Addition of ethyl diazoacetate to the allenylidene ligand of [Ru(η5-C5H5)(C=C=CPh 2)(CO)(PPr3i)]BF4: Synthesis of ruthenium organometallic compounds containing new cyclic unsaturated η1-carbon ligands

Article abstract of DOI:10.1021/om980476f

The allenylidene complex [Ru(η⁵-C₅H₅)(C=C=CPh ₂)(CO)(PPr₃ⁱ)]BF₄ (1) reacts with ethyl diazoacetate to give the cyclic carbene derivative [Ru(η⁵-C₅H₅){=CCH=C(OEt)OC=CPh ₂}(CO)(PPr₃ⁱ)]BF₄ (2). The structure of 2 was determined by an X-ray investigation, revealing a Ru-C distance of 2.017(6) A?. Treatment of 2 with sodium methoxide and methyllithium gives rise to the derivatives Ru(η⁵-C₅H₅){C=CHC(R)(OEt)OC=CPh ₂}(CO)(PPr₃ⁱ) (R = OMe (3), Me (4)). When a tetrahydrofuran solution of 3 is passed through an Al₂O₃ column, the lactonyl complex Ru(η⁵-C₅H₅){C=CHC(O)OC=CPh ₂}(CO)(PPr₃ⁱ) (5) is obtained. Complex 3 reacts with HBF₄·OEt₂ to regenerate 2 by selective elimination of methanol. The protonation of 4 with HBF₄·OEt₂ produces the elimination of ethanol and the formation of [Ru(η⁵-C₅H₅)-{=CCH=C(CH ₃)OC=CPh₂}(CO)(PPr₃ⁱ)]BF₄ (6). The structure of 6 was also determined by an X-ray investigation, revealing a Ru-C distance of 2.010(6) A?. The related cyclic carbene compound [Ru(η⁵-C₅H₅){=CCH=C(OH)OC=CPh ₂}(CO)(PPr₃ⁱ)]BF₄ (7) has been prepared by reaction of 5 with HBF₄-OEt₂.

Full text of DOI:10.1021/om980476f

Organometallics 1998, 17, 4959-4965
4959
Ad d ition of Eth yl Dia zoa ceta te to th e Allen ylid en e
Liga n d of [Ru (η5-C5H5)(CdCdCP h 2)(CO)(P P r i )]BF 4:
3
Syn th esis of Ru th en iu m Or ga n om eta llic Com p ou n d s
Con ta in in g New Cyclic Un sa tu r a ted η1-Ca r bon Liga n d s
Miguel A. Esteruelas,*,† Angel V. Go´mez,† Ana M. Lo´pez,†
M. Carmen Puerta,‡ and Pedro Valerga‡
Departamento de Quı´mica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n,
Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain, and Departamento de Ciencia de
Materiales e Ingenierı´a Metalu´rgica y Quı´mica Inorga´nica, Universidad de Ca´diz,
11510 Puerto Real, Ca´diz, Spain
Received J une 9, 1998
The allenylidene complex [Ru(η5-C5H5)(CdCdCPh2)(CO)(PPri )]BF4 (1) reacts with ethyl
3
diazoacetate to give the cyclic carbene derivative [Ru(η5-C5H5){dCCHdC(OEt)OCdCPh2}-
(CO)(PPri )]BF4 (2). The structure of 2 was determined by an X-ray investigation, revealing
3
a Ru-C distance of 2.017(6) Å. Treatment of 2 with sodium methoxide and methyllithium
gives rise to the derivatives Ru(η5-C5H5){CdCHC(R)(OEt)OCdCPh2}(CO)(PPri ) (R ) OMe
3
(3), Me (4)). When a tetrahydrofuran solution of 3 is passed through an Al2O3 column, the
lactonyl complex Ru(η5-C5H5){CdCHC(O)OCdCPh2}(CO)(PPri ) (5) is obtained. Complex 3
3
reacts with HBF4‚OEt2 to regenerate 2 by selective elimination of methanol. The protonation
of 4 with HBF4‚OEt2 produces the elimination of ethanol and the formation of [Ru(η5-C5H5)-
{)CCHdC(CH3)OC)CPh2}(CO)(PPri )]BF4 (6). The structure of 6 was also determined by
3
an X-ray investigation, revealing a Ru-C distance of 2.010(6) Å. The related cyclic carbene
compound [Ru(η5-C5H5){dCCHdC(OH)OCdCPh2}(CO)(PPri )]BF4 (7) has been prepared by
3
reaction of 5 with HBF4‚OEt2.
Sch em e 1
In tr od u ction
We have previously shown that the solvato complex
[Ru(η5-C5H5){η1-OC(CH3)2}(CO)(PPri )]BF4 reacts with
3
1,1-diphenyl-2-propyn-1-ol to afford the allenylidene
derivative [Ru(η5-C5H5)(CdCdCPh2)(CO)(PPri )]BF4,
3
which adds water, alcohols, thiols, and benzophenone
imine to afford R,â-unsaturated hydroxycarbene, alkox-
ycarbene, (alkylthio)carbene, and 2-azaallenyl com-
pounds, respectively. By deprotonation with sodium
methoxide, the hydroxycarbene compound gives an acyl
derivative, and the alkoxycarbene, (alkylthio)carbene,
and 2-azaallenyl complexes yield functionalized allenyl
derivatives.1
In solution at room temperature, the alkoxyallenyl
complex Ru(η5-C5H5){C(OCH2CHdCH2)dCdCPh2}(CO)-
(PPri ) isomerizes into the tricyclic tetraenyl derivative
3
Ru(η5-C5H5)(9-phenyl-3,3a,4,4a-tetrahydronaphtho[2,3-
nation with HBF4‚OEt2, this compound gives the tricy-
clic carbene [Ru(η5-C5H5)(9-phenyl-1,3,3a,4,4a,9a-hexahy-
dronaphtho[2,3-c]-1-furanylidene)(CO)(PPri3)]BF4, which
in solution at room temperature also isomerizes to afford
the acyclic alkoxycarbene [Ru(η5-C5H5){dC(OCH2[1-
c]-1-furanyl)(CO)(PPri ) by an intramolecular Diels-
3
Alder reaction, where the Câ-Cγ double bond and one
of the two phenyl groups of the allenyl unit acts as an
inner-outer ring diene and the CHdCH2 double bond
of the alkoxy fragment acts as a dienophile. By proto-
phenyl-3,4-dihydro-3-na phthyl])H}(CO)(PPri )]BF4
3
(Scheme 1) by a concerted intramolecular hydrogen
† Universidad de Zaragoza-CSIC.
transfer reaction.2
‡ Universidad de Ca´diz.
