chem. Soc., Dalton Trans. 1996, 377.
(19) Blackmore, T.; Bruce, M. I.; Stone, F. G. A. J . Chem. Soc. 1971,
2376.
(22) Coto, A.; J ime´nez-Tenorio, M.; Puerta, M. C.; Valerga, P.
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322, 221.

506 Organometallics, Vol. 23, No. 3, 2004
J ime´nez-Tenorio et al.
the phosphine ligand, and the bridging Cl. The distances
between the Cp* ring plane and the metal are 1.886(4)
Å for Ru(1) and 1.877(3) Å for Ru(2), respectively. Both
ruthenium atoms are chiral centers. The priority order
in the first coordination sphere is Cp* > Cl > P > C.
Consequently, the chirality in the represented complex
is SS. Since the space group is the centrosymmetric P21/
c, its enantiomer RR is also contained in the unit cell.
The other possible diastereomer, RS, was identified in
solution and will be discussed below. This is the first
reported structure of a binuclear ruthenium complex
with two Cp*Ru fragments linked only by one single
atom bridging ligand. Bond distances Ru(1)-Cl(1) and
Ru(2)-Cl(1) are very similar, 2.4952(19) and 2.4976-
(19) Å, as expected. They are comparable with, although
slightly longer than, those observed in binuclear com-
plexes with two bridging ligands [{Cp*Ru(C2F4)(µ-Cl)}2],
2.462(1) and 2.448(1) Å,24 and [{Cp*Ru(py) (µ-Cl)}2]+,
2.427(1) and 2.442(1) Å,25 and even closer to 2.4750(8)
and 2.4788(8) Å found in [{(C5Me4Et)Ru(C2H4)(µ-
Cl)}2].26
F igu r e 1. ORTEP diagram of cation [{Cp*Ru(CO)(PEt3)}2-
(µ-Cl)]+ in compound 4 showing the non-hydrogen atom-
numbering scheme. Selected bond distances (Å) and angles
(deg) for compound 4: Ru(1)-Cl 2.4952(19); Ru(2)-Cl
2.4976(19); Ru(1)-P(1) 2.328(2); Ru(2)-P(2) 2.340(2); Ru-
(1)-C(11) 1.854(9); Ru(2)-C(28) 1.860(10); Ru(1)-Cl-Ru-
(2) 137.33(8); P(1)-Ru(1)-Cl 86.66(7); C(11)-Ru(1)-P(1)
86.6(3); C(11)-Ru(1)-Cl 97.0(2); Cl-Ru(2)-P(2) 88.21(7);
P(2)-Ru(2)-C(28) 88.0(2); Cl-Ru(2)-C(28) 95.4(3).
The IR spectra of 3 and 4 show intense ν(CO) peaks
at 1942 and 1944 cm-1, respectively. In the 1H NMR
spectrum of 3 the methyl hydrogens of C5Me5 were
observed as one broad singlet at 1.59 ppm, which
probably consists of two close signals. The 31P{1H} NMR
spectrum shows two singlets at 38.2 and 39.5 ppm, with
approximately equal intensities, indicating two non-
Sch em e 1. P r op osed Rea ction Sequ en ce for th e
F or m a tion of 3 a n d 4
1
equivalent phosphorus atoms. The H NMR spectrum
of compound 4 shows two close signals for Cp* protons
at 1.68 and 1.69 ppm; the coupling constants with
phosphorus could be measured, giving similar values
(1.61 and 1.65 Hz, respectively). In the 31P{1H} NMR
spectrum two singlets appear at 33.95 and 34.72 ppm
corresponding, as in the case of 3, to the diastereomers
(RR or SS) and RS. The 13C{1H} NMR spectra are very
similar in both cases, and they can be compared with
that of 1 except by the fact that for complexes 3 and 4
phosphine carbons produce broader, although yet un-
resolved signals due to the presence of the two diaster-
eomers. In addition, the integrals for the different NMR
spectra give a ratio of approximately 1:1 for the two
diastereomers, in agreement with a pseudostatistical
distribution of RR, RS, SR (identical to RS), and SS.
The isolation or even the unequivocal identification
of coordinatively unsaturated complexes is not an easy
task. The 16-electron species [Cp*Ru(PR3)2]+ (PR3
)
PMeiPr2, PEt3) have already been characterized,27
whereas the complex [Cp*Ru(dippe)]+3 shows an agostic
interaction with one isopropylic proton. In other cases,
binuclear complexes such as [{CpRu(P2)}2(µ-N2)][BAr′4]
(P2 ) dippe or 2 PMeiPr2)4 or [{Cp*Ru}2(µ-Cl)( µ-dppm)2]-
[BAr′4] (dppm ) 1,1-bis(diphenylphosphino)methane)8
are obtained. Cp produces less electron richness at the
Ru center than Cp*, and hence coordinatively unsatur-
ated species containing the fragment {CpRu} are much
more reactive and difficult to isolate than those contain-
ruthenium 16-electron complexes already described in
the literature are characteristically blue or deep violet,
whereas in the processes described above these colors
were not observed during reaction. It is likely that in
this case the 16-electron species are extremely reactive
and they rapidly react with the starting complex to
generate dimer derivatives 3 and 4 (Scheme 1).
