Preparation and Characterization of 4-Azoniaheptatrienyl, 4-Azaheptatrienyl, Ruthenapyrrolinone, and Pyrrolinyl Complexes of Ruthenium

Article abstract of DOI:10.1021/om030518m

The allenylidene complex [Ru(η⁵-C₅H ₅)(=C=C=CPh₂)(CO)(PⁱPr₃)]BF ₄ (1) adds the N-H bond of diallylamine to afford the N-allyl-4-azonia-1,3,6-heptatrienyl derivative [Ru(η⁵-C ₅H₅)-{C(CH=CPh₂)=N(CH₂CH=CH ₂)₂}(CO)(PⁱPr₃)]BF₄ (2). Treatment of 2 with sodium methoxide in tetrahydrofuran produces the deprotonation of the NCH₂ group of one of the allyl groups and the formation of a 1:1 mixture of the ruthenapyrrolinone complex (R _Ru,R_C- S_Ru,S_C)-Ru(η ⁵-C₅H₅)[=C(CH=CPh₂)=N(CH ₂CH=CH₂)CH(CH=CH₂)C=O}(PⁱPr ₃) (3) and the pyrrolinyl compound (R_Ru,S_C- S_Ru,R_C)-Ru(η⁵-C₅H ₅){C=CHCPh₂CH(CH=CH₂)NCH₂CH=CH ₂}-(CO)(PⁱPr₃) (4). Protonation of 4 with HBF₄·OEt₂ in diethyl ether initially leads to the heterocyclic derivative (R_Ru,S_C- S_Ru,R _C)-[Ru(η⁵-C₅H₅){C=N(CH ₂CH=CH₂)CH(CH=CH₂)-CPh₂CH ₂}(CO)(PⁱPr₃)BF₄ (5), containing a C-N double bond. In dichloromethane, complex 5 is unstable and evolves into the N-allyl-4-azonia-1,3,5-heptatrienyl complex [Ru(η⁵-C ₅H₅)-{C(CH=CPh₂)=N(CH=CHCH₃)CH ₂CH=CH₂}(CO)(PⁱPr₃)]BF₄ (6). The process involves the opening of the five-membered heterocycle and a proton transfer from the -CH₂CN- group to the =CH₂ carbon atom of the vinyl substituent of the heterocycle. Complex 1 also reacts with allylamine. The reaction leads to the 4-azonia-1,3,6-heptatrienyl derivative [Ru(η⁵-C₅H₅){C(CH=CPh ₂)=NH(CH₂CH=CH₂)}(CO)(PⁱPr ₃)]BF₄ (7). In contrast to 2, the deprotonation of 7 with sodium methoxide in tetrahydrofuran takes place at the nitrogen atom. In toluene at 70 °C, the resulting 4-aza-1,3,6-heptatrienyl complex Ru(η⁵-C₅H₅){C(CH=CPh₂)=NCH ₂CH=CH₂}(CO)(PⁱPr₃) (8) isomerizes into the conjugated 4-aza-1,3,5-heptatrienyl derivative Ru(η ⁵-C₅H₅){C(CH=CPh₂)=NCH=CHCH ₃}(CO)(PⁱPr₃) (9), as a result of a 1,3-sigmatropic rearrangement in the allyl unit. Complexes 3, 4, 5, and 9 have been characterized by X-ray diffraction analysis.

Full text of DOI:10.1021/om030518m

5274
Organometallics 2003, 22, 5274-5284
P r ep a r a tion a n d Ch a r a cter iza tion of
4-Azon ia h ep ta tr ien yl, 4-Aza h ep ta tr ien yl,
Ru th en a p yr r olin on e, a n d P yr r olin yl Com p lexes of
Ru th en iu m
Mar´ıa L. Buil,* Miguel A. Esteruelas,* Ana M. Lo´pez, and Enrique On˜ate
Departamento de Quı´mica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n,
Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain
Received J uly 2, 2003
The allenylidene complex [Ru(η5-C5H5)(dCdCdCPh2)(CO)(PiPr3)]BF4 (1) adds the N-H
bond of diallylamine to afford the N-allyl-4-azonia-1,3,6-heptatrienyl derivative [Ru(η5-C5H5)-
{C(CHdCPh2)dN(CH2CHdCH2)2}(CO)(PiPr3)]BF4 (2). Treatment of 2 with sodium methoxide
in tetrahydrofuran produces the deprotonation of the NCH2 group of one of the allyl groups
and the formation of a 1:1 mixture of the ruthenapyrrolinone complex (RRu,RC- SRu,SC)-
Ru(η5-C5H5)[,C(CHdCPh2),N(CH2CHdCH2)CH(CHdCH2)CdO}(PiPr3) (3) and the pyr-
rolinyl compound (RRu,SC- SRu,RC)-Ru(η5-C5H5){CdCHCPh2CH(CHdCH2)NCH2CHdCH2}-
(CO)(PiPr3) (4). Protonation of 4 with HBF4‚OEt2 in diethyl ether initially leads to the
heterocyclic derivative (RRu,SC- SRu,RC)-[Ru(η5-C5H5){CdN(CH2CHdCH2)CH(CHdCH2)-
CPh2CH2}(CO)(PiPr3)BF4 (5), containing a C-N double bond. In dichloromethane, complex
5 is unstable and evolves into the N-allyl-4-azonia-1,3,5-heptatrienyl complex [Ru(η5-C5H5)-
{C(CHdCPh2)dN(CHdCHCH3)CH2CHdCH2}(CO)(PiPr3)]BF4 (6). The process involves the
opening of the five-membered heterocycle and a proton transfer from the -CH2CN- group
to the dCH2 carbon atom of the vinyl substituent of the heterocycle. Complex 1 also reacts
with allylamine. The reaction leads to the 4-azonia-1,3,6-heptatrienyl derivative [Ru(η5-
C5H5){C(CHdCPh2)dNH(CH2CHdCH2)}(CO)(PiPr3)]BF4 (7). In contrast to 2, the deproto-
nation of 7 with sodium methoxide in tetrahydrofuran takes place at the nitrogen atom. In
toluene at 70 °C, the resulting 4-aza-1,3,6-heptatrienyl complex Ru(η5-C5H5){C(CHd
CPh2)dNCH2CHdCH2}(CO)(PiPr3) (8) isomerizes into the conjugated 4-aza-1,3,5-heptatrienyl
derivative Ru(η5-C5H5){C(CHdCPh2)dNCHdCHCH3}(CO)(PiPr3) (9), as a result of a 1,3-
sigmatropic rearrangement in the allyl unit. Complexes 3, 4, 5, and 9 have been characterized
by X-ray diffraction analysis.
In tr od u ction
metals, especially from ruthenium(II) complexes,3
brings along an alternative alkyne activation route. The
reactivity of the vinylidene-metal moiety is dominated
by the electrophilicity and nucleophilicity of the CR and
Câ atoms, respectively.4 As a result, one of the N-H
bonds of primary amines adds across the highly polar-
ized CR-Câ double bond of the vinylidene to afford
“aminocarbene derivatives”.5
EHT-MO calculations on the allenylidene compounds
LnMdCdCdCR2 indicate that the carbon atoms of the
unsaturated chain are alternatively electron-poor and
electron-rich, starting from the metal center.6 Hence,
electrophilic centers are located at the CR and the Cγ
atoms, while the Câ atom is a nucleophilic site. In
The hydroamination of alkynes in the presence of
transition metal complexes is an attractive route to
prepare numerous classes of organonitrogen molecules.1
Two basic approaches have been employed to effect
aminations and involve either alkyne or amine activa-
tion routes. Alkyne activation is generally accomplished
with late transition metals, which render π-alkyne
intermediates. The coordination of the alkyne to the
metallic center enhances its electrophilic character,
making the alkyne susceptible to undergoing the direct
nucleophilic addition of the amine.2
The evidence that vinylidene-metal intermediates are
easily formed from terminal alkynes and transition
* Corresponding author. Fax: 34 976761187; E-mail: maester@
unizar.es.
(1) (a) Mu¨ler, T. E.; Beller, M. Chem. Rev. 1988, 98, 675. (b) Pohlki,
F.; Doye, S. Chem. Soc. Rev. 2003, 32, 104. (c) Bytschkov, I.; Doye, S.
Eur. J . Org. Chem. 2003, 935.
(2) See for example: (a) Kadota, I.; Shibuya, A.; Lutete, L. M.;
Yamamoto, Y. J . Org. Chem. 1999, 64, 4570. (b) Hartung, C. G.; Tillack,
A.; Trauthwein, H.; Beller, M. J . Org. Chem. 2001, 66, 6339.