The allenylidene complex [Ru(η5-C5H5)(CdCdCPh2)-
(1) Esteruelas, M. A.; Go´mez, A. V.; Lahoz, F. J .; Lo´pez, A. M.;
On˜ate, E.; Oro, L. A. Organometallics 1996, 15, 3423.
(CO)(PPri )]BF4 also reacts with acetone in the presence
3
10.1021/om980476f CCC: $15.00 © 1998 American Chemical Society
Publication on Web 10/24/1998

4960 Organometallics, Vol. 17, No. 23, 1998
Esteruelas et al.
of base. The reaction product is the functionalized
CdCPh2)(CO)(PPri )]BF4, we now report the synthesis
3
alkynyl derivative Ru(η5-C5H5){CtCC(Ph)2CH2C(O)-
of new heteroatom-containing cyclic metal carbene
compounds which, in contrast to the above, are doubly
R,â-unsaturated with endocyclic and exocyclic carbon-
carbon double bonds. In addition, we describe the
synthesis of the first organometallic compound contain-
ing a cyclic ortho ester alkenyl ligand, and a new
unsaturated lactonyl ligand.
CH3}(CO)(PPri ), which affords the cyclic carbene com-
3
pound [Ru(η5-C5H5){)CCH2C(Ph)2CHdC(CH3)O}(CO)-
(PPri )]BF4 by addition of HBF4‚OEt2 (eq 1).3
3
Resu lts a n d Discu ssion
1. Rea ction of [Ru (η5-C5H5)(CdCdCP h 2)(CO)-
(P P r i3)]BF 4 w ith Eth yl Dia zoa ceta te. Treatment of
red dichloromethane solutions of [Ru(η5-C5H5)(CdCd
CPh2)(CO)(PPri )]BF4 (1) with 3 equiv of ethyl diazoac-
3
etate at 40 °C leads to dark purple solutions, from which
the cyclic carbene complex [Ru(η5-C5H5){dCCHdC(OEt)-
OCdCPh2}(CO)(PPri )]BF4 (2) is isolated as a result of
a 1,3-addition of the organic reagent at the CR-Câ
double bond of the allenylidene ligand of 1 (eq 2).
Heteroatom-containing cyclic metal-carbene com-
plexes have been previously prepared via metal ω-ha-
loacyl, carbamoyl, alkoxycarbonyl, or imido intermedi-
ates,4 opening of epoxides by deprotonated Fischer type
carbene complexes,5 activation of homopropargylic al-
cohols with low-valent d6 complexes,6 and direct activa-
tion of tetrahydrofuran.7 Pyranylidene-metal com-
plexes require the initial preparation of propenylidene-
metal derivatives or alkynyl-carbene complexes to react
with â-dicarbonyl derivatives, acrylates, or enol ethers.8
R,â-Unsaturated cyclic carbenes have been obtained
from a (4-methoxy-2-oxacyclopentylidene)chromium(0)
compound via methanol elimination, by addition of alkyl
radicals generated from epoxides and [Cp2TiCl]2,9 and
via direct activation of (Z)- and (E)-enynols.10
3
Although the reactivity of transition-metal allenylidene
compounds is presently attracting considerable inter-
est,11 related reactions have not been previously carried
out.
As a continuation of our work on the chemical
Complex 2 was obtained as a dark purple solid in 77%
yield and characterized by MS, elemental analysis, IR,
31P{1H}, and 13C{1H} NMR spectroscopy, and X-ray
diffraction. A view of the molecular geometry is shown
in Figure 1. Selected bond distances and angles are
listed in Table 1.
The geometry around the ruthenium center is close
to octahedral with the cyclopentadienyl ligand occupying
three sites of a face, and the angles formed by the
triisopropylphosphine, the carbonyl group, and the
unsaturated η1-carbon ligand are close to 90°.
properties of the allenylidene complex [Ru(η5-C5H5)(Cd
(2) Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.; On˜ate, E.; Ruiz,
N. Organometallics 1998, 17, 2297.
(3) Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.; Modrego, J .; On˜ate,
E. Organometallics 1997, 16, 5826.
(4) (a) King, R. B. J . Am. Chem. Soc. 1963, 85, 1922. (b) Casey, C.
P.; Anderson, R. L. J . Am. Chem. Soc. 1971, 93, 3554. (c) Motschi, H.;
Angelici, R. J . Organometallics 1982, 1, 343. (d) Michelin, R. A.;
Zanotto, L.; Braga, D.; Sabatino, P.; Angelici, R. J . Inorg. Chem. 1988,
27, 93.
(5) (a) Casey, C. P.; Brunsvold, W. R.; Scheck, D. M. Inorg. Chem.
1977, 16, 3059. (b) Lattuada, L.; Licandro, E.; Maiorana, S.; Molinari,
H.; Papagni, A. Organometallics 1991, 10, 807. (c) Kelley, C.; Lugan,
N.; Terry, M. R.; Geoffroy, G. L.; Haggerty, B. S.; Rheingold, A. L. J .
Am. Chem. Soc. 1992, 114, 6735.
(6) (a) Parlier, A.; Rudler, H. J . Chem. Soc., Chem. Commun. 1986,
514. (b) Do¨tz, K. H.; Sturm, W.; Alt, H. G. Organometallics 1987, 6,
1424. (c) Davies, S. G.; McNally, J . P.; Smallridge, A. J . Adv.
Organomet. Chem. 1990, 30, 1. (d) Le Bozec, H.; Ouzzine, K.; Dixneuf,
P. H. Organometallics 1991, 10, 2768. (e) Quayle, P.; Rahman, S.;
Ward, E. L. M.; Herbert, J . Tetrahedron Lett. 1994, 35, 3801. (f)
Gamasa, M. P.; Gimeno, J .; Gonza´lez-Cueva, M.; Lastra, E. J . Chem.
Soc., Dalton Trans. 1996, 2547. (g) Leung, W. H.; Chan, E. Y. Y.;
Williams, I. D.; Wong, W. T. Organometallics 1997, 16, 3234. (h) Liang,
K. W.; Li, W. T.; Peng, S. M.; Wang, S. L.; Liu, R. S. J . Am. Chem.
Soc. 1997, 119, 4404. (i) Bianchini, C.; Marchi, A.; Mantovani, N.;
Marvelli, L.; Masi, D.; Peruzzini, M.; Rosi, R. Eur. J . Inorg. Chem.
1998, 211.
(7) (a) Boutry, O.; Gutierrez, E.; Monge, A.; Nicasio, M. C.; Pe´rez,
P. J .; Carmona, E. J . Am. Chem. Soc. 1992, 114, 7288. (b) Gutierrez,
E.; Monge, A.; Nicasio, M. C.; Poveda, M. L.; Carmona, E. J . Am. Chem.