Recrystallization of 4 from diethyl ether/petroleum
ether afforded crystals suitable for single-crystal X-ray
diffraction. An ORTEP view of the dinuclear complex
cation [{Cp*Ru(CO)(PEt3)}2(µ-Cl)]+ is presented in Fig-
ure 1 including a selection of bond lengths and angles
in the footnote. The structure can be described as a
three-legged piano stool around each metal center. The
geometry of each ruthenium center can be described as
formally octahedral with the Cp* ligand occupying three
coordination positions and the others occupied by CO,
(24) Curnow, O. J .; Hughes, R. P.; Mairs, E. N.; Rheingold, A. L.
Organometallics 1993, 12, 3102.
(25) Chaudret, B.; J alo´n, F.; Pe´rez-Manrique, M.; Lahoz, F.; Plou,
F. J .; Sa´nchez-Delgado, R. New J . Chem. 1990, 14, 331.
(26) Koelle, D.; Kang, D. S.; Englert, U. J . Organomet. Chem. 1991,
420, 227.
(27) Aneetha, H.; J ime´nez-Tenorio, M.; Puerta, M. C.; Valerga, P.
Organometallics H.; J ime´nez-Tenorio, M.; Puerta, M. C.; Valerga, P.
Organometallics 2002, 21, 628.

Dinuclear Complexes [{Cp*Ru(CO)(PR3)}2(µ-Cl)]+
Organometallics, Vol. 23, No. 3, 2004 507
ing {Cp*Ru}. In addition, the stability of the moiety
{Cp*Ru(PP)} depends also on the phosphine ligands.
For instance, the five-membered chelate ring makes
[Cp*Ru(dippe)]+ more stable than the complex [Cp*Ru-
(dppm)]+, with a four-membered chelate ring, which has
not been isolated. On the other hand, [Cp*Ru(CO)-
(PR3)]+ should be more electrophilic than [Cp*Ru-
(PR3)2]+ because of the strong π-acceptor character of
carbonyl ligand.
The reaction of 1 with a solution of NaBAr′4 in a 1:1
acetone/fluorobenzene mixture leads to the yellow com-
pound [Cp*Ru{η1-OC(CH3)2}(CO)(PMeiPr2)][BAr′4] (5).
The presence of the CO ligand is indicated by a sharp
ν(CO) band at 1951 cm-1, and the band corresponding
to coordinated acetone appears at 1660 cm-1 in the IR
spectrum. Its 1H NMR spectrum shows the signals
corresponding to proton resonances of Cp* and phos-
phine ligands and also one singlet at 2.23 ppm corre-
sponding to the six hydrogen atoms of coordinated
acetone. A singlet at 39.56 ppm is observed in the 31P-
{1H } NMR spectrum as expected. The 13C{1H } NMR
spectrum displays one singlet at 213.5 ppm for the
carbonyl carbon atom and another resonance at 32.2 for
methyl carbon atoms in coordinated acetone. In addi-
tion, the CO resonance appears as a doublet at 205 ppm
with J C-P ) 19.53 Hz. These spectral data are in
agreement with those reported by Esteruelas2a for the
complex [CpRu(CO){η1-OC(CH3)2}(PiPr3)]+, which was
prepared by protonation of the monohydride complex
[CpRu(CO)(PiPr3)H] with HBF4 in acetone and subse-
quent displacement of the dihydrogen ligand.
As indicated above, the coordinatively unsaturated
species [Cp*Ru(CO)(PMeiPr2)]+ was not isolated but can
be generated in situ by reaction of compound 1 and
NaBAr′4 in fluorobenzene. This species reacts with
alkenes yielding η2-alkene complexes. In this way,
complexes 6, 7, and 8 were isolated as crystalline
[BAr′4]- salts. These compounds are air-stable both in
solution and in the solid state.
The identity of compound 6 was established by X-ray
crystallography. The ORTEP diagram of the cation is
depicted in Figure 2. Its structure can be described as
an overall three-legged piano stool geometry. All Ru-C
distances of the pentamethylcyclopentadiene moiety are
rather uniform, ranging from 2.219(5) to 2.280(5) Å, the
distance Ru(1)-Cp* ring being 1.893(2) Å, which is
comparable with values found for compound 4. The
C(11)-C(12) bond length of 1.416(13) Å compares well
with the values found for other ruthenium η2-ethylene
complexes, i.e., 1.43(2) Å for [Cp*Ru(C2H4)(dippe)]+ 13
and 1.439 Å for [Ru(C2H4)(PMe3)4].28 Free ethylene
ligand has a C-C bond distance of 1.337 Å, only slightly
shorter than in coordinated ethylene. It shows the slight
activation of C2H4 by coordination to the Ru center. The
angle C(11)-Ru(1)-C(12) is 37.5(3)°. Bond lengths Ru-
C(11) and Ru-C(12) are very similar (2.197(8) and
2.204(7) Å), showing a symmetric coordination of the
ethylene ligand to the metal.