(3) Puerta, M. C.; Valerga, P. Coord. Chem. Rev. 1999, 193-195,
977.
(4) Bruce, M. I. Chem. Rev. 1991, 91, 197.
(5) (a) Gamasa, M. P.; Gimeno, J .; Mart´ın-Vaca, B.; Borge, J .; Garc´ıa-
Granda, S.; Pe´rez-Carren˜o, E. Organometallics 1994, 13, 4045. (b)
Bianchini, C.; Peruzzini, M.; Romerosa, A.; Zanobini, F. Organome-
tallics 1995, 14, 3152. (c) Bianchini, C.; Purches, G.; Zanobini, F.;
Peruzzini, M. Inorg. Chim. Acta 1998, 272, 2261.
10.1021/om030518m CCC: $25.00 © 2003 American Chemical Society
Publication on Web 10/31/2003

4-Azoniaheptatrienyl Complexes of Ru
Organometallics, Vol. 22, No. 25, 2003 5275
agreement with this and with the behavior of vinylidene
compounds, the addition of the N-H bond of primary
and secondary amines to the CR-Câ double bond of the
allenylidene ligand of [Ru(η5-C5H5)(dCdCdCPh2)(CO)(Pi-
Pr3)]BF4 and other electronically related rhenium and
tungsten compounds has been observed.7 The X-ray
structure determination of the complex [Ru(η5-C5H5)-
{C(CHdCPh2)dNEt2}(CO)(PiPr3)]BF4 and the analysis
of the ellipticities of the Ru-CR and CR-N bonds of the
model compound [Ru(η5-C5H5){C(CHdCH2)dNH2}(CO)-
(PH3)]+ suggest that the resulting complexes from the
N-H addition are better described as azoniabutadienyl
species, where the contribution of the aminocarbene
resonance form is not relevant.8
In the presence of bases, there is a marked difference
in behavior between the tertiary azoniabutadienyl
complexes [Ru(η5-C5H5){C(CHdCPh2)dNR2}(CO)(Pi-
Pr3)]BF4 and the secondary azoniabutadienyl com-
pounds [Ru(η5-C5H5){C(CHdCPh2)dN(R)H}(CO)(PiPr3)]-
BF4. Treatment of [Ru(η5-C5H5){C(CHdCPh2)dNR2}-
(CO)(PiPr3)]BF4 with sodium methoxide produces the
deprotonation of the CHdCPh2 group of the unsaturated
η1-carbon donor ligand and the formation of the corre-
sponding aminoallenyl derivatives Ru(η5-C5H5){C(NR2)d
CdCPh2}(CO)(PiPr3). Under the same conditions, the
deprotonation of [Ru(η5-C5H5){C(CHdCPh2)dN(R)H}-
(CO)(PiPr3)]BF4 takes place at the nitrogen atom. Thus,
the reactions of the latter with sodium methoxide lead
to the azabutadienyl derivatives Ru(η5-C5H5){C(CHd
CPh2)dNR}(CO)(PiPr3).8
In reactions with secondary and primary amines
containing a second nucleophilic atom, the allenylidene
ligand of [Ru(η5-C5H5)(dCdCdCPh2)(CO)(PiPr3)]BF4 is
active not only at the CR-Câ double bond but also at
the Cγ atom. The additions afford 1,2,3-diheterocycliza-
tion products. The stability of the formed cycles depends
on the nature of the amine. The reactions with pyrazoles
lead to pyrazolo[1,2-a] pyrazolyl complexes, which yield
functionalized alkynyl derivatives by treatment with
sodium methoxide.9 However, the reactions with 2-ami-
nopyridine and thioisonicotinamide give rise to poly-
heterocycles, which are stable in basic medium, as a
consequence of the presence of a NH bond in one of the
heterocycles. The NH bond can be deprotonated, pre-
venting in this way the ring opening.10
(η5-C5H5)(dCdCdCPh2)(CO)(PiPr3)]BF4, followed by the
deprotonation of the resulting azoniabutadienyl deriva-
tives, affords 2-azabicyclo[3.1.0]hexen-2-enyl, dihydro-
pyridiniumyl, and dihydronaphthopyrrolyl complexes.11
These heterocycles are the result of the addition of the
nitrogen atom of the amines to the CR atom of the
allenylidene and one or two C-C couplings. The number
of C-C bonds formed depends on both the nature of the
amine (primary or secondary) and the substituents at
the CR atom of the propargyl unit.
Allylamines contain a C-C double bond instead of a
C-C triple bond, and the NCH2 group is fairly acidic.
In the search for new reactions and novel types of
organometallic compounds, we have now studied the
reactivity of [Ru(η5-C5H5)(dCdCdCPh2)(CO)(PiPr3)]BF4
toward diallylamine and allylamine. In this paper, we
report the formation of 4-azonia-1,3,6-heptatrienyl de-
rivatives which have one more potential site of depro-
tonation than the previously reported azoniabutadienyl
derivatives. They allow the preparation of novel conju-
gated and nonconjugated 4-azaheptatrienyl, metalla-
heterocyclic, and heterocyclic compounds.
Resu lts a n d Discu ssion
1. Diallylam in e. Similarly to other secondary amines,
the N-H bond of this amine is added to the CR-Câ
double bond of the allenylidene ligand of [Ru(η5-C5H5)-
(dCdCdCPh2)(CO)(PiPr3)]BF4 (1). Thus, at room tem-
perature, the addition of 1.1 equiv of diallylamine to a
dichloromethane solution of 1 leads to the tertiary
N-allyl-4-azonia-1,3,6-heptatrienyl derivative [Ru(η5-
C5H5){C(CHdCPh2)dN(CH2CHdCH2)2}(CO)(PiPr3)]-
BF4 (2), which was isolated as a yellow solid in 94% yield
according to eq 1.
N-Heterocycles are also generated by deprotonation
of azoniabutadienyl ligands when the initial amine
contains a remote C-C triple bond. Thus, we have
recently shown that the addition of primary and second-
ary propargylamines to the allenylidene ligand of [Ru-
In agreement with the presence of C-N and C-C
double bonds in 2, its IR spectrum in Nujol shows bands
at 1639 and 1598 cm-1. The C-N double bond prevents
the rotation of the N(allyl)2 unit in solution at room
1
temperature. Thus, in the H NMR spectrum in chlo-
(6) (a) Berke, H.; Huttner, G.; Von Seyerl, J . Z. Naturforsch. 1981,
36B, 1277. (b) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Gonza´lez-
Cueva, M.; Lastra, E.; Borge, J .; Garc´ıa-Granda, S.; Pe´rez-Carren˜o,
E. Organometallics 1996, 15, 2137. (c) Edwards, A. J .; Esteruelas, M.
A.; Lahoz, F. J .; Modrego, J .; Oro, L. A.; Schrickel, J . Organometallics
1996, 15, 3556. (d) Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.;
Modrego, J .; On˜ate, E. Organometallics 1997, 16, 5826. (e) Baya, M.;
Crochet, P.; Esteruelas, M. A.; Gutie´rrez-Puebla, E.; Lo´pez, A. M.;
Modrego, J .; On˜ate, E.; Vela, N. Organometallics 2000, 19, 2585.
(7) (a) Bruce, M. I. Chem. Rev. 1998, 98, 2797. (b) Cadierno, V.;
Gamasa, M. P.; Gimeno, J . Eur. J . Inorg. Chem. 2001, 571. (c)
Mantovani, N.; Marvelli, L.; Rossi, R.; Bertolasi, V.; Bianchini, C.; de
los R´ıos, I.; Peruzzini, M. Organometallics 2002, 21, 2382.
roform-d, resonances corresponding to two inequivalent
allyl groups are observed, at 5.81 and 5.70 (CHd), 5.60,
5.54, 5.28, and 5.10 (CH2d), and 4.83 and 4.78 (CH2)
ppm. The resonance due to the CHd proton of the CHd
CPh2 unit appears at 6.73 ppm. The 13C{1H} NMR
1
spectrum agrees well with the H NMR spectrum; the
allyl groups display six resonances at 128.7 and 128.6
(CHd), 123.3 and 123.1 (CH2d), and 64.4 and 57.8 (CH2)
ppm. The CR atom of the η1-carbon donor ligand gives
rise to a doublet at 244.9 ppm, with a C-P coupling
constant of 9.4 Hz, while the resonances due to the CHd
(8) Bernad, D. J .; Esteruelas, M. A.; Lo´pez, A. M.; Modrego, J .;
Puerta, M. C.; Valerga, P. Organometallics 1999, 18, 4995.