Soc. 1994, 116, 791.
(8) (a) Camps, F.; Moreto, J . M.; Ricart, S.; Vin˜as, J . M.; Molins, E.;
Miravitlles, C. J . Chem. Soc., Chem. Commun. 1989, 1560. (b) J uneau,
K. N.; Hegedus, L. S.; Roepke, F. W. J . Am. Chem. Soc. 1989, 111,
4762. (c) Wang, S. L. B.; Wulff, W. D. J . Am. Chem. Soc. 1990, 112,
4550. (d) Faron, K. L.; Wulff, W. D. J . Am. Chem. Soc. 1990, 112, 6419.
(9) Merlic, C. A.; Xu, D. J . Am. Chem. Soc. 1991, 113, 9855.
(10) Ruiz, N.; Peron, D.; Dixneuf, P. H. Organometallics 1995, 14,
1095.
The ruthenium and the five atoms of the five-
membered ring of the cyclic carbene ligand are almost
planar. The deviations from the best plane are 0.050-
(6) (C(7)), 0.135(6) (C(8)), -0.006(7) (C(9)), 0.064(6)
(C(10)), -0.082(5) (O(2)), and -0.0008(6) Å (Ru(1)). The
Ru(1)-C(7) distance (2.017(6) Å) is significantly longer
than those found in the R,â-unsaturated acyclic carbene
complex [RuCl(dCHCHdCPh)(CO)(PPri ) ]BF4 (1.874-
3 2
(3) Å)12 and the alkoxycarbene compound [Ru(η3-
(11) For some recent examples see: (a) Touchard, D.; Pirio, N.;
Dixneuf, P. H. Organometallics 1995, 14, 4920. (b) Cadierno, V.;
Gamasa, M. P.; Gimeno, J .; Borge, J .; Garc´ıa-Granda, S. Organome-
tallics 1997, 16, 3178. (c) Crochet, P.; Demerseman, B.; Vallejo, M. I.;
Gamasa, M. P.; Gimeno, J .; Borge, J .; Garc´ıa-Granda, S. Organome-
tallics 1997, 16, 5406. (d) Cadierno, V.; Gamasa, M. P.; Gimeno, J .;
Lo´pez-Gonza´lez, M. C.; Borge, J .; Garc´ıa-Granda, S. Organometallics
1997, 16, 4453. (e) Bohanna, C.; Callejas, B.; Edwards, A. J .; Esteru-
elas, M. A.; Lahoz, F. J .; Oro, L. A.; Ruiz, N.; Valero, C. Organometallics
1998, 17, 373. (f) Roth, G.; Reindl, D.; Gockel, M.; Troll, C.; Fischer,
H. Organometallics 1998, 17, 1393.
(12) Esteruelas, M. A.; Lahoz, F. J .; On˜ate, E.; Oro, L. A.; Zeier, B.
Organometallics 1994, 13, 4258.

Ru Compounds Containing New Cyclic η1-C Ligands
Organometallics, Vol. 17, No. 23, 1998 4961
Sch em e 2
proposed. Thus, the value of the Ru(1)-C(7) distance
suggests that for an adequate description of the bonding
situation in 2 a second resonance form such as b
(Scheme 2) should be considered. This is also supported
by the C(7)-C(10) (1.393(8) Å) and C(9)-C(10) (1.378-
(8) Å) distances, which are between those expected for
single and double C(sp2)-C(sp2) bonds. In contrast to
the C(7)-C(10) and C(9)-C(10) bond lengths, the C(7)-
C(8) (1.471(8) Å) and C(8)-C(11) (1.343(9) Å) distances
agree well with the mean values reported for single and
double C(sp2)-C(sp2) bonds (1.48 and 1.34 Å).12
The contribution of the resonance form b to the
structure of 2 can be also proposed on the basis of the
13C{1H} NMR spectrum of this complex, which shows a
doublet at 226.2 ppm with a C-P coupling constant of
11.3 Hz. This signal, assigned to C(7), appears about
60 ppm toward a field higher than those reported for
the typical CR resonances of carbene compounds.18 In
F igu r e 1. Molecular diagram for [Ru(η5-C5H5){dCCHd
C(OEt)OCdCPh2}(CO)(PPri )]BF4 (2). Thermal ellipsoids
3
1
are shown at 50% probability.
the H NMR spectrum of 2, the most noticeable reso-
nance is a singlet at 7.15 ppm, corresponding to the
hydrogen atom bonded to C(10).
Ta ble 1. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for th e Com p lex [Ru (η5-C5H5)-
As a result of the significant contribution of the
resonance form b to the structure of 2, the C(9) atom of
the cyclic carbene ligand has a marked electrophilic
character. Thus, in tetrahydrofuran as solvent, complex
2 reacts with nucleophiles to give cyclic alkenyl deriva-
tives containing an exocyclic carbon-carbon double
bond conjugated with the alkenyl unit. The new ligands
result from the addition of nucleophiles at the C(9) atom.
The treatment of 2 with sodium methoxide at room
{dCCHdC(OEt)OCdCP h 2}(CO)(P P r i3)]BF 4 (2)
Bond Lengths
Ru-P
2.357(2)
2.285(8)
2.235(8)
2.248(9)
2.247(8)
2.256(8)
1.826(8)
2.017(6)
1.165(8)
O(2)-C(8)
O(2)-C(9)
O(3)-C(9)
O(3)-C(24)
C(7)-C(8)
C(7)-C(10)
C(8)-C(11)
C(9)-C(10)
1.421(7)
1.326(7)
1.282(8)
1.467(8)
1.471(8)
1.393(8)
1.343(9)
1.378(8)
Ru-C(1)
Ru-C(2)
Ru-C(3)
Ru-C(4)
Ru-C(5)
Ru-C(6)
Ru-C(7)
O(1)-C(6)
temperature gives Ru(η5-C5H5){CdCHC(OMe)(OEt)-
Bond Angles
88.4(2)
91.5(2)
99.1(3)
104.9(5)
115.2(5)
170.9(6)
135.7(5)
121.3(4)
OCdCPh2}(CO)(PPri ) (3) in 67% yield, while the reac-
3
P-Ru-C(6)
C(8)-C(7)-C(10)
O(2)-C(8)-C(7)
O(2)-C(8)-C(11)
C(7)-C(8)-C(11)
O(2)-C(9)-O(3)
O(2)-C(9)-C(10)
O(3)-C(9)-C(10)
C(7)-C(10)-C(9)
102.9(5)
108.7(5)
113.8(5)
137.0(6)
113.5(6)
113.0(6)
133.4(6)
109.0(6)
tion of 2 with methyllithium at -60 °C affords Ru(η5-
P-Ru-C(7)
C(6)-Ru-C(7)
C(8)-O(2)-C(9)
C(9)-O(3)-C(24)
Ru-C(6)-O(1)
Ru-C(7)-C(8)
Ru-C(7)-C(10)
C5H5){CdCHC(Me)(OEt)OCdCPh2}(CO)(PPri ) (4) in
3
56% yield (Scheme 3).