F igu r e 2. ORTEP diagram of cation [Cp*Ru(η2-H2Cd
CH2)(CO)(PMeiPr2)]+ in compound 6 showing the non-
hydrogen atom-numbering scheme. Selected bond distances
(Å) and angles (deg) for compound 6: Ru-C(11) 2.197(8);
Ru-C(12) 2.204(7); C(11)-C(12) 1.416(13); C(11)-H(11A)
0.94(8); C(11)-H(11B) 0.87(9); C(12)-H(12A) 0.97; C(12)-
H(12B) 0.97; C(11)-Ru-C(12) 37.5(3); C(12)-C(11)-Ru
71.5(5); C(11)-C(12)-Ru 71.0(5); C(12)-Ru-P(1) 104.0(3).
stable in solution under argon atmosphere, making their
characterization possible. Whereas the coordination of
ethylene in 6 is irreversible, the analogous [Cp*Ru(η2-
C2H4)(dippe)]+ 13 is labile and loses C2H4, so its char-
acterization in solution was made under ethylene
atmosphere. The instability of ethylene-Cp*Ru adducts
was also observed for [Cp*Ru(η2-C2H4)(P∼O)][BPh4]
(P∼O ) (1,2-dioxan-2-ylmethyl)(diphenylphosphine)),29
which is stable only under an atmosphere of ethylene,
whereas other cyclopentadienylruthenium complexes
such as [CpRu(η2-C2H4)(PPh3)2]+ 30 and [CpRu(η2-C2H4)-
(PMe3)2]+ 31 are stable species. It seems that the effects
of fragments [Cp*Ru(CO)(P)]+ and [CpRu(PP)]+ on the
lability of bound ethylene are similar. Whereas com-
pound 7 is stable in solution, [CpRu(CH2dCHPh)-
(PEt3)2][BPh4] was characterized in acetone only in the
presence of styrene.14 The protons of the C2H4 ligand
1
appear in the H NMR spectrum of 6 as two multiplets
at 2.42 and 2.52 ppm. The ethylene carbon atoms appear
as one singlet at 47.32 ppm in the 13C{1H } NMR
spectrum. This signal was observed for the complexes
[CpRu(η2-C2H4)(PEt3)2]+ and [Cp*Ru(η2-C2H4)(dippe)]+
at 39.9 and 33.3 ppm, respectively.13 A similar chemical
shift was observed for complex [Cp*Ru(η2-C2H4)(P∼O)]+
(δ ) 46.9 ppm).
Three multiplets at 2.19, 3.23, and 4.65 ppm are
observed in the 1H NMR spectrum of compound 7
corresponding to the styrene ligand, and similarly at
2.32, 3.02, and 3.19 ppm for the methyl acrylate deriva-
tive 8. In the 13C{1H } NMR spectra two singlets at
41.77 and 74.18 ppm for compound 7 and similarly at
The crystalline compounds 6, 7, and 8 display in their
IR spectra the characteristic strong band corresponding
to ν(CO). In addition, bands attributed to the coordi-
nated alkene were observed at 1611, 1620, and 1707
cm-1 for 6, 7, and 8, respectively. These compounds are
(29) Lindner, E.; Haustein, M.; Fawzi, R.; Steinmann, M.; Wegner,
P. Organometallics 1994, 13, 5021.
(30) Bruce, M. I.; Hambley, T. W.; Rodgers, J . R.; Snow, M. R.; Wong,
F. S. Aust. J . Chem. 1982, 35, 1323.
(31) Mynott, R.; Lehmkuhl, H.; Kreuzer, E. M.; J oussen, E. Angew.
Chem., Int. Ed. Engl. 1990, 29, 289.
(28) Dewar, M. S. J . Bull Soc. Chim. 1953, 18, C 79.

508 Organometallics, Vol. 23, No. 3, 2004
J ime´nez-Tenorio et al.
2
K): δ 1.11 (m, 12 H, PCH(CH3)2, 1.32 (d, 3 H, J HP ) 8.4 Hz,
52.43 and 46.33 ppm for compound 8 are observed,
corresponding to the primary and secondary C atoms
of the alkene ligand. This is the difference that was
found in relation to compound 6, where the two double-
bonded carbon atoms are equivalent.
In the 31P{1H } NMR spectra only one signal is
observed in all cases, showing that they are not a
mixture of products. Of the two possible endo and exo
isomers, only one is obtained, and probably it is the exo
because of steric features.
Compounds 1 and 2 react with anhydrous SnCl2 in
CH2Cl2, yielding the neutral trichlorostannyl complexes
[Cp*Ru(CO)(PMeiPr2)(SnCl3)] (9) and [Cp*Ru(CO)(PEt3)-
(SnCl3)] (10), yellow and orange, respectively. These
compounds are generated by insertion of SnCl2 into the
Ru-Cl bond, a process that is well-known and has been
thoroughly studied15 due to the ability of the trichlo-
rostannyl ligand to promote or modify the catalytic
activity of transition metal complexes.16 The 31P{1H }
NMR spectra of both compounds consist of one singlet
at 26.13 and 37.62 ppm, respectively, showing small
satellites due to coupling of the phosphorus atom to the
NMR active 117Sn and 119Sn nuclei. The coupling
constants are J (P,117Sn) ) 347 Hz and J (P,119Sn) ) 322
Hz for compound 9. For compound 10, these coupling
constants are 355.4 and 340.49 Hz. Consistent with this,
the 119Sn NMR spectra of 9 and 10 display one doublet
in both cases, at δ ) 44.19 ppm (J P-Sn ) 346 Hz) for 9
and δ ) 36.77 ppm (J P-Sn ) 354.36 Hz) for 10,
respectively, due to coupling of the 119Sn nucleus with
the phosphorus atom.