(9) Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.; On˜ate; E.
Organometallics 1998, 17, 3567.
(10) Bernad, D. J .; Esteruelas, M. A.; Lo´pez, A. M.; Oliva´n, M.;
On˜ate, E.; Puerta, M. C.; Valerga, P. Organometallics 2000, 19, 4327.
(11) Buil, M. L.; Esteruelas, M. A.; Lo´pez, A. M.; On˜ate, E.
Organometallics 2003, 22,162.

5276 Organometallics, Vol. 22, No. 25, 2003
Buil et al.
Sch em e 1
The chemical behavior of the allenylidene ligand of 1
is much more versatile than the chemical behavior of
the vast majority of the allenylidene ligands of the iron
triad complexes.14 This fact has been ascribed to the
π-acidic nature of the carbonyl group, which enhances
the reactivity associated with the allenylidene spine.
The preparation of the ruthenapyrrolinone complex 3
proves that the carbonyl ligand of 1 not only plays an
indirect role in the reactivity of the allenylidene group
but also can be determinant to the formation of novel
organometallic compounds, playing a direct role.
The high degree of stereocontrol in the formation of
both 3 and 4 should be pointed out. As a result of the
prochirality of the NCH2 carbon atoms, two pairs of
enantiomers of each isomer could be formed during the
reaction. However, according to the 1H and 31P{1H}
NMR spectra of the crude reaction, only one pair of 3
and one pair of 4 are obtained. This suggests that the
configuration of the ruthenium atom of 1, and therefore
of 2, determines the configuration of the asymmetric
NCH- carbon atom of the heterocycles of 3 and 4.
The pair of the ruthenapyrrolinone complex 3 was
separated from the crude reaction by extraction in
pentane. The treatment of the isomeric mixture of 3 and
4 with this solvent affords an orange solution and a
yellow solid. The cooling of the solution at -20 °C gives
rise to pure orange crystals of the pair of 3, while the
crystallization in toluene-pentane of the yellow solid
yields pure yellow crystals of the pair of 4. The X-ray
diffraction analysis of the crystals indicates that 3 is
the racemic mixture RRu,RC-SRu,SC; while 4 is the
racemic mixture SRu,RC-RRu,SC.
CPh2 unit are observed at 137.9 (CH) and 141.3 (CPh2)
ppm, as singlets. The 31P{1H} NMR spectrum contains
a singlet at 63.1 ppm.
The above-mentioned spectroscopic data agree well
with those reported for related tertiary ruthenium-
azoniabutadienyl complexes.8,11 However, in the pres-
ence of bases, there are marked differences in behavior
between the known compounds of this type and 2. In
contrast to the general trend, the deprotonation of 2
does not occur at the CHdCPh2 group but at one of the
NCH2-carbon atoms. Although the allyl units are in-
equivalent, the deprotonation of both moieties is equally
favored. As a result, the treatment at room temperature
of 2 with sodium methoxide in tetrahydrofuran affords
a 1:1 isomeric mixture of the ruthenapyrrolinone com-
Figure 1 shows a view of the molecular geometry of
the enantiomer RRu,RC of 3. Selected bond distances and
angles are listed in Table 1.
The geometry around the ruthenium center is close
to octahedral, with the cyclopentadienyl ligand occupy-
ing three sites of a face. The angles formed by the
triisopropylphosphine and the CR atoms of the five-
membered ring are close to 93°, while the C(1)-Ru-
C(22) angle is 79.9(3)°. The ruthenapyrrolinone skeleton
is almost planar. The deviations from the best plane are
0.054(3)° (Ru), -0.058(3)° (C(1)), 0.026(4)° (N), 0.033-
(4)° (C(16)), and -0.055(4)° (C(22)).
The Ru-C(1) distance (1.884(6) Å) is similar to the
related bond lengths in the R, â-unsaturated carbene
compound [RuCl(CHCHdCPh2)(CO)(PiPr3)2]BF4 (1.874(3)
Å),15 the alkoxycarbene complex [Ru(κ3N-HBpz3)-
{C(OCH3)CH2CO2CH3}(dippe)]BPh4 (1.86(2) Å),16 and
the cyclopentadienylcarbene complexes [Ru(η5-C5H5)-
{C(OCH3)CH2CH3}(PPh3)2]PF6 (1.956(6) Å)17 and [Ru-
(η5-C5H5){C(OCH3)CH2Ph}(CHIRAPHOS)]PF6 (1.93(2)
plex (RRu,RC- SRu,SC)-Ru(η5-C5H5)[,C(CHdCPh2),
N(CH2CHdCH2)CH(CHdCH2)CdO}(PiPr3) (3) and the
pyrrolinyl compound (RRu,SC- SRu,RC)-Ru(η5-C5H5)-
{CdCH CP h 2 CH (CH dCH 2 )N CH 2 CH dCH 2 }(CO)-
(PiPr3) (4).
The formation of 3 involves the deprotonation of the
allyl group disposed trans to the CHdCPh2 unit, fol-
lowed by the intramolecular attack of the deprotonated
NCH-carbon atom to the carbonyl ligand. Complex 4 is
the result of the deprotonation of the allyl group trans
disposed to the metallic center and the subsequent
intramolecular nucleophilic attack of the deprotonated
NCH-carbon atom to the CPh2-carbon atom of the CHd
CPh2 moiety (Scheme 1).12 Both the formation of 3 and
the formation of 4 can be rationalized as dipolar 1,5-
electrocyclizations.13 This type of reactions has no
precedents in transition metal-allenylidene chemistry.
(13) (a) Bird, C. W.; Cheesman, G. W. H. In Comprehensive
Heterocyclic Chemistry; Katritzky, A. R., Rees, C. W., Eds.; Perga-
mon: Oxford, 1984; Vol. 4, Part 3, p 105. (b) Esteban, S.; Cornego, P.;
Barthelemy, C. Quı´mica Orga´nica Heterocı´clica; Universidad de Edu-
cacio´n a Distancia: Madrid, 1992; p 191.
(14) (a) Esteruelas, M. A.; Lo´pez, A. M. In Recent Advances in
Hydride Chemistry; Peruzzini, M., Poli, R., Eds.; Elsevier: Amsterdam,
2001; Chapter 7, pp 189-284. (b) Baya, M.; Buil, M. L.; Esteruelas,
M. A.; Lo´pez, A. M.; On˜ate, E.; Rodr´ıguez, J . R. Organometallics 2002,
21, 1841.
(15) Esteruelas, M. A.; Lahoz, F. J .; On˜ate, E.; Oro, L. A.; Zeir, B.
Organometallics 1994, 13, 4258.
(16) J ime´nez-Tenorio, M. A.; J ime´nez-Tenorio, M.; Puerta, M. C.;
Valerga, P. Organometallics 1997, 16, 5528.
(12) Only the enantiomers of 3 and
enantiomer of 2 are shown.
4
resulting from the SRu
(17) Bruce, M. I.; Humphrey, M. G.; Snow, M. R.; Tiekink, E. R. T.
J . Organomet. Chem. 1986, 314, 213.

4-Azoniaheptatrienyl Complexes of Ru
Organometallics, Vol. 22, No. 25, 2003 5277
Ta ble 1. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for th e En a n tiom er RRu ,RC
Ru (η5-C5H5)[,C(CHdCP h 2),N(CH2CHd
CH2)CH(CHdCH2)CdO}(P iP r 3) (3)
Ru-P
2.306(2)
1.884(6)
1.984(7)
2.310(8)
2.301(7)
2.274(6)
2.224(7
2.252(7)
1.219(7)
1.367(8)
N-C(16)
1.472(9)
1.451(8)
1.473(9)
1.336(9)
1.506(10)
1.530(10)
1.278(11)
1.477(11)
1.297(12)
Ru-C(1)
Ru-C(22)
Ru-C(32)
Ru-C(33)
Ru-C(34)
Ru-C(35)
Ru-C(36)
O-C(22)
N-C(1)
N-C(19)
C(1)-C(2)
C(2)-C(3)
C(16)-C(17)
C(16)-C(22)
C(17)-C(18)
C(19)-C(20)
C(20)-C(21)
P-Ru-C(1)
P-Ru-C(22)
P-Ru-Ma
C(1)-Ru-C(22)
C(1)-Ru-M
C(22)-Ru-M
Ru-C(1)-N
Ru-C(1)-C(2)
Ru-C(22)-O
92.96(18) N-C(1)-C(2)
113.9(6)
110.2(6)
108.0(6)
112.4(6)
113.0(6)
129.5(6)
131.6(7)
117.6(6)
93.8(2)
125.6
N-C(16)-C(17)
N-C(16)-C(22)
N-C(19)-C(20)
C(1)-N-C(16)
C(1)-N-C(19)
C(1)-C(2)-C(3)
C(16)-N-C(19)
C(16)-C(17)-C(18) 125.4(8)
C(17)-C(16)-C(22) 113.4(6)
C(19)-C(20)-C(21) 126.2(8)
79.9(3)
129.1
122.7
122.9(5)
122.9(5)
128.2(5)
F igu r e 1. Molecular diagram of the enantiomer RRu,RC
Ru(η5-C5H5)[,C(CHdCPh2),N(CH2CHdCH2)CH(CHd
CH2)CdO}(PiPr3) (3). Thermal ellipsoids are shown at 50%
Ru-C(22)-C(16) 115.4(5)
O-C(22)-C(16)
probability.