The presence of an ortho ester alkenyl ligand in 3 is
strongly supported by the 1H and 13C{1H} NMR spectra.
In the 1H NMR spectrum, the resonance due to the
alkenyl dCH proton appears at 5.78 ppm as a singlet,
while the OCH3 resonance is observed at 3.27 ppm, also
as a singlet, and the resonances of the OCH2CH3 group
are observed at 4.03 (CH2) and 1.23 (CH3) ppm. In the
13C{1H} NMR spectrum, the resonance corresponding
to the CR atom of the alkenyl unit appears at 144.5 ppm
as a doublet with a C-P coupling constant of 12.8 Hz,
while the resonance due to the Câ atom is observed at
142.3 ppm as a singlet. The ortho ester carbon atom of
the cycle gives rise to a singlet at 117.9 ppm. The
chemical shift of this resonance agrees well with those
observed in molecular ortho esters.19
HBpz3){dC(OMe)CH2CO2Me}(dippe)]BPh4 (1.86(2) Å).13
However, the Ru(1)-C(7) distance is similar to the
ruthenium-carbon bond lengths found in the complexes
[Ru{C(dCHPh)OC(O)CH3}(CO){κ1-OC(CH3)2}(PPri ) ]-
3 2
BF4 (1.967(8) Å),14 Ru3(CO)10(µ2-SMe)(µ2-η2-NC6H4SC)
(2.075(9) Å),15 [{Ru(η5-C5Me5)(µ-SPri)}2(µ-C18H15)]BF4
(2.04(3) and 1.98(2) Å),16 and [{Ru(η5-C5Me5)(µ-SPri)}2-
(µ-C16H18)]OTf (2.06(1) and 2.04(1) Å),17 where a ruthe-
nium-carbon bond between single and double has been
(13) J ime´nez-Tenorio, M. A.; J ime´nez-Tenorio, M.; Puerta, M. C.;
Valerga, P. Organometallics 1997, 16, 5528.
(14) Esteruelas, M. A.; Lahoz, F. J .; On˜ate, E.; Oro, L. A.; Zeier, B.
Organometallics 1994, 13, 1669.
(15) Renouard, C.; Stoeckli-Evans, H.; Su¨ss-Fink, G. J . Organomet.
Chem. 1995, 492, 179.
(16) Matsuzaka, H.; Hirayama, Y.; Nishio, M.; Mizobe, Y.; Hidai,
M. Organometallics 1993, 12, 36.
(17) Matsuzaka, H.; Takagi, Y.; Hidai, M. Organometallics 1994,
13, 13.
(18) See for example: (a) Esteruelas, M. A.; Lahoz, F. J .; On˜ate, E.;
Oro, L. A.; Valero, C.; Zeier, B. J . Am. Chem. Soc. 1995, 117, 7935. (b)
Schwab, P.; Grubbs, R. H.; Ziller, J . W. J . Am. Chem. Soc. 1996, 118,
100. (c) Wilhelm, T.; Belderrain, T. R.; Brown, S. N.; Grubbs, R. H.
Organometallics 1997, 16, 4001.

4962 Organometallics, Vol. 17, No. 23, 1998
Esteruelas et al.
Sch em e 3
In the 1H NMR spectrum of 4, the most noticeable
resonances are two singlets at 5.93 and 1.50 ppm
corresponding to the alkenyl dCH proton and the
methyl group. In the 13C{1H} NMR spectrum the
resonances of the RuCdCH unit appear at 150.2 (Câ)
and 139.3 (CR) as doublets with C-P coupling constants
of 4.6 and 12.9 Hz, respectively. The COEt carbon gives
rise to a singlet at 109.0 ppm, similar to the chemical
shift observed for the related carbon atom of 3.
F igu r e 2. Molecular diagram for [Ru(η5-C5H5){d
CCHdC(CH3)OCdCPh2}(CO)(PPri )]BF4 (6). Thermal el-
3
lipsoids are shown at 50% probability.
Complex 3 is isolated at -78 °C by addition of
methanol to its tetrahydrofuran solutions, where the
complex is stable. When this addition is carried out at
Ta ble 2. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for th e Com p lex [Ru (η5-C5H5)-
{dCCHdC(CH3)OCdCP h 2}(CO)(P P r i3)]BF 4 (6)
room temperature, a mixture of 3 and Ru(η5-C5H5){Cd
Bond Lengths
Ru-P
2.372(2)
2.010(6)
1.845(7)
2.281(7)
2.295(7)
2.244(7)
2.237(8)
2.266(7)
O(1)-C(3)
O(1)-C(5)
O(2)-C(19)
C(1)-C(2)
C(1)-C(5)
C(2)-C(3)
C(3)-C(4)
C(5)-C(6)
1.353(7)
1.437(6)
1.145(7)
1.409(8)
1.464(8)
1.360(8)
1.468(9)
1.349(8)
CHC(O)OCdCPh2}(CO)(PPri ) (5) is obtained. Complex
3
Ru-C(1)
Ru-C(19)
Ru-C(20)
Ru-C(21)
Ru-C(22)
Ru-C(23)
Ru-C(24)
5 is isolated as a microcrystalline pure yellow solid in
78% yield, by passing a tetrahydrofuran solution of 3
through an Al2O3 column. The formation of 5 involves
the loss of ethyl methyl ether from 3 (eq 3), in agreement
with the trend shown by organic ortho esters to elimi-
nate ethers.20
Bond Angles
90.9(2)
P-Ru-C(1)
P-Ru-C(19)
C(1)-Ru-C(19)
C(3)-O(1)-C(5)
Ru-C(1)-C(2)
Ru-C(1)-C(5)
C(2)-C(1)-C(5)
C(1)-C(2)-C(3)
O(1)-C(3)-C(2)
O(1)-C(3)-C(4)
C(2)-C(3)-C(4)
O(1)-C(5)-C(1)
O(1)-C(5)-C(6)
C(1)-C(5)-C(6)
110.9(5)
110.8(5)
117.1(5)
132.0(6)
107.9(5)
113.8(5)
138.1(5)
89.9(2)
99.2(2)
106.5(4)
121.3(4)
135.7(4)
103.0(5)
of 4 with HBF4‚OEt2 leads to [Ru(η5-C5H5){dCCHd
The most significant spectroscopic feature of 5 is the
presence of a ν(CO) band at 1717 cm-1 in the IR
spectrum, which corresponds to the carbonyl group of
C(CH3)OCdCPh2}(CO)(PPri )]BF4 (6), by protonation of
3
the ethoxy group of 4 (eq 4). Complex 6 was obtained
as a dark green solid in 92% yield.