PCH3), 2.11 (m, 1 H, PCH(CH3)2), 2.24 (m, 1 H, PCH(CH3)2),
1.74 (d, 15 H, J HP ) 1.6 Hz, C5(CH3)5). 31P{1H} NMR (161.89
4
MHz, CDCl3, 298 K): δ 41.82 (s). 13C{1H} NMR (75.4 MHz,
1
CDCl3, 298 K): δ 7.8 (d, J CP ) 25.9 Hz, PCH3), 10.48 (s, C5-
2
2
(CH3)5), 17.7 (d, J CP ) 14.7 Hz, PCH(CH3)2), 18.4 (d, J CP
)
18.0 Hz, PCH(CH3)2), 27.0 (d, 1J CP ) 26.8 Hz, PCH(CH3)2), 28.2
1
2
(d, J CP ) 22.9 Hz, PCH(CH3)2), 99.63 (d, J CP ) 1.8 Hz, C5-
2
(CH3)5), 207.4 (d, J CP ) 20.4 Hz, CO).
[Cp *Ru Cl(CO)(P Et3)] (2). To a solution of {Cp*RuCl2}2
(0.80 g, 2.94 mmol) in tetrahydrofuran (25 mL) were added
triethylphosphine (0.9 mL, 6.0 mmol) and Zn powder (ca. 1.0
g). The mixture was stirred for 45 min at room temperature
and then filtered through Celite. CO was bubbled through the
orange solution, then it was stirred for 30 min. The solvent
was removed in vacuo, and the resulting sticky residue was
washed with petroleum ether several times in order to remove
the released phosphine. A yellow solid was obtained, which
was dried in vacuo. Yield: 0.480 g, 60%. Anal. Calcd for C17H30
-
ClOPRu: C, 48.8; H, 7.24. Found: C, 48.7; H, 7.27. IR
(Nujol): ν(CO) 1931(s) cm-1. H NMR (400 MHz, CDCl3, 298
1
K): δ 1.06 (m, 9 H, PCH2CH3), 1.82 (m, 6 H, PCH2CH3), 1.78
(d, 15 H, 4J HP ) 1.5 Hz, C5(CH3)5). 31P{1H} NMR (161.89 MHz,
CDCl3, 298 K): δ 36 (s). 13C{1H} NMR (100.6 MHz, CDCl3,
298 K): δ 7.95 (s, PCH2CH3), 10.12 (s, C5(CH3)5), 18.70 (m,
PCH2CH3), 95.80 (d, J CP ) 1.4 Hz, C5(CH3)5), 207.86 (d, J CP
) 18.5 Hz, CO).
2
2
[{Cp *Ru (CO)(P MeiP r 2)}2(µ-Cl)][BAr ′4] (3). To a solution
of 1 (0.170 g, 0.39 mmol) in fluorobenzene (10 mL) was added
solid NaBAr′4 (0.34 g, 0.39 mmol). The reaction mixture was
stirred at room temperature for 30 min. A color change from
yellow-orange to dark red was observed. Sodium chloride was
removed by filtration through Celite. The filtrate was concen-
trated under reduced pressure to a volume of ca. 1 mL, then
layered with petroleum ether and left undisturbed at room
temperature. Red crystals were obtained by slow diffusion of
petroleum ether into the fluorobenzene. The crystals were
separated from the supernatant liquor, washed with petroleum
ether, and dried in an argon stream. Yield: 0.46 g, 70%. Anal.
Calcd for C68H76BClF24O2P2Ru2: C, 48.3; H, 4.53. Found: C,
Exp er im en ta l Section
All synthetic operations were performed under a dry argon
atmosphere, using conventional Schlenck techniques. Tetrahy-
drofuran, diethyl ether, and petroleum ether (boiling point
range 40-60 °C) were distilled from the appropiate drying
agents. Fluorobenzene was purchased from Aldrich and ac-
etone (0.01% water max.) from SDS. All solvents were deoxy-
47.9; H, 4.58. IR (Nujol): ν(CO) 1942(s) cm-1, ν(Ar′) 1609 cm-1
.
1H NMR (400 MHz, CDCl3, 298 K): δ 1.12 (m, 30 H, PCH-
(CH3)2 and PCH3) 1.59 (s, 30 H, C5(CH3)5), 2.07 (m, 4 H,
PCH(CH3)2). 31P{1H} NMR (161.89 MHz, CDCl3, 298 K): δ 38.2
(s), 39.5 (s). 13C{1H} NMR (100.6 MHz, CDCl3, 298 K): δ 7.70
(m, PCH3), 10.19 (m, C5(CH3)5), 18.50 (m, PCH(CH3)2), 26.84
(m, PCH(CH3)2), 96.12 (s, C5(CH3)5), 207.33 (d, 2J CP ) 19.5 Hz,
CO).