116.1(6)
a
Sch em e 2
M is the midpoint of the C(32)-C(36) Cp ligand.
Å).18 However, it is about 0.1 Å shorter than the Ru-C
distances found in the compounds fac,cis-[(PNP)RuCl2-
{C[NH{(S)-(-)-CH(Me)(1-naphthyl)}]CH2Ph}] (1.99(2)
Å)19 and Ru(η5-C5H5)I(CO){C(NHMe)Ph} (2.009(6) Å),20
which have been described as aminocarbene derivatives,
and about 0.14 Å shorter than the Ru-C bond length
reported for the azoniabutadienyl species [Ru(η5-C5H5)-
{C(CHdCPh2)dNEt2}(CO)(PiPr3)]BF4 (2.063(6) Å).8
The N-C(1) distance (1.367(8) Å) is about 0.1 Å
shorter than the N-C(19) and N-C(16) single-bond
lengths (1.451(8) and 1.472(9) Å, respectively), while it
is about 0.04 Å longer than the C-N distances found
in the “aminocarbene complexes” fac,cis-[(PNP)RuCl2-
{C[NH{(S)-(-)-CH(Me)(1-naphthyl)}]CH2Ph}] (1.32(2)
Å)19 and Ru(η5-C5H5)I(CO){C(NHMe)Ph} (1.301(7) Å)20
and the azoniabutadienyl derivative [Ru(η5-C5H5)-
{C(CHdCPh2)dNEt2}(CO)(PiPr3)]BF4 (1.306(7) Å).8 The
angles around the nitrogen atom are between 113.0(6)°
and 129.5(6)°, whereas the angles around C(1) are
between 113.9(6)° and 122.9(5)°.
the related bond lengths in the acyl derivative [Ru(η5-
C5H5){C(O)CHdCPh2}(CO)(PiPr3)]BF4 (1.502(3), 2.060-
(2), and 1.212(3) Å, respectively).21 In agreement with
the sp2-hybridization at C(22), the angles around this
atom are between 115.4(5)° and 128.2(5)°.
The IR and 1H, 13C{1H}, and 31P{1H} NMR spectra
of 3 are consistent with the structure shown in Figure
1. In the IR spectrum in Nujol, the most noticeable
absorption is that corresponding to the ν(CdO) vibra-
1
tion, which appears at 1581 cm-1. The H NMR spec-
trum in benzene-d6 shows the resonance corresponding
to the C(16)-H proton of the ruthenapyrrolinone skel-
eton at 4.02 ppm, as a doublet with a H-H coupling
constant of 8.7 Hz. In the 13C{1H} NMR spectrum, the
C(1) and C(22) carbon atoms display doublets at 262.2
and 259.8 ppm, with C-P coupling constants of 11.5 and
14.3 Hz, respectively, while the C(16) carbon atom gives
rise to a singlet at 91.9 ppm. The 31P{1H} NMR
spectrum contains a singlet at 67.9 ppm.
According to the previously mentioned structural
parameters, the bonding situation in the sequence Ru-
C(1)-N can be described as aminocarbene, with a
significant contribution of the resonance form B (Scheme
2). The contribution of the latter to the structure of 3 is
much smaller than the contribution of the related form
Figure 2 shows a view of the molecular geometry of
the enantiomer SRu,RC of the pyrrolinyl complex 4.
Selected bond distances and angles are listed in Table
2. The geometry around the ruthenium center is close
to octahedral, with the cyclopentadienyl ligand occupy-
ing a face. The P-Ru-C(36) and P-Ru-C(1) angles are
87.84(12)° and 89.83(10)°, respectively. These values
agree well with the ideal value of 90°. However the
C(1)-Ru-C(36) angle (99.65(15)°) strongly deviates
from 90°, suggesting that the heterocycle and the
carbonyl ligands experience a large steric hindrance.
to the structures of fac,cis-[(PNP)RuCl2{C[NH{(S)-(-)-
CH(Me)(1-naphthyl)}]CH2Ph}] and Ru(η5-C5H5)I(CO)-
{C(NHMe)Ph}.
The C(16)-C(22) (1.530(10) Å), Ru-C(22) (1.984(7) Å),
and O-C(22) (1.219 (7) Å) distances compare well with
(18) Consiglio, G.; Morandini, F.; Ciani, G. F.; Sirani, A. Organo-
metallics 1986, 5, 1976.
(19) Bianchini, C.; Masi, D.; Romerosa, A.; Zanobini, F.; Peruzzini,
M. Organometallics 1999, 18, 2376.
(20) Adams, H.; Bailey, N. A.; Ridgway, C.; Taylor, B. F.; Walters,
S. J .; Winter, M. J . J . Organomet. Chem. 1990, 394, 349.
(21) Esteruelas, M. A.; Go´mez, A. V.; Lahoz, F. J .; Lo´pez, A. M.;
On˜ate, E.; Oro, L. A. Organometallics 1996, 15, 3423.

5278 Organometallics, Vol. 22, No. 25, 2003
Buil et al.
Sch em e 3
F igu r e 2. Molecular diagram of the enantiomer SRu,RC
are statistically identical. They are about 0.07 Å longer
than the N-C(1) distance in 3 and support the existence
of N-C single bonds between the nitrogen and the C(1)
and C(19) atoms. The N-C(16) bond length (1.482(4)
Å) agrees well with a N-C(sp3) single bond.
R u (η5 -C 5 H 5 ){C dC H C P h 2 C H (C H dC H 2 )N C H 2 C H d
CH2}(CO)(PiPr3) (4). Thermal ellipsoids are shown at 50%
probability.
Ta ble 2. Selected Bon d Len gth s (Å) a n d An gles
The 1H, 13C{1H}, and 31P{1H} NMR spectra of 4 in
benzene-d6 are consistent with the structure shown in
(d eg) for th e En a n tiom er SRu ,RC
Ru (η5-C5H5){CdCHCP h 2CH(CHdCH2)NCH2CHd
CH2}(CO)(P iP r 3) (4)
1
Figure 2. In the H NMR spectrum the most noticeable
resonance is a singlet at 4.50 ppm, corresponding to the
C(2)-H proton. In the 13C{1H} NMR spectrum the C(1)
atom displays a doublet at 156.5 ppm, with a C-P
coupling constant of 12.7 Hz, while the C(2), C(16), and
C(3) atoms give rise to singlets at 115.4, 73.2, and 64.1
ppm, respectively. The 31P{1H} NMR spectrum contains
a singlet at 68.6 ppm.
Complex 4 reacts with tetrafluoroboric acid. The
addition of 1.0 equiv of this acid to a diethyl ether
solution of 4 gives the cationic derivative (RRu,SC-
Ru-P
2.3274(11)
2.077(4)
2.266(3)
2.272(3)
2.258(4)
2.246(4)
2.261(4)
1.796(4)
1.180(4)
1.430(4)
N-C(16)
1.482(4)
1.429(4)
1.346(4)
1.522(5)
1.555(5)
1.496(5)
1.312(5)
1.446(6)
1.271(6)
Ru-C(1)
Ru-C(31)
Ru-C(32)
Ru-C(33)
Ru-C(34)
Ru-C(35)
Ru-C(36)
O-C(36)
N-C(1)
N-C(19)
C(1)-C(2)
C(2)-C(3)
C(3)-C(16)
C(16)-C(17)
C(17)-C(18)
C(19)-C(20)
C(20)-C(21)
P-Ru-C(1)
P-Ru-C(36)
P-Ru-Ma
C(1)-Ru-C(36)
C(1)-Ru-M
C(36)-Ru-M
Ru-C(1)-N
Ru-C(1)-C(2)
N-C(1)-C(2)
89.83(10)
87.84(12)
129.9
99.65(15)
118.1
N-C(16)-C(3)
N-C(16)-C(17)
C(1)-N-C(16)
C(1)-N-C(19)
C(1)-C(2)-C(3)
C(2)-C(3)-C(16)
C(3)-C(16)-C(17)
C(16)-N-C(19)
103.0(3)
111.7(3)
109.1(3)
124.9(3)
113.6(3)
99.2(3)
S
Ru,RC)-[Ru(η5-C5H5){CdN(CH2CHdCH2)CH(CHdCH2)-
CPh2CH2}(CO)(PiPr3)BF4 (5), which was isolated as a
yellow solid in 85% yield. Complex 5, which is an isomer
of 2, is the result of the addition of the proton of the
acid to the C(2) atom of 4 (Scheme 3).