1
the lactonyl ligand. The H NMR spectrum shows the
characteristic dCH resonance of the alkenyl unit at 6.19
ppm, which is observed as a singlet. In the 13C{1H}
NMR spectrum the CR and Câ atoms of the alkenyl unit
give rise to a doublet at 178.1 ppm, with a C-P coupling
constant of 13.6 Hz and a singlet at 135.4 ppm,
respectively.
2. P r oton a tion of 3-5. Treatment at room tem-
perature of the ortho ester alkenyl complex 3 with 1
equiv of HBF4‚OEt2 in diethyl ether as solvent regener-
ates 2, by selective protonation of the methoxy group of
3. However, under the same conditions, the treatment
A view of the molecular geometry of 6 is shown in
Figure 2. Selected bond distances and angles are listed
in Table 2. As for 2, the geometry around the ruthe-
nium center is close to octahedral with the cyclopenta-
dienyl ligand occupying three sites of a face, and the
angles formed by the triisopropylphosphine, the carbo-
nyl group, and the unsaturated η1-carbon ligand are
close to 90°.
(19) See for example: (a) Dequeker, E.; Compernolle, F.; Toppet,
S.; Hoornaert, G. Tetrahedron 1995, 51, 5877. (b) Li, S.; Dory, Y. L.;
Deslongchamps, P. Tetrahedron 1996, 52, 14841.
(20) De Wolfe, R. H. Synthesis 1974, 153.

Ru Compounds Containing New Cyclic η1-C Ligands
Organometallics, Vol. 17, No. 23, 1998 4963
In this case, the ruthenium and the five atoms of the
five-membered ring of the cyclic carbene ligand are also
almost planar. The deviations from the best plane are
-0.057(6) (C(1)), -0.079(6) (C(2)), 0.016 (C(3)), -0.098-
(6) (C(5)), 0.067(4) (O(1)), and 0.0006(5) Å (Ru(1)).
Furthermore, the Ru(1)-C(1) (2.010(6) Å), C(1)-C(2)
(1.409(8) Å), C(2)-C(3) (1.360(8) Å), C(1)-C(5) (1.464-
(8) Å), and C(5)-C(6) (1.349(8) Å) distances are statisti-
cally identical with the related bond lengths in 2,
suggesting that the resonance form b (Scheme 2) also
makes a significant contribution to the structure of 6.
The spectroscopic data for 6 agree well with the
structure shown in Figure 2 and with the spectroscopic
C(OEt)OCdCPh2}(CO)(PPri )]+ shows a marked elec-
trophilic character, adding nucleophiles. This property
3
is responsible for the formation of Ru(η5-C5H5){CdCHC-
(OMe)(OEt)OCdCPh2}(CO)(PPri ), which, as far as we
3
know, is the first organometallic compound containing
an ortho ester alkenyl ligand.
In agreement with the trend shown by the organic
ortho esters to eliminate ethers, this ortho ester alkenyl
complex loses ethyl methyl ether, in the presence of
Al2O3, to afford the lactonyl derivative Ru(η5-C5H5){Cd
CHC(O)OCdCPh2}(CO)(PPri ), which by reaction with
1
data found for 2. Thus, in the H NMR spectrum, the
3
resonance due to the hydrogen atom bonded to C(2)
appears at 7.65 ppm, as a singlet, and the 13C{1H} NMR
spectrum shows at 236.3 ppm a doublet with a C-P
coupling constant of 11.0 Hz, corresponding to C(1).
The lactonyl complex 5 also reacts with HBF4‚OEt2.
The addition at -60 °C of 4 equiv of HBF4‚OEt2 to
dichloromethane solutions of 5 affords [Ru(η5-C5H5)-
HBF4‚OEt2 gives [Ru(η5-C5H5){dCCHdC(OH)OCdCPh2}-
(CO)(PPri )]BF4.
3
In conclusion, we report a new reaction within the
transition-metal allenylidene chemistry, which allows
the preparation of organometallic compounds containing
new organic fragments, including doubly R,â-unsatur-
ated cyclic carbene, ortho ester alkenyl, and lactonyl
ligands.
{dCCHdC(OH)OCdCPh2}(CO)(PPri )]BF4 (7), which
3
was isolated as a dark purple solid in 89% yield, by
addition of diethyl ether (eq 5).
Exp er im en ta l Section
All reactions were carried out with rigorous exclusion of air
using Schlenk-tube techniques. Solvents were dried by the
usual procedures and distilled under argon prior to use. The
starting material [Ru(η5-C5H5)(CdCdCPh2)(CO)(PPri3)]BF4 (1)
was prepared by the published method.1
In the NMR spectra, chemical shifts are expressed in ppm
downfield from Me4Si (1H and 13C) and 85% H3PO4 (31P).
Coupling constants, J , are given in hertz.
The IR spectrum of 7 in Nujol shows the ν(OH)
absorption at about 3030 cm-1, as a very broad band.
In addition two absorptions due to [BF4]- at 1151 and
1130 cm-1 are observed. The splitting of the expected
Td symmetry of the [BF4]- group suggests that the anion
interacts with the -OH proton of the cyclic carbene
ligand. A similar phenomenon has been observed in
acyclic hydroxycarbene complexes.1 In the 1H NMR
spectrum the resonance due to the dCH proton of the
alkenyl unit of the carbene appears at 6.86 ppm as a
singlet. The 13C{1H} NMR spectrum contains a doublet
at 210.4 ppm with a C-P coupling constant of 11.9,
corresponding to the RudC carbon atom, in agreement
with the 13C{1H} NMR spectra of 2 and 6.
P r epar ation of [Ru (η5-C5H5){dCCHdC(OEt)OCdCP h 2}-
(CO)(P P r i3)]BF 4 (2). A solution of 1 (1 g, 1.58 mmol) in 15
mL of dichloromethane was treated with ethyl diazoacetate
(500 µL, 4.75 mmol). The temperature was increased to 313
K until evolution of nitrogen ceased, and the color changed
from dark red to dark purple. The solution was concentrated
to ca. 2 mL, and by slow addition of diethyl ether, a dark purple
solid precipitated. Yield: 860 mg (77%). Anal. Calcd for
C34H42BF4O3PRu: C, 56.91; H, 5.90. Found: C, 56.60; H, 5.95.