20
genated inmediately before use. The complexes {Cp*RuCl2}2
and Na[BAr′4]32 were prepared according to reported proce-
dures. Tetrahydrofuran solutions of [Cp*RuCl(PMeiPr2)]21 and
[Cp*RuCl(PEt3)2]22 were generated in situ and used straight-
forwardly. IR spectra were recorded in Nujol mulls on a
Perkin-Elmer Spectrum 1000 spectrophotometer. NMR spectra
were taken on Varian Unity 400 MHz or Varian Gemini 300
MHz equipment using the appropriate deuterated solvent.
Chemical shifts are given in ppm from SiMe4 (1H and 13C{1H}),
[{Cp *R u (CO)(P E t3)}2(µ-Cl)][BAr ′4] (4). This compound
was obtained in a fashion analogous to that for 3, starting from
2 (0.130 g, 0.3 mmol) and NaBAr′4 (0.3 g, 0.33 mmol) in
fluorobenzene (10 mL). Yield: 0.45 g, 70%. Anal. Calcd for
85% H3PO4 (31P{1H}), or SnBu4 119Sn{1H}). Microanalyses
(
were performed by the Serveis Cientı´fico-Te`cnics, Universitat
of Barcelona.
C
66H72BClF24O2P2Ru2: C, 47.6; H, 4.36. Found: C, 47.5; H,
4.40. IR (Nujol): ν(CO) 1944(s) cm-1, ν(Ar′) 1609 cm-1. 1H NMR
(400 MHz, CDCl3, 298 K): δ 1.04 (m, 18 H, PCH2CH3), 1.78
4
[Cp*Ru Cl(CO)(P MeiP r 2)] (1). To a solution of {Cp*RuCl2}2
(0.800 g, 2.94 mmol) in tetrahydrofuran (20 mL) were added
diisopropylmethylphosphine (0.50 mL, 3.30 mmol) and Zn
powder (ca. 1 g). The mixture was stirred for 45 min at room
temperature and then filtered through Celite. CO was bubbled
through this solution for 2 min. The solvent was removed
under vacuum, and the residue extracted with diethyl ether.
The solution was concentrated to the point of incipient
crystallization, and then it was stored at -30 °C. After 24 h a
microcrystalline yellow solid was formed, which was filtered
and dried in vacuo. Yield: 0.72 mg, 90%. Anal. Calcd for
(m, 12 H, PCH2CH3), 1.68 (d, 15H, J HP ) 1.61 Hz, C5(CH3)5).
31P{1H} NMR (161.89 MHz, CDCl3, 298 K): δ 33.95 (s), 34.72
(s). 13C{1H} NMR (100.6 MHz, CDCl3, 298 K): δ 7.82 (m,
PCH2CH3), 10.02 (s, C5(CH3)5), 17.80 (m, PCH2CH3), 95.62 (s,
2
C5(CH3)5), 206.90 (d, J CP ) 18.2 Hz).
[Cp *Ru {η1-OC(CH3)2}(CO)(P MeiP r 2)][BAr ′4] (5). To a
solution of 1 (0.1 g, 0.23 mmol) in 6 mL of fluorobenzene were
added NaBAr′4 (0.2 g, 0.23 mmol) and 6 mL of dry acetone.
The mixture reaction was stirred for 15 min. Sodium chloride
was removed by filtration through Celite. After concentration
of the resulting solution to a volume of ca. 1 mL, petroleum
ether was added and the resulting solution was left undis-
turbed at room temperature. A microcrystalline orange solid
was formed, which was separated from the supernatant liquor,
washed with petroleum ether, and dried in an argon stream.
Yield: 0.16 g, 70%. Anal. Calcd for C53H50BF24O2PRu: C, 48.31;
C
18H32ClOPRu: C, 49.9; H, 7.46. Found: C, 49.8; H, 7.49. IR
1
(Nujol): ν(CO) 1940(s) cm-1. H NMR (400 MHz, CDCl3, 298
(32) Brookhart, M.; Grant, B.; Volpe, A. F., J r. Organometallics 1992,
11, 3920.

Dinuclear Complexes [{Cp*Ru(CO)(PR3)}2(µ-Cl)]+
Organometallics, Vol. 23, No. 3, 2004 509
H, 3.82. Found: C, 48.1; H, 3.79. IR (Nujol): ν(CO) 1951(s)
cm-1, ν(OdC(CH3)2) 1660 cm-1, ν(Ar′) 1609 cm-1. 1H NMR (400
MHz, CDCl3, 298 K): δ 1.05 (m, 12 H, PCH(CH3)2), 1.12 (d, 3
MHz, CDCl3, 298 K): δ 41.20 (s). 13C{1H} NMR (75.4 MHz,
1
CDCl3, 298 K): δ 8.59 (d, J CP ) 31.4 Hz, PCH3), 9.34 (s, C5-
(CH3)5), 18.15, 18.67, 19.32, 19.50 (s, PCH(CH3)2), 27.42 (d,
1
1J CP ) 27.6 Hz, PCH(CH3)2), 30.25 (d, J CP ) 26.3 Hz, PCH-
2
H, J HP ) 8.75 Hz, PCH3), 2.06 (m, 2 H, PCH(CH3)2), 1.62 (d,
4
15 H, J HP ) 1.53 Hz, C5(CH3)5), 2.23 (s, 6 H, OC(CH3)2). 31P-
(CH3)2), 46.33 (s, CH2dCHCOOMe), 52.43 (s, dCHCOOCH3)
2
{1H} NMR (161.89 MHz, CDCl3, 298 K): δ 39.56 (s). 13C{1H}
102.9 (s, C5(CH3)5), 72.02 (s, COOCH3), 204.6 (d, J CP ) 19.3
1
Hz, CO).