122.9
130.1(2)
122.7(3)
107.1(3)
113.6(3)
116.2(3)
The crystallization of the yellow solid in methanol-
toluene affords crystals suitable for an X-ray diffraction
study. Figure 3 shows a view of the structure of the
cation of the enantiomer RRu,Sc of 5. Selected bond
distances and angles are collected in Table 3. The
geometry around the ruthenium atom is like that of 4,
i.e., close to octahedral with the cyclopentadienyl ligand
occupying one face. In this case, the heterocycle experi-
ences steric hindrance with both the carbonyl and the
phosphine ligands. This is revealed by the angles C(1)-
Ru-C(27) (94.19(18)°) and P-Ru-C(1) (96.25(12)°),
which are greater than the ideal value of 90°. As a
consequence of the opening of these angles, the P-Ru-
C(27) angle is reduced to 86.00(16)°.
The Ru-C(1) distance (2.010(4) Å) is about 0.12 Å
longer than the Ru-C(1) bond length in 3 and only 0.06
Å shorter than the Ru-C(1) distance in 4. The Ru-C(1)
distance in 5 compares well with the Ru-C distance in
the azoniabutadienyl derivative [Ru (η5-C5H5){C(CHd
CPh2)dNEt2}(CO)(PiPr3)]BF4 (2.063(6) Å), where the
contribution of the R,â-unsaturated aminocarbene reso-
nance form to the structure of the complex is not
relevant.8 The N-C(1) distance (1.317(4) Å) is statiscally
a
M is the midpoint of the C(31)-C(35) Cp ligand.
This appears to be a consequence of the presence of an
allyl substituent at the nitrogen atom.
The heterocycle contains a double bond between the
C(1) and C(2) atoms (1.346(4) Å). The Ru-C(1) distance
(2.077(4) Å), which is about 0.2 Å longer than the Ru-
C(1) bond length in 3, compares well with those found
in the alkenyl complexes [Ru{(E)-CHdCHCMe3}Cl(CO)-
(Me2Hpz)(PPh3)2] (2.063(7) Å)22a and [Ru{(E)-CHd
CHCMe3}(CO){NHdC(Me)(Me2Hpz)}(PPh3)2]PF6 (2.067-
(8) Å).22b This distance lies between those reported for
the allenyl derivatives Ru(η5-C5H5){C(CtCPh)dCd
CPh2}(CO)(PiPr3) (2.004(5) Å)6d and [Ru(η5-C5H5)-
{C(PHPh2)dCdCPh2}(CO)(PiPr3)]BF4 (2.139(5) Å),22c
where a Ru-C(sp2) single bond is proposed to exist. The
N-C(1) (1.430(4) Å) and N-C(19) (1.429(4) Å) distances
(22) (a) Romero, A.; Santos, A.; Vegas, A. Organometallics 1988, 7,
1988. (b) Lo´pez, J .; Santos, A.; Romero, A.; Echavarren, A. M. J .
Organomet. Chem. 1993, 443, 221. (c) Esteruelas, M. A.; Go´mez, A.
V.; Lo´pez, A. M.; Modrego, J .; On˜ate, E. Organometallics 1998, 17,
5434.

4-Azoniaheptatrienyl Complexes of Ru
Organometallics, Vol. 22, No. 25, 2003 5279
C-P coupling constant of 9.6 Hz, while the C(16), C(2),
and C(3) atoms display singlets at 75.5, 56.1, and 55.1
ppm, respectively. The 1H NMR spectrum is complex
1
and uninformative; according to the H-13C HETCOR
NMR spectrum, the resonances corresponding to the
CH2 protons of the five membered hetero-ring are
observed at 5.17 and 4.20 ppm.
The isomerization of 5 affords the N-allyl-4-azonia-
1,3,5-heptatrienyl derivative [Ru(η5-C5H5){C(CHd
CPh2)dN(CHdCHCH3)CH2CHdCH2}(CO)(PiPr3)]BF4 (6
in Scheme 3). The process involves the opening of the
five-membered hetero-ring, formally as a consequence
of the split of the C(3)-C(16) bond, along with a proton
transfer from C(2) to C(18). In dichloromethane at room
temperature, the transformation of 5 into 6 is quantita-
tive after 2 h.
During the isomerization of 5 into 6, the formation of
spectroscopically detectable concentrations of 2 was not
observed, suggesting that 6 is more stable than 2 from
a thermodynamic point of view. In accordance with this,
in dichloromethane at room temperature, the transfor-
mation of 6 into 2 does not occur, even after a week.
However, the isomerization of 2 into 6 is also not
observed. In agreement with the kinetic inertia of 2,
several studies have indicated that the isomerization
of N,N-allylamines into the corresponding enamines
usually requires the presence of t-BuOK, LDA, or KH
as catalysts.24 Such a 1,3 sigmatropic rearrangement
has been also observed in a byproduct during the ring-
closing metathesis of N,N-diallyltosylamide catalyzed
by the complex [p-(cymene)RuCl(PCy3)(dCdCdCPh2)]-
BF4.25
F igu r e 3. Molecular diagram of the cation of the enanti-
omer RRu,SC [Ru(η5-C5H5){CdN(CH2CHdCH2)CH(CHd
CH2)CPh2CH2}(CO)(PiPr3)BF4 (5). Thermal ellipsoids are
shown at 50% probability.
Ta ble 3. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for th e En a n tiom er RRu ,SC
[Ru (η5-C5H5){CdN(CH2CHdCH2)CH(CHd
CH2)CP h 2CH2}(CO)(P iP r 3)BF 4 (5)
Ru-P
2.3434(13)
2.010(4)
2.257(4)
2.245(4)
2.246(4)
2.247(5)
2.231(4)
1.837(4)
1.317(4)
N(1)-C(16)
N(1)-C(19)
C(1)-C(2)
1.492(5)
1.468(5)
1.525(6)
1.557(6)
1.547(6)
1.488(6)
1.305(6)
1.476(6)
1.313(6)
Ru-C(1)
Ru-C(22)
Ru-C(23)
Ru-C(24)
Ru-C(25)
Ru-C(26)
Ru-C(27)
N(1)-C(1)
C(2)-C(3)
C(3)-C(16)
C(16)-C(17)
C(17)-C(18)
C(19)-C(20)
C(20)-C(21)
Complex 6 was isolated as a yellow solid. The pres-
ence of the N-allyl-4-azonia-1,1-diphenyl-1,3,5-heptatrien-
P-Ru-C(1)
P-Ru-C(27)
P-Ru-Ma
C(1)-Ru-C(27)
C(1)-Ru-M
C(27)-Ru-M
Ru-C(1)-N
Ru-C(1)-C(2)
96.25(12)
86.00(16)
127.5
94.19(18)
117.3
126.7
131.1(3)
123.6(3)
N(1)-C(1)-C(2)
N(1)-C(16)-C(17)
C(1)-N(1)-C(16)
C(1)-N(1)-C(19)
C(1)-C(2)-C(3)
C(2)-C(3)-C(16)
C(3)-C(16)-C(17)
C(16)-N(1)-C(19)
104.3(4)
108.5(4)
116.0(4)
126.7(4)
108.0(4)
98.7(4)
1
3-yl ligand is strongly supported by the IR and the H
and 13C{1H} NMR spectra. The IR spectrum in Nujol
shows bands at 1640 and 1599 cm-1, corresponding to
the C-N and C-C double bonds. In the 1H NMR
spectrum in dichloromethane-d2, the resonance due to
the protons of the methyl group appears at 1.92 ppm,
as a double doublet with H-H coupling constants of 6.9
and 1.5 Hz, whereas the resonance corresponding to the
olefinic dCHCH3 proton is observed at 6.08 ppm, as a
doublet quartet, by spin coupling with the methyl
protons and the NCHd proton. The value of the coupling
constant corresponding to the latter (13.8 Hz) is con-
sistent with a trans disposition of the methyl group and
nitrogen atom at the carbon-carbon double bond. Ac-
cording to the 1H-1H COSY and 1H-13C HETCOR
spectra, the resonance corresponding to the NCHd
proton lies at 7.06 ppm, masked between the phenyl
resonances. The allyl substituent displays resonances
at 5.65 (CHd), 5.26 and 4.72 (CH2), and 5.23-5.14 (d
CH2) ppm. The resonance due to the CHd proton of the
CHdCPh2 unit appears at 6.79 ppm, as a singlet. In
the 13C{1H} NMR spectrum, the resonances correspond-
ing to the propenyl group of the azoniaheptatrienyl
skeleton are observed at 137.1 (NCHd), 120.9 (d
116.4(4)
116.0(3)
a
M is the midpoint of the C(22)-C(26) Cp ligand.