IR (Nujol, cm-1): ν(CO) 1935 (vs), ν(CdC) 1593 (m), ν(CdC-
O) 1544 (vs), ν(BF4) 1053 (vs, br). 1H NMR (300 MHz, 293 K,
CDCl3): δ 7.54-7.34 (8H, Ph), 7.15 (s, 1H, RuCdCH), 7.14
(m, 2H, Ph), 5.36 (s, 5H, Cp), 4.67 (dc, 1H, J (HH) ) 7.2, J (HH)
) 10.5, OCHHCH3), 4.54 (dc, 1H, J (HH) ) 7.2, J (HH) ) 10.5,
OCHHCH3), 2.17 (m, 3H, PCHCH3), 1.42 (vt, 3H, J (HH) ) 7.2,
OCH2CH3), 1.17 (dd, 9H, J (HH) ) 7.2, J (PH) ) 14.1, PCHCH3),
1.09 (dd, 9H, J (HH) ) 7.2, J (PH) ) 14.4, PCHCH3). 31P{1H}
NMR (121.4 MHz, 293 K, CDCl3): δ 62.1 (s). 13C{1H} NMR
(75.4 MHz, 293 K, CDCl3, plus HETCOR): δ 226.2 (d, J (PC)
) 11.3, RudC), 202.8 (d, J (PC) ) 20.4, CO), 171.6 [s, dC(OEt)-
OCdCPh2], 159.8 [s, dC(OEt)OCdCPh2], 149.0 [s, dC(OEt)-
OCdCPh2], 139.8, 137.7 (both s, Cipso,Ph), 131.9, 131.6, 130.9,
128.2 (all s, Ph), 124.3 (s, CH)), 88.3 (s, Cp), 71.9 (s, OCH2),
27.2 (d, J (PC) ) 23.4, PCHCH3), 19.8, 19.4 (both s, PCHCH3),
14.1 (s, CH3). MS (FAB+): m/z 631 (M+).
Con clu d in g Rem a r k s
This study has revealed that heteroatom-containing
cyclic metal-carbene complexes can also be prepared
by reaction of transition-metal allenylidene compounds
with alkyl diazoacetates. As distinguished from the
complexes of this type previously reported, the new
derivatives are doubly unsaturated with endocyclic and
exocyclic carbon-carbon double bonds.
The X-ray analysis of the structures of the cations
P r ep a r a t ion of R u (η5-C5H5){CdCHC(OMe)(OE t )OCd
CP h 2}(CO)(P P r i3) (3). A solution of 2 (390 mg, 0.54 mmol)
in 15 mL of tetrahydrofuran was treated with sodium meth-
oxide (59 mg, 1.1 mmol), and the mixture was stirred for 10
min. The color changed from dark purple to orange, and
solvent was removed under vacuum. Dichloromethane (10
mL) was added, and the suspension was filtered to eliminate
sodium tetrafluoroborate. Solvent was evaporated and the
residue was washed with methanol at 198 K to afford a pale
[Ru(η5-C5H5){dCCHdC(R)OCdCPh2}(CO)(PPri3)]+ (R )
OEt, Me) suggests that the resonance form [Ru(η5-
C5H5){-CdCHC+(R)OCdCPh2}(CO)(PPri )] makes a
3
significant contribution to the structure of these com-
pounds. In agreement with this proposal, the C-R
carbon atom of the complex [Ru(η5-C5H5){dCCHd

4964 Organometallics, Vol. 17, No. 23, 1998
Esteruelas et al.
Ta ble 3. Su m m a r y for Cr ysta l Da ta Collection
a n d Str u ctu r e An a lysis for th e Com p lexes
yellow solid. Yield: 241 mg (67%). Anal. Calcd for C35H45O4-
PRu: C, 63.52; H, 6.85. Found: C, 63.11; H, 6.91. IR (Nujol,
cm-1): ν(CO) 1933 (vs), ν(CdC-O) 1724 (m). 1H NMR (300
MHz, 293 K, C6D6): δ 7.58-7.05 (10H, Ph), 5.78 (s, 1H, RuCd
CH), 4.75 (s, 5H, Cp), 4.03 (m, 2H, OCH2CH3), 3.27 (s, 3H,
OCH3), 2.20 (m, 3H, PCHCH3), 1.23 (vt, 3H, J (HH) ) 7.2,
OCH2CH3), 0.94 (dd, 9H, J (HH) ) 7.4, J (PH) ) 15.6, PCHCH3),
0.92 (dd, 9H, J (HH) ) 8.0, J (PH) ) 15.4, PCHCH3). 31P{1H}
NMR (121.4 MHz, 293 K, C6D6): δ 64.3 (s). 13C{1H} NMR (75.4
MHz, 293 K, C6D6, plus HETCOR): δ 205.8 (d, J (PC) ) 22.6,
CO), 164.6 [s, C(OMe)(OEt)OCdCPh2], 145.3 (s, Cipso,Ph), 144.5
(d, J (PC) ) 12.8, RuCd), 142.3 (s, CHd), 131.2, 127.5, 126.2,
125.8 (all s, Ph), 122.3 [s, C(OMe)(OEt)OCdCPh2], 117.9 [s,
C(OMe)(OEt)OCdCPh2], 86.1 (s, Cp), 58.6 (s, OCH2), 50.5 (s,
OCH3), 26.1 (d, J (PC) ) 22.9, PCHCH3), 20.0, 19.8 (both s,
PCHCH3), 16.2 (s, CH3).
[Ru (η5-C5H5){dCCHdC(OEt)OCdCP h 2}-
(CO)(P P r i3)]BF 4 (2) a n d [Ru (η5-C5H5)-
{dCCHdC(CH3)OCdCP h 2}(CO)(P P r i3)]BF 4 (6)
formula
C34H42BF4O3PRu C35H46BF4O3PRu
717.55 733.59
fw
cryst size (mm)
color, shape
cell measmts (25 reflns) (deg) 12.4 e 2θ e 18.3
cryst syst
space group
cell params
a (Å)
b (Å)
c (Å)
R (deg)
â (deg)
γ (deg)
V
0.35 × 0.27 × 0.05 0.37 × 0.22 × 0.10
deep red, plate
dark green, plate
12.4 e 2θ e 15.2
triclinic
triclinic
P1h (No. 2)
P1h (No. 2)
10.778(2)
18.085(4)
9.325(2)
99.31(2)
107.47(2)
103.43(2)
1633.0(7)
2
12.236(5)
14.073(6)
10.270(7)
104.15(4)
100.36(4)
80.54(4)
1673(1)
2
P r ep a r a t ion of R u (η5-C5H 5){CdCH C(Me)(OE t )OCd
CP h 2}(CO)(P P r i3) (4). A solution of 2 (285 mg, 0.40 mmol)
in 15 mL of tetrahydrofuran at 213 K was treated with
methyllithium (350 µL, 1.6 M in diethyl ether, 0.56 mmol),
and immediately, the color changed from dark purple to orange
and solvent was removed under vacuum. Toluene (15 mL) was
added and the suspension was filtered to eliminate lithium
tetrafluoroborate. Solvent was evaporated, and the residue
was washed with methanol at 198 K to afford a white solid.