NMR (75.4 MHz, CDCl3, 298 K): δ 6.80 (d, J CP ) 26.2 Hz,
PCH3), 10.09 (s, C5(CH3)5,), 17.1 (s, PCH(CH3)2), 17.82 (s, PCH-
[Cp *Ru (CO)(P MeiP r 2)(Sn Cl3)] (9). To a solution of 1 (0.06
g, 0.14 mmol) in 5 mL of dichloromethane was added an excess
of SnCl2 (0.04 g, 0.22 mmol). The reaction mixture was stirred
for 6 h at room temperature. A color change from yellow-orange
to pale yellow was observed. This solution was filtered through
Celite, and the filtrate was concentrated under reduced
pressure to a volume of ca. 1 mL. Then it was layered with
petroleum ether and left undisturbed at room temperature. A
microcrystalline pale yellow solid was formed, which was
filtered off and dried in vacuo. Yield: 0.100 g, 85%. Anal. Calcd
for C18H32POCl3SnRu: C, 32.9; H, 4.91. Found: C, 33.2; H,
4.85. IR (Nujol): ν(CO) 1935(s) cm-1. 1H NMR (400 MHz, CD2-
1
(CH3)2) 26.5 (d, J CP ) 25.3 Hz, PCH(CH3)2), 32.2 (s, (CH3)2-
2
CO), 96.3 (s, C5(CH3)5), 205.4 (d, CO, J CP ) 19.5 Hz), 213.5
(s, (CH3)2CO).
[Cp *Ru (η2-H2CdCH2)(CO)(P MeiP r 2)][BAr ′4] (6). Ethyl-
ene was bubbled through a solution of 1 (0.1 g, 0.23 mmol) in
fluorobenzene (8 mL) for 1 min. Then NaBAr′4 (0.2 g, 0.23
mmol) was added, and ethylene was bubbled through the
solution for a further 1 min. The mixture was stirred at room
temperature for 30 min. The color turned from yellow-orange
to colorless. Sodium chloride was removed by filtration through
Celite. The filtrate was concentrated under reduced pressure
to a volume of ca. 1 mL, then layered with petroleum ether
and left undisturbed at room temperature. White crystals were
obtained by slow diffusion of petroleum ether. These were
separated from the supernatant liquor and dried in an argon
Cl2, 298 K): δ 1.12 (m, 12 H, PCH(CH3)2), 1.47 (d, 3 H, 2J HP
)
4
7.9 Hz, PCH3) 2.08 (m, 2 H, PCH(CH3)2), 1.98 (d, 15 H, J HP
)1.51 Hz). 31P{1H} NMR (161.89 MHz, CD2Cl2, 298 K): δ 26.13
119
117
(t, 2J P
) 347 Hz, 2J P
) 332.8 Hz). 119Sn{1H} NMR
Sn
Sn
2
(149.158 MHz, CD2Cl2, 298 K): δ 44.19 (d, J PSn )346.6 Hz).
stream. Yield: 0.215 g, 60%. Anal. Calcd for C52H48PBOF24
Ru: C, 48.5; H, 3.76. Found: C, 48.7; H, 3.70. IR (Nujol): ν-
(CO) 1995(s) cm-1, ν(CdC) 1611 cm-1, ν(Ar′) 1609 cm-1 1H
-
13C{1H} NMR (100.6 MHz, CDCl3, 298 K): δ 10.43 (d, J CP
)
1
2
29.6 Hz, PCH3), 11.18 (s, C5(CH3)5), 16.69 (d, J CP ) 5.8 Hz,
.
2
PCH(CH3)2), 18.91 (d, J CP ) 16.7 Hz, PCH(CH3)2), 18.95 (d,
NMR (400 MHz, CDCl3, 298 K): δ 1.09 (m, 12 H, PCH(CH3)2),
1.23 (d, 3 H, 2J HP ) 8.44 Hz, PCH3), 2.07 (m, 2 H, PCH(CH3)2),
1.63 (s, 15 H, C5(CH3)5), 2.42 and 2.52 (m, 2 H, C2H2). 31P{1H}
2J CP ) 17.6 Hz, PCH(CH3)2), 97.98 (s, C5(CH3)5), 204.65 (d, 2J CP
) 16.2 Hz, CO).
[Cp *Ru (CO)(P Et3)(Sn Cl3)] (10). This compound, isolated
as a microcrystalline orange solid, was prepared as described
for 9, starting from [Cp*RuCl(CO)(PEt3)] (2) (0.06 g, 0.14
mmol) and SnCl2 (0.04 g, 0.22 mmol) in 5 mL of CH2Cl2.