identical with the length of the C-N double bond in the
above-mentioned azoniabutadienyl derivative (1.306(7)
Å) and about 0.17 Å shorter than the N-C(19) (1.468-
(5) Å) and N-C(16) (1.492(5) Å) distances, which are
statistically identical and agree well with C(sp3)-N
single bonds. The angles around the N atom are between
116.0(4)° and 126.7(4)°. The C(1)-C(2) (1.525(6) Å),
C(2)-C(3) (1.557(6) Å), and C(3)-C(16) (1.547(6) Å)
distances are consistent with C(1)-C(2), C(2)-C(3), and
C(3)-C(16) single bonds.23
In the solid state, complex 5 is stable at room
temperature. However in dichloromethane as solvent,
it evolves to afford a new isomer (vide infra). As a
1
consequence, the 31P{1H}, 13C{1H}, and H NMR spectra
of 5 were recorded at -80 °C. At this temperature, the
31P{1H} NMR spectrum contains a singlet at 61.3 ppm.
In the 13C{1H} NMR spectrum, the most noticeable
resonances are those corresponding to the carbon atoms
of the five-membered skeleton of the heterocycle. The
C(1) atom gives rise to a doublet at 243.5 ppm, with a
(24) (a) Sauer, J .; Prahl, H. Tetrahedron Lett. 1966, 2863. (b) Riviere,
M.; Lattes, A. Bull. Soc. Chim. Fr. 1968, 4430. (c) Sauer, J .; Prahl, H.
Chem. Ber. 1969, 102, 1917. (d) Beeken, P.; Fowler, F. W. J . Org. Chem.
1980, 45, 1336. (e) Eish, J . J .; Shah, J . H. J . Org. Chem. 1991, 56,
2955.
(25) Fu¨rstner, A.; Liebl, M.; Lehmann, C. W.; Picquet, M.; Kunz,
R.; Bruneau, C.; Touchard, D.; Dixneuf, P. H. Chem. Eur. J . 2000, 6,
1847.
(23) Orpen, A. G.; Brammer, L.; Allen, F. H.; Kennard, O.; Watson,
D. G.; Taylor, R. J . Chem. Soc., Dalton Trans. 1989, S1.

5280 Organometallics, Vol. 22, No. 25, 2003
Buil et al.
Sch em e 4
of metallaheterocyclic or heterocyclic compounds related
to 3 and 4 was not observed.
The behavior of 7 is the same as that previously
reported for secondary azoniabutadienyl derivatives,
where the deprotonation at the nitrogen atom is favored
with regard to the deprotonation at the CHdCPh2 unit.
The comparison of the behavior of 7 with that of 2
indicates that in secondary 4-azonia-1,3,6-heptatrien-
3-yl derivatives the deprotonation at the nitrogen atom
is more favored than the deprotonation at the NCH2-
carbon atom of the allyl group. So, since the comparison
of the behavior of 2 with that of the previously reported
tertiary azoniabutadienyl compounds shows that the
deprotonation at the NCH2- carbon atom is more
favored than the deprotonation at the CHdCPh2 unit,
the results here reported reveal that in 4-azonia-1,3,6-
heptatrien-3-yl ligands the Bro¨nsted acidity decreases
in the sequence NH > NCH2 > CHdCPh2.
The most noticeable feature in the IR spectrum of 8
in Nujol is the absence of any ν(NH) band. The ν(CdN)
and ν(CdC) vibrations are observed at 1599 and 1541
CHCH3), and 15.5 (CH3) ppm, as singlets, whereas those
corresponding to the allyl substituent appear at 128.5
(CHd), 121.8 (dCH2), and 57.7 (NCH2) ppm also as
singlets. The Ru-C carbon atom gives rise to a doublet
at 247.8 ppm, with a C-P coupling constant of 9.4 Hz,
while the resonances due to CH and CPh2 carbon atoms
of the CHdCPh2 unit are observed at 138.2 and 138.9
ppm, respectively. The 31P{1H} NMR spectrum contains
a singlet at 63.1 ppm.
2. Allyla m in e. Similarly to diallylamine, one of the
N-H bonds of allylamine is added to the CR-Câ double
bond of the allenylidene ligand of 1 to afford the
secondary 4-azonia-1,3,6-heptatrienyl derivative [Ru(η5-
C5H5){C(CHdCPh2)dNH(CH2CHdCH2)}(CO)(PiPr3)]-
BF4 (7 in Scheme 4), which was isolated as a yellow solid
in 86% yield.
The IR spectrum of 7 in Nujol shows a ν(NH) band at
3316 cm-1, along with ν(CdN) and ν(CdC) bands at
1613 and 1545 cm-1. In the 1H NMR spectrum in
chloroform-d, the most noticeable resonances are those
due to the dNH proton and the dCH hydrogen atom of
the CHdCPh2 unit, which are observed as singlets at
9.92 and 6.55 ppm, respectively. The resonances corre-
sponding to the allyl group appear at 5.91 (CHd), 5.28
and 5.27 (dCH2), and 4.37 (CH2). In the 13C{1H} NMR
spectrum the CR atom displays a doublet at 243.3 ppm,
with a C-P coupling constant of 10.6 Hz, while the
olefinic carbon atoms of the unit CHdCPh2 give rise to
singlets at 141.3 (dCPh2) and 133.8 (dCH) ppm. The
allyl resonances are observed at 129.0 (CHd), 121.3
(dCH2), and 55.1 (NCH2) ppm, also as singlets. The 31P-
{1H} NMR spectrum shows a singlet at 63.1 ppm.
According to the behavior observed for 2 and those
previously reported for the azoniabutadienyl ligands
stabilized by the [Ru(η5-C5H5)(CO)(PiPr3)]+ metallic
fragment,8 at first glance, the 4-azonia-1,3,5-heptatrie-
nyl ligand of 7 could have three Bro¨nsted acidic cen-
ters: the NH group, the dCH- of the CHdCPh2 moiety,
and the CH2- unit of the allyl group. However, the
addition of 2.0 equiv of sodium methoxide to a tetrahy-
drofuran solution of 7 selectively deprotonates the
nitrogen atom. The reaction affords the neutral 4-aza-
1,3,6-heptatrienyl complex Ru(η5-C5H5){C(CHdCPh2)d
NCH2CHdCH2}(CO)(PiPr3) (8 in Scheme 4), which was
isolated as a yellow solid in 70% yield. The formation
1
cm-1. The H NMR spectrum in benzene-d6 shows the
CHd resonance of the CHdCPh2 unit at 6.85 ppm, as
a singlet, whereas the resonances corresponding to the
allyl unit are observed at 6.25 (CHd), 5.31 and 5.12 (d
CH2), and 4.47 and 4.25 (CH2) ppm. The 13C{1H} NMR
spectrum shows a doublet at 195.4 with a C-P coupling
constant of 11.5 Hz, corresponding to the CR atom. The
resonances due to the CHd and dCPh2 carbon atoms
of the CHdCPh2 unit are observed as singlets at 141.2
and 141.6 ppm, respectively. The allyl carbon atoms also
display singlets at 139.0 (CHd), 113.8 (dCH2), and 60.9
(NCH2) ppm. The 31P{1H} NMR spectrum shows a
singlet at 68.9 ppm.
In solution complex 8 is unstable and isomerizes into
the conjugated 4-aza-1,3,5-heptatrienyl derivative Ru-
(η5-C5H5){C(CHdCPh2)dNCHdCHCH3}(CO)(PiPr3) (9
in Scheme 4). In benzene-d6 at 70 °C, the transformation
is almost quantitative after 24 h. The formation of 9
involves a 1,3-hydrogen shift within the allyl unit of 8.