Yield: 144 mg (56%). Anal. Calcd for C35H45O3PRu: C, 65.09;
H, 7.02. Found: C, 65.25; H, 6.55. IR (Nujol, cm-1): ν(CO)
1932 (vs), ν(CdC-O) 1723 (m), ν(CdC) 1593 (m). 1H NMR
(300 MHz, 293 K, C6D6): δ 7.62-7.04 (10H, Ph), 5.93 (s, 1H,
RuCdCH), 4.76 (s, 5H, Cp), 3.73 (dc, 1H, J (HH) ) 7.2, J (HH)
) 9.0, OCHHCH3), 3.60 (dc, 1H, J (HH) ) 7.2, J (HH) ) 9.0,
OCHHCH3), 2.25 (m, 3H, PCHCH3), 1.50 (s, 3H, C(CH3)(OEt)),
1.23 (vt, 3H, J (HH) ) 7.2, OCH2CH3), 0.96, (dd, 9H, J (HH) )
7.5, J (PH) ) 13.5, PCHCH3), 0.92 (dd, 9H, J (HH) ) 7.2, J (PH)
) 12.6, PCHCH3). 31P{1H} NMR (121.4 MHz, 293 K, C6D6):
δ 64.9 (s). 13C{1H} NMR (75.4 MHz, 293 K, C6D6, plus
DEPT): δ 206.0 (d, J (PC) ) 23.0, CO), 166.7 [s, C(Me)(OEt)-
OCdCPh2], 150.2 (d, J (PC) ) 4.6, CHd), 146.0, 143.1 (both s,
Z
F
calcd (g cm-3
)
1.459
1.456
λ(Mo KR) (Å)
µ(Mo KR) (cm-1
F(000)
0.710 69
5.72
740
0.710 69
5.60
760
)
abs cor
DIFABS22
0.823-1.416
3, 100
DIFABS22
0.891-1.144
4, 100
transmissn factors
stds: no., interval
decay (%)
-2.40
290(1)
-3.30
290(1)
temp (K)
scan method
ω/2θ
ω
scan speed (ω) (deg min-1
2θ interval (deg)
no. of measd rflns
no. of unique rflns
no. of obsd rflns (I > 3σI)
no. of params
)
4
4
5 < 2θ e 50
5521
5233 (Rint ) 0.044) 5801 (Rint ) 0.137)
3855
397
5 < 2θ e 50.1
5801
4271
366
rfln/param ratio
refinements
9.71
11.67
full-matrix ls on F full-matrix ls on F
Ra
0.0524
0.0655
0.055
0.067
-2
b
Rw (w ) σF
)
GOF
1.856
+0.91, -0.84
2.26
+1.05, -1.08
residual peaks (e Å-3
)
C
ipso,Ph), 139.3 (d, J (PC) ) 12.9, RuCd), 131.6, 127.6, 126.0,
a
b
R ) Σ(|Fo| - |Fc|)/Σ|Fo|. Rw ) [(Σw(|Fo| - |Fc|)2/ΣwFo2)]1/2
.
125.5 (all s, Ph), 116.7 [s, C(Me)(OEt)OCdCPh2], 109.0 [s,
C(Me)(OEt)OCdCPh2], 86.2 (d, J (PC) ) 1.8, Cp), 58.0 (s,
OCH2), 25.8 (d, J (PC) ) 22.1, PCHCH3), 23.1 (s, C(CH3)(OEt)-
OCdCPh2], 20.0, 19.4 (both s, PCHCH3), 16.2 (s, OCH2CH3).
MS (FAB+): m/z 646 (M+).
10 mL of diethyl ether was treated with tetrafluoroboric acid
(12 µL, 0.09 mmol, 54% in diethyl ether). Immediately, the
color changed from pale yellow to green, and a dark green solid
precipitated. Yield: 54 mg (92%). IR (Nujol, cm-1): ν(CO)
1946 (vs), ν(CdC-O) 1712 (s), ν(BF4) 1059 (vs, br). 1H NMR
(300 MHz, 293 K, CDCl3): δ 7.65 (s, 1H, dCH), 7.61-7.12
(10H, Ph), 5.36 (s, 5H, Cp), 2.33 (s, 3H, CH3), 2.12 (m, 3H,
PCHCH3), 1.12 (dd, 9H, J (HH) ) 7.2, J (PH) ) 14.4, PCHCH3),
1.04 (dd, 9H, J (HH) ) 7.2, J (PH) ) 14.4, PCHCH3). 31P{1H}
NMR (121.4 MHz, 293 K, CDCl3): δ 62.7 (s). 13C{1H} NMR
(75.4 MHz, 293 K, CDCl3, plus DEPT): δ 236.3 (d, J (PC) )
11.0, RuCd), 202.7 (d, J (PC) ) 19.8, CO), 173.1, 166.1 [both
s, dC(Me)OCdCPh2], 155.6 [s, dC(Me)OCdCPh2], 143.8 (d,
J (PC) ) 2.8, CH)), 140.1, 138.4 (both s, Cipso,Ph), 137.8, 133.2,
132.8, 132.1, 129.5, 128.4, 127.6 (all s, Ph), 88.9 (s, Cp), 27.4
(d, J (PC) ) 24.0, PCHCH3), 19.6, 19.4 (both s, PCHCH3), 14.4
(s, CH3). MS (FAB+): m/z 601 (M+).
P r ep a r a t ion of R u (η5-C5H 5){CdCH C(O)OCdCP h 2}-
(CO)(P P r i3) (5). Chromatography of 3 (90 mg, 0.14 mmol)
on a 10 cm alumina column, using tetrahydrofuran as eluent,
afforded a yellow band. Solvent was removed under vacuum,
and the residue was washed with diethyl ether, affording 5
as a yellow solid. Yield: 64 mg (78%). Anal. Calcd for
C
32H37O3PRu: C, 63.88; H, 6.20. Found: C, 63.58; H, 6.15.