Yield: 0.125 g, 85%. Anal. Calcd for C17H30POCl3SnRu: C,
31.7; H, 4.70. Found: C, 31.9; H, 4.80. IR (Nujol): ν(CO) 1930-
NMR (161.89 MHz, CDCl3, 298 K): δ 42.13 (s). 13C{1H} NMR
3
(75.4 MHz, CDCl3, 298 K): δ 8.90 (s, PCH3), 9.19 (d, J CP
)
3.6 Hz, C5(CH3)5), 18.10, 18.57, 18.85, 19.17 (s, PCH(CH3)2),
1
1
28.21 (d, J CP ) 27.41 Hz, PCH(CH3)2), 28.58 (d, J CP ) 27.5
Hz, PCH(CH3)2), 47.32 (s, C2H2), 101.6 (s, C5(CH3)5), 206.8 (d,
2J CP ) 18.5 Hz, CO).
1
(s) cm-1. H NMR (400 MHz, CD2Cl2, 298 K): δ 1.02 (m, 9 H,
[Cp *Ru (η2-H2CdCHP h )(CO)(P MeiP r 2)][BAr ′4] (7). An
excess of styrene (28 µL, 0.3 mmol) and NaBAr′4 (0.2 g, 0.23
mmol) were added to a solution of 1 (0.1 g, 0.23 mmol) in 5
mL of fluorobenzene. The mixture was stirred for 30 min at
room temperature. Sodium chloride was removed by filtration
through Celite. The filtrate was concentrated under reduced
pressure to a volume of ca. 1 mL, then layered with petroleum
ether and left undisturbed at room temperature. A white solid
was obtained, which was filtered off, washed, and dried.
Yield: 0.2 g, 60%. Anal. Calcd for C58H52PBOF24Ru: C, 51.1;
H, 3.84. Found: C, 51.5; H, 3.88. IR (Nujol): ν(CO) 2002(s)
cm-1, ν(CdC) 1620 cm-1, ν(Ar′) 1609 cm-1. 1H NMR (400 MHz,
CDCl3, 298 K): δ 1.11 (m, 12 H, PCH(CH3)2), 1.26 (d, 3 H,
2J HP ) 8.39 Hz, PCH3), 2.20 (m, 2 H, PCH(CH3)2), 1.76 (s, 15
PCH2CH3), 1.96 (m, 6 H, PCH2CH3), 1.91 (d, 15 H, 4J HP ) 1.60,
C5(CH3)5). 31P{1H} NMR (161.89 MHz, CD2Cl2, 298 K): δ 37.62
(t, 2J P
) 355.40 Hz, 2J P
) 340.49 Hz). 119Sn{1H} NMR
119
117
Sn
Sn
(149.158 MHz, CD2Cl2, 298 K): δ 36.77 (d, 2J PSn ) 354.36 Hz).
2
13C{1H} NMR (100.6 MHz, CDCl3, 298 K): δ 8.28 (d, J CP
)
2.9 Hz, PCH2CH3), 10.84 (s, C5(CH3)5), 20.92 (m, PCH2CH3),
95.80 (d, J CP ) 1.4 Hz, C5(CH3)5), 207.86 (d, J CP ) 18.5 Hz,
CO).
2
2
X-r a y Str u ctu r e Deter m in a tion s. Crystals of 4 and 6
were obtained by recrystallization from ethyl ether/petroleum
ether and fluorobenzene/petroleum ether, respectively. Crystal
data and experimental details are given in Table 1. X-ray
diffraction data were collected on a Bruker SMART APEX
3-circle diffractometer with CCD area detector at the Servicio
Central de Ciencia y Tecnolog´ıa de la Universidad de Ca´diz.
Hemispheres of the reciprocal space were measured by omega
scan frames with δ(ω) 0.30°. Correction for absorption and
crystal decay (insignificant) were applied by a semiempirical
method from equivalents using the program SADABS.33 The
structures were solved by direct methods, completed by
subsequent difference Fourier synthesis, and refined on F2 by
full matrix least-squares procedures using the program SHELX-
TL.34 All non-hydrogen atoms were refined with anisotropic
displacement coefficients. CF3 groups of the [BAr′4]- anion
showed orientation disorder in both cases. All CF3 groups for
compound 4 and six of eight for compound 6 were refined as
pairs of CF3 with complementary orientations. The remaining
two orientation disordered CF3 groups were approximated with
two split F atoms in each one. For compound 6 the four
hydrogen atoms in the ethylene ligand were localized in
4
H, J HP ) 1.22 Hz, C5(CH3)5), 2.19 (m, 1 H, H2CdCHPh), 3.23
(m, 1 H, H2CdCHPh), 4.65 (m, 1 H, H2CdCHPh), 7.1-7.4 (m,
5 H, Ph). 31P{1H} NMR (161.89 MHz, CDCl3, 298 K): δ 42.48
(s). 13C{1H} NMR (75.4 MHz, CDCl3, 298 K): δ 9.35 (s, PCH3),
9.83 (s, C5(CH3)5), 18.15, 18.93, 19.69, 19.82 (s, PCH(CH3)2),
1
1
29.09 (d, J CP ) 26.1 Hz, PCH(CH3)2), 29.54 (d, J CP ) 26.10
Hz, PCH(CH3)2), 41.77 (s, H2CdCHPh), 74.18 (s, H2CdCHPh),
2
101.5 (s, C5(CH3)5), 205.7 (d, J CP ) 19.6 Hz, CO).