In this context, we note that the treatment of secondary
allylamines with sodium-alkyl reagents promotes the
deprotonation of the nitrogen atom, to afford sodium
amides where the allyl group has undergone a 1,3-
sigmatropic rearrangement.26 In contrast the treatment
of secondary allylamines with lithium-alkyl reagents
promotes a double deprotonation, which takes place at
both the nitrogen atom and the dCH2 carbon atom of
the allyl group. In this case, the deprotonation is not
accompanied by the isomerization of the allyl chain.27
Complex 9 was isolated at -78 °C from a saturated
pentane solution, as yellow microcrystals. In the absence
of the solvent, the crystals are unstable and evolve into
a yellow oil. Crystals containing two benzene-d6 mol-
ecules and suitable for an X-ray diffraction study were
obtained in a NMR tube, from a benzene-d6 solution.
Figure 4 shows a view of the structure of this compound,
and selected bond distances and angles are collected in
Table 4.
(26) Andrews, P. C.; Calleja, S. M.; Maguire, M.; Nichols, P. J . Eur.
J . Inorg. Chem. 2002, 1583.
(27) (a) Yus, M.; Foubelo, F.; Falvello, L. R. Tetrahedron: Asymmetry
1995, 6, 2081. (b) Andrews, P. C.; Calleja, S. M.; Maguire, M. J . Chem.
Soc., Dalton Trans. 2002, 3640.

4-Azoniaheptatrienyl Complexes of Ru
Organometallics, Vol. 22, No. 25, 2003 5281
to the C(1), C(6), C(2), C(5), C(3), and C(4) carbon atoms,
respectively, of the azaheptatrienyl skeleton. The 31P-
{1H} NMR spectrum contains a singlet at 69.2 ppm.
Con clu d in g Rem a r k s
We have recently reported that, from the organome-
tallic and organic synthesis point of view, the potential-
ity of the transition metal allenylidene compounds can
become greater than that of the carbene complexes of
type LnMdCR2.11 This paper gives new evidence point-
ing in this direction. The hydroamination of the alle-
nylidene ligand of [Ru(η5-C5H5)(dCdCdCPh2)(CO)(Pi-
Pr3)]BF4 with allylamines increases the number of
reactive centers of the starting complex, including the
carbonyl group, and generates 4-azonia-1,3,6-heptatrie-
nyl species with three alternative Bro¨nsted acidic points.
As a consequence of the versatile chemistry of this new
F igu r e 4. Molecular diagram of the complex Ru(η5-C5H5)-
{C(CHdCPh2)dNCHdCHCH3}(CO)(PiPr3) (9). Thermal el-
lipsoids are shown at 50% probability.
type of species, the novel metallaheterocycle Ru(η5-
C5H 5)[,C(CH dCP h 2),N (CH 2CH dCH 2)CH (CH d
CH2)CdO}(PiPr3), the heterocycles Ru(η5-C5H5){Cd
CHCPh2CH(CHdCH2)NCH2CHdCH2}(CO)(PiPr3) and
[Ru (η5 -C5 H 5 ){CdN (CH 2 CH dCH 2 )CH (CH dCH 2 )-
Ta ble 4. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for th e Com p lex Ru (η5-C5H5){C(CHdCP h 2)d
NCHdCHCH3}(CO)(P iP r 3) (9)
Ru-P
2.3245(11)
2.071(4)
2.276(4)
2.274(4)
2.261(4)
2.251(4)
2.265(4)
Ru-C(24)
N-C(1)
1.831(4)
1.303(4)
1.404(5)
1.491(5)
1.331(5)
1.343(5)
Ru-C(1)
Ru-C(19)
Ru-C(20)
Ru-C(21)
Ru-C(22)
Ru-C(23)
N-C(2)
C(1)-C(5)
C(2)-C(3)
C(5)-C(6)
CPh2CH2}(CO)(PiPr3)BF4, and the conjugated azahep-
tatrienyl derivative Ru(η5-C5H5){C(CHdCPh2)dNCHd
CHCH3}(CO)(PiPr3) have been discovered and fully
characterized, including X-ray diffraction analysis.
P-Ru-C(1)
P-Ru-C(24)
P-Ru-Ma
C(1)-Ru-C(24)
C(1)-Ru-M
C(24)-Ru-M
Ru-C(1)-N
92.02(10)
94.47(12)
126.0
91.79(15)
118.1
Ru-C(1)-C(5)
N-C(1)-C(5)
N-C(2)-C(3)
C(1)-N-C(2)
C(1)-C(5)-C(6)
C(2)-C(3)-C(4)
118.6(3)
121.2(3)
122.2(4)
118.9(3)
129.8(4)
124.1(4)
Exp er im en ta l Section
125.3
120.1(3)
All reactions were carried out with rigorous exclusion of air
using standard Schlenk techniques. Solvents were dried by
known procedures and distilled under argon prior to use. The
starting material [Ru(η5-C5H5)(CdCdCPh2)(CO)(PiPr3)]BF4 (1)
was prepared as described.21 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 atom labels for complexes 3, 4, 5, and 9 are the same as
those in Figures 1-4, respectively.
a
M is the midpoint of the C(22)-C(26) Cp ligand.
The geometry around the ruthenium center is close
to octahedral, with the cyclopentadienyl ligand occupy-
ing a face. The angles formed by the triisopropylphos-
phine, the carbonyl, and the azaheptatrienyl ligands are
between 91.79(15)° (C(1)-Ru-C(24)) and 94.47(12)° (P-
Ru-C(24)), indicating that, in this case, the ligands do
not experience a significant steric hindrance.
The azaheptatrienyl ligand coordinates to the ruthe-
nium center by the C(1) atom, which is disposed in R
position with regard to the nitrogen. The Ru-C(1)
distance (2.071(4) Å) is statiscally identical with the
Ru-C(1) bond length in 4 and consistent with a Ru-
C(sp2) single bond. The bond lengths in the sequence
C(3)-C(2)-N-C(1)-C(5)-C(6)(1.331(5),1.404(5),1.303(4),
1.491(5), and 1.343(5) Å) support the 4-aza-1,3,5-hep-
tatrienyl formulation. Both C(2)-C(3) and N-C(1)
double bonds show an E configuration.
P r ep a r a tion of [Ru (η5-C5H5){C(CHdCP h 2)dN(CH2CHd
CH2)2}(CO)(P iP r 3)]BF 4 (2). A deep red solution of [Ru(η5-
C5H5)(dCdCdCPh2)(CO)(PiPr3)]BF4 (1) (200 mg, 0.32 mmol)
in 6 mL of dichloromethane was treated with diallylamine
(43.5 µL, 0.352 mmol). The mixture was stirred for 15 min at
room temperature, and the solution became yellow. The
solvent was removed in vacuo, and the residue was treated
with 6 mL of diethyl ether at -70 °C to afford a pale yellow
suspension. The solution was decanted, and the solid was
washed twice with diethyl ether and dried in vacuo. Yield: 220
mg (94%). Anal. Calcd for C36H44BF4NOPRu: C, 59.34; H, 6.50;
N, 1.92. Found: C, 59.10; H, 6.65; N, 1.97. IR (Nujol, cm-1):
ν(CO) 1936(vs), ν(CdN) and ν(CdC) 1639(m) and 1598(w), ν-
(BF4) 1105(br). 1H NMR (300 MHz, 293 K, CDCl3): δ 7.51-
7.05 (m, 10H, Ph), 6.73 (s, 1H, dCH), 5.81 (m, 1H, CHdCH2),
The 1H NMR spectrum of 9 in chloroform-d agrees
well with the structure shown in Figure 4. The methyl
group of the azaheptatrienyl skeleton displays a doublet
at 1.70 ppm, with a H-H coupling constant of 6.9 Hz,
whereas the C(3)HdC(2)H unit gives rise to a doublet
at 7.38 (C(2)H) ppm and a double quartet at 5.89 (C(3)H)
ppm, with a trans H-H coupling constant of 13.2 Hz.