IR (Nujol, cm-1): ν(CO) 1935 (vs), ν(CdO) 1717 (vs). 1H NMR
(300 MHz, 293 K, C6D6): δ 7.50-7.06 (10H, Ph), 6.19 (s, 1H,
RuCdCH), 4.63 (s, 5H, Cp), 1.85 (m, 3H, PCHCH3), 0.75 (dd,
9H, J (HH) ) 7.1, J (PH) ) 13.1, PCHCH3), 0.74 (dd, 9H, J (HH)
) 7.1, J (PH) ) 13.1, PCHCH3). 31P{1H} NMR (121.4 MHz,
293 K, C6D6): δ 64.4 (s). 13C{1H} NMR (75.4 MHz, 293 K,
C6D6, plus APT): δ 205.1 (d, J (PC) ) 22.1, CO), 178.1 (d, J (PC)
) 13.6, RuCd), 167.6 [s, C(O)OCdCPh2], 159.6 [s, C(O)OCd
CPh2], 143.5, 140.6 (both s, Cipso,Ph + C(O)OCdCPh2), 135.4
(s, CH)), 131.7-127.7 (all s, Ph), 86.5 (s, Cp), 26.5 (d, J (PC)
) 23.0, PCHCH3), 19.6, 19.4 (both s, PCHCH3). MS (FAB+):
m/z 602 (M+).
P r ep a r a tion of Ru [(η5-C5H5){dCCHdC(OH)OCdCP h 2}-
(CO)(P P r i3)]BF 4 (7). A solution of 5 (56 mg, 0.09 mmol) at
213 K in 5 mL of dichloromethane was treated with tetrafluo-
roboric acid (50 µL, 0.36 mmol, 54% in diethyl ether). The
mixture was stirred for 15 min, and the color changed from
yellow to purple. Solvent was concentrated to ca. 1 mL, and
10 mL of diethyl ether was very slowly added. A dark purple
solid precipitated, which was repeatedly washed with diethyl
P r epar ation of [Ru (η5-C5H5){dCCHdC(CH3)OCdCP h 2}-
(CO)(P P r i3)]BF 4 (6).21 A solution of 4 (55 mg, 0.09 mmol) in
ether at 213 K. Yield: 57 mg (89%). Anal. Calcd for C32H38
BF4O3PRu: C, 55.70; H, 5.55. Found: C, 55.78; H, 5.16. IR
-
(21) All our attempts to achieve a valid elemental analysis deter-
mination for complex 6 were unsuccessful. Even when we tried with
crystals of the same crop that was used for the X-ray diffraction study,
we could not obtain a satisfactory value.
(22) Walker, N.; Stuart, D. Acta Crystallogr. 1983, A39, 158.

Ru Compounds Containing New Cyclic η1-C Ligands
Organometallics, Vol. 17, No. 23, 1998 4965
(Nujol, cm-1): ν(OH) 3030 (br), ν(CO) 1949 (vs), ν(CdC-O)
1717 (s), ν(BF4) 1151, 1130 (s). 1H NMR (300 MHz, 293 K,
CDCl3): δ 7.46-7.09 (10H, Ph), 6.86 (s, 1H, dCH), 5.19 (s,
5H, Cp), 2.22 (m, 3H, PCHCH3), 1.14, (dd, 9H, J (HH) ) 7.5,
J (PH) ) 14.4, PCHCH3), 1.08 (dd, 9H, J (HH) ) 6.9, J (PH) )
13.8, PCHCH3). 31P{1H} NMR (121.4 MHz, 293 K, CDCl3): δ
63.1 (s). 13C{1H} NMR (75.4 MHz, 293 K, CDCl3, plus
DEPT): δ 210.4 (d, J (PC) ) 11.9, RuCd), 203.7 (d, J (PC) )
20.7, CO), 172.4, 158.6 [both s, dC(OH)OCdCPh2], 143.4 [s,
dC(OH)OCdCPh2], 140.3, 138.2 (both s, Cipso,Ph), 131.6, 130.3,
129.7, 127.9 (all s, Ph), 129.4 (s, CHd), 87.2 (s, Cp), 26.5 (d,
J (PC) ) 23.5, PCHCH3), 19.5, 19.4 (both s, PCHCH3).
The structures were solved by the Patterson method. All
non-hydrogen atoms of 2 and 6 (except the BF4 anion of (6))
-
were anisotropically refined on F by the full-matrix least-
squares method. The tetrafluoroborate anion of 6 was isotro-
pically refined by considering two different orientations, one
fluorine in two positions F(4A) and F(4B) with complementary
occupations. The hydrogen atoms of 2 and 6 were included in
calculated positions and not refined. Sets of 3855 (2) and 4271
(6) observed reflections (I > 3σ(I)), with 397 (2) and 366 (6)
variable parameters, were used in the last cycles of refine-
ments. Final values of R ) 0.052, Rw ) 0.065 (2), and R )
0.055, Rw ) 0.067 (6) were obtained. Details of structure
solution and refinement can also be found in Table 3. All
calculations were carried out using the TEXSAN software
package on a VAX 3520 computer at the “Servicio Central de
Ciencia y Tecnolog´ıa de la Universidad de Ca´diz”.
X-r a y Str u ctu r e An a lysis of Com p lexes [Ru (η5-C5H5)-
{dCCHdC(OEt)OCdCP h 2}(CO)(P P r i3)]BF 4 (2) a n d [Ru -
(η5-C5H5){dCCHdC(CH3)OCdCP h 2}(CO)(P P r i3)]BF4 (6). A
deep red crystal of C34H42BF4O3PRu (2) (0.27 × 0.05 × 0.35
mm) and a dark green crystal of C35H46BF4O3PRu (6) (0.37 ×
0.22 × 0.10 mm) were mounted on glass fibers and transferred
to a Rigaku AFC6S diffractometer. Graphite-monochromated
Mo KR radiation was used.
Ack n ow led gm en t. We thank the DGES (Project
PB-95-0806, Programa de Promocio´n General del Cono-
cimiento) for financial support.
Cell constants were obtained from a least-squares refine-
ment using the setting angles of 25 carefully centered reflec-
tions (2 and 6). The systems were determined to be triclinic,
space group P1h. The data were collected using the ω/2θ (2)
and ω (6) scan methods. The intensities of 3 standard
reflections were measured after every 100 reflections to apply
the decay correction. Lorentz-polarization and absorption
correction (DIFABS method) were also applied. A summary
of experimental details is given in Table 3.
Su p p or tin g In for m a tion Ava ila ble: Tables of atomic
coordinates, anisotropic and isotropic thermal parameters,
experimental details of the X-ray study, bond distances and
angles, and selected least-squares planes for complexes 2 and
6 (9 pages). Ordering information is given on any current
masthead page.
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