[Cp*Ru (η2-H2CdCHCOOCH3)(CO)(P MeiP r 2)][BAr ′4] (8).
This complex, isolated as a white solid, was prepared as
described for 7 starting from 1 (0.1 g, 0.23 mmol), methyl
acrylate (28 µL, 0.3 mmol), and NaBAr′4 (0.2 g, 0.23 mmol).
Yield: 0.19 g, 63%. Anal. Calcd for C54H50PBOF24Ru: C, 49.8;
H, 3.84. Found: C, 49.1; H, 3.79. IR (Nujol): ν(CO) 1995(s)
cm-1, ν(CdO) 1707 cm-1, ν(Ar′) 1609 cm-1. 1H NMR (400 MHz,
CDCl3, 298 K): δ 1.18 (m, 12 H, PCH(CH3)2), 1.42 (d, 3 H,
2J HP ) 8.92 Hz, PCH3), 1.81 (m, 2 H, PCH(CH3)2), 1.72 (d, 15
H, 4J HP ) 1.34 Hz, C5(CH3)5), 2.32 (m, 1 H, H2CdCHCOOCH3),
3.02 (m, 1 H, H2CdCHCOOCH3), 3.19 (m, 1 H, H2Cd
CHCOOCH3), 3.72 (s, 3 H, COOCH3). 31P{1H} NMR (161.89
(33) Sheldrick G. M. SADABS, version of 2001; University of
Goettingen: Germany.
(34) SHELXTL, version 6.10, Crystal Structure Analysis Package;
Bruker AXS: Madison, WI, 2000.

510 Organometallics, Vol. 23, No. 3, 2004
J ime´nez-Tenorio et al.
Ta ble 1. Cr ysta l Da ta a n d Deta ils of th e Str u ctu r e Deter m in a tion for Com p ou n d s 4 a n d 6
4
6
formula
fw
C
34H59ClO2 P2Ru2 1+, C32H12BF24 1-
C20H36NOPRu 1+, C32H12BF24 1-
1286.75
1662.57
cryst syst
monoclinic
triclinic
space group
unit cell params a, b, c (Å)
P21/c (No. 14)
a ) 21.267(4)
b ) 18.870(3)
c ) 19.103(3)
R ) 90
P1h (No. 2)
a ) 13.5449(10)
b ) 13.7047(10)
c ) 17.4456(13)
R ) 103.465(2)
â ) 111.8560(10)
γ ) 97.466(2)
2837.6(4)
R, â, γ (deg)
â ) 102.186(4)
γ ) 90
V (Å3)
7493(2)
Z
4
2
δ(calc) (g/cm3)
1.474
0.581
3356
1.507
0.420
1296
-1
µ(Mo KR) (mm
F(000)
)
cryst size (mm)
T (K)
0.13 × 0.32 × 0.34
0.22 × 0.27 × 0.42
293
293
λ (Å)
θmin-θmax (deg)
Mo KR 0.71073
1.7, 23.3
Mo KR 0.71073
1.6, 25.6
dataset (h,k,l limits)
no. of total, unique data, R(int)
no. of obsd data (I > 2σI)
no. of reflns, no. of params
R, wR2, GOF
-23:23; -20:20; -20:21
49 964, 10 692, 0.055
9350
10 692, 1107
0.0803, 0.1724, 1.09
1/[σ2(Fo2) + (0.0638P)2 + 27.1900P]
where P ) (Fo2 + 2Fc2)/3
0.23, 0.02
-15:16; -16:16; -21:21
25 473, 10 484, 0.038
8636
10 484, 943
0.0751, 0.1686, 1.08
1/[σ2(Fo2) + (0.0701P)2 + 2.7532P]
where P ) (Fo2 + 2Fc2)/3
0.16, 0.02
w
max. and av shift/error
min. and max. resd dens (e/Å3)
-0.92, 1.94
-0.62, 0.80
regular difference Fourier maps. Hydrogen atoms bonded to
C(11) were allowed to refine with thermal parameters related
to Uiso for C(11). All the remaining hydrogen atoms in both
compounds were refined using the SHELX riding model. The
program ORTEP-335 was used for plotting.
de Educacio´n y Ciencia de la J unta de Andaluc´ıa (P.A.I.
research group FQM188) for financial support, and
J ohnson Matthey plc for generous loans of ruthenium
trichloride.
Su p p or tin g In for m a tion Ava ila ble: Crystallographic
tables and ORTEP diagrams for compounds 4 and 6. Data are
also given as crystallographic information files (CIF). This
material is avalaible free of charge via the Internet at
http://pubs.acs.org.
Ack n ow led gm en t. We thank the Ministerio de
Ciencia y Tecnolog´ıa (DGICYT, Project BQU2001-4046;
M.D.P. for grant BES2002-1422) and the Consejer´ıa
(35) Faruggia, L. J . ORTEP-3 for Windows version 1.076. J . Appl.
Crystallogr. 1997, 30, 565.
OM034186X