The resonance corresponding to the C(5)H proton ap-
pears at 7.03 ppm, as a singlet. In the 13C{1H} NMR
spectrum, the most noticeable resonances are a doublet
(J (C-P) ) 12.9 Hz) at 206.1 ppm and five singlets at
144.4, 142.3, 140.6, 118.5, and 15.3 ppm, corresponding
3
5.70 (m, 1H, CHdCH2), 5.60 (d, J H-H ) 17.1, 1H, dCH2, H
3
cis to NCH2), 5.54 (d, J H-H ) 10.5, 1H, dCH2, H trans to
3
NCH2), 5.28 (d, J H-H ) 10.2, 1H, dCH2, H trans to NCH2),
5.10 (d, 3J H-H ) 16.5, 1H, dCH2, H cis to NCH2), 4.83 (m, 1H,
NCH2), 4.78 (m, 1H, NCH2), 4.70 (s, 5H, Cp), 4.64 (m, 1H,
NCH2), 4.36 (m, 1H, NCH2), 2.31 (m, 3H, PCHCH3), 1.21 (dd,
18H, J H-H ) 7.2, J P-H ) 14.7, PCHCH3). 13C{1H} NMR (75.4
MHz, 293 K, CDCl3): δ 244.9 (d, J P-C ) 9.4, Ru-CR), 204.3 (d,
J P-C ) 18.2, CO), 141.3 (s, dCPh2), 138.7 and 138.2 (both s,
C
ipso Ph), 137.9 (s, dCH), 130.2, 129.3, 128.4, 128.3 (all s, Ph),
128.7 and 128.6 (both s, CHd), 123.3 and 123.1 (both s, d

5282 Organometallics, Vol. 22, No. 25, 2003
Buil et al.
19A
19B
19A
20
CH2), 86.4 (s, Cp), 64.4 and 57.8 (both s, NCH2), 28.6 (d, J P-C
) 23.2, PCHCH3), 20.1 and 19.9 (both s, PCHCH3). 31P{1H}
NMR (121.4 MHz, 293 K, CDCl3): δ 63.1 (s).
(dd, 1H, J H
) 15.2, J H
) 3.9, NCHH19A), 4.69 (d,
19B
-H
-H
) 9.9, CH16), 4.50 (s, 1H, dCH2), 3.78 (dd, J H
16
17
19A
1H, J H
-H
-H
) 15.2, J H
293 K, plus APT, plus HETCOR, C6D6): δ 209.7 (d, J P-C
) 6.7, NCHH19B). 13C{1H} NMR (75.4 MHz,
19B
20
-H
)
Dep r ot on a t ion
of
[R u (η5-C5H 5){C(CHdCP h 2)dN-
21.7, CO), 156.5 (d, J P-C ) 12.7, Ru-C1), 150 and 148.9 (both
s, Cipso), 139.2 (s, C20Hd), 138.1 (s, C17Hd), 130.5, 128.3, 127.4,
127.1, 126.4, 126.0, 125.2 (all s, CPh), 116.8 (s, dC18H2), 115.7
(s, dC21H2), 115.4 (s, C2Hd), 86.4 (s, Cp), 73.2 (s, NC16H), 64.1
(s, C3Ph2), 53.7 (s, NC19H2), 26.6 (d, J P-C ) 22.6, PCHCH3),
20.9 and 19.8 (both s, PCHCH3). 31P{1H} NMR (121.4 MHz,
293 K, C6D6): δ 68.6 (s). MS (FAB+): m/z 642 (M+ + H).
(CH2CHdCH2)2}(CO)(P iP r 3)]BF 4 (2) w ith Sod iu m Meth -
oxid e. F or m a t ion of t h e Isom er ic Mixt u r e (RR u ,RC-
S
Ru ,SC)-Ru (η5-C5H5)[,C(CHdCP h 2),N(CH2CHdCH2)CH-
(CHdCH2)CdO}(P iP r 3) (3) a n d (RRu ,SC- SRu ,RC)-Ru (η5-
C 5H 5){C dC H C P h 2C H (C H dC H 2)N C H 2C H dC H 2}(C O )-
(P iP r 3) (4). A pale yellow solution of [Ru(η5-C5H5){C(CHd
CPh2)dN(CH2CHdCH2)2}(CO)(PiPr3)] (2) (400 mg, 0.55 mmol)
in 6 mL of tetrahydrofuran was treated with sodium methoxide
(59.8 mg, 1.09 mmol). The mixture was stirred for 15 min at
room temperature, and the color changed to deep red. The
solvent was removed in vacuo. Dichloromethane was added,
and the suspension was filtered to eliminate sodium tetrafluo-
roborate. The solvent was removed in vacuo, and the residue
was treated with 6 mL of pentane to afford an orange
suspension. The solution was decanted, and the solid was
washed twice with pentane and dried in vacuo. The solid
P r ep a r a t ion of (RR u ,SC- SR u ,RC)-[R u (η5-C5H 5){CdN-
(CH2CHdCH2)CH(CHdCH2)CP h 2CH2}(CO)(P iP r 3)BF 4 (5).
An orange suspension of Ru(η5-C5H5){CdCHCPh2CH(CHd
CH2)NCH2CHdCH2}(CO)(PiPr3) (4) (110 mg, 017 mmol) in 6
mL of diethyl ether was treated with tetrafluoroboric acid (23.5
µL, 017 mmol). After 5 min at room temperature a yellow solid
was formed. The mixture was stirred for 15 min. The solution
was decanted, and the solid was washed twice with diethyl
ether and dried in vacuo. Yield: 106 mg (85%). Anal. Calcd
for C36H47NOPRuBF4: C, 59.34; H, 6.50; N, 1.92. Found: C,
58.86; H, 6.08, N, 2.10. IR (Nujol, cm-1): ν(CO) 1947 (s), ν-
obtained was a mixture of two isomers, Ru(η5-C5H5)[,C(CHd
CPh2),N(CH2CHdCH2)CH(CHdCH2)CdO}(PiPr3) (3) and Ru-
1
(CdC) and ν(CdN) 1642 and 1593. H NMR (300 MHz, CD2-
Cl2, 193 K): δ 7.37-7.05 (m, 10H, Ph), 5.94 (m, 1H, CH20d),
5.73 (br, 1H, dCH17), 5.71 (br, 1H, dCH2 or dCH218), 5.47
21
(η5-C5H5){CdCHCPh2CH(CHdCH2)NCH2CHdCH2}(CO)(Pi-
Pr3) (4) in a 1:1 molar ratio. Yield: 282 mg (80%). Washing
the mixture several times with pentane leads to the separation
of the two isomers. Complex 4 was obtained as a yellow solid
and complex 3 was obtained as pure orange crystals from a
saturated solution of the mixture in pentane at -20 °C.
(br, 1H, NCH16), 5.46 (br, 1H, dCH2 or dCH218), 5.34 (s, 5H,
21
Cp), 5.17 (br, 1H, CHH2A), 4.20 (m, 1H, CHH2B), 3.92 (m, 1H,
NC19H2), 3.81 (m, 1H, NC19H2), 2.16 (br, 3H, PCHCH3), 1.10
(br, 18H, PCHCH3). 13C{1H} NMR (75.4 MHz, CD2Cl2, 193 K
plus APT plus HETCOR): δ 243.5 (d, J P-C ) 9.6, Ru-C1), 204.8
(d, J P-C ) 17.9, Ru-CO), 143.9 and 141.1 (both s, Cipso), 129.7
and 129.1 (both s, C20Hd and C17Hd), 128.4, 128.2, 128.0,
127.3, 126.8, and 126.4 (all s, CPh), 124.6 and 124.3 (both s,
dC18H2 and dC21H2), 75.5 (s, NC16H), 65.6 (s, NC19H2), 56.1
(s, C2H2), 55.1 (s, C3Ph2), 18.8 (br, PCHCH3), 14.8 (s, PCHCH3).
31P{1H} NMR (121.4 MHz, CD2Cl2, 193 K): δ 61.3 (s).
Sp ectr oscop ic d a ta for 3:28 IR (Nujol, cm-1): ν(CdC)
1635, ν(CO) 1581 (s). 1H NMR (300 MHz, C6D6, 293 K): δ
16
17
17
18A
7.41-7.02 (m, 10H, Ph), 5.73 (ddd, 1H, J H
) 8.7, J H
-H
-H
19A
17
18B
20
) 10.2, J H
) 17.1, CH17d), 5.52 (dddd, 1H, J HH
)
-H
-H
) 8.7, J H
) 11.1, J H
) 17.7, CH20d
20
5.7, J H
-H
19B
20
21A
20
21B
-H
20
-H
21B
21A
21A
21A
CH2), 5.30 (dd, 1H, J H
H trans to NCH2), 5.24 (dd, 1H, J H
) 11.1, J H
) 1.8, CHdCH
,
-H
-H
20
P r ep a r a t ion of [R u (η5-C5H 5){C(CH dCP h 2)dN(CH d
CHCH3)CH2CHdCH2}(CO)(P iP r 3)]BF 4 (6). A yellow solu-
21B
21A
21B
) 17.7, J H
)
-H
-H
1.8, CHdCH21B, H cis to NCH2), 4.87 (s, 5H, Cp), 4.84 (d, 1H,
18A
17
18B
17
J H
) 10.2, CHdCH18A H cis to H17), 4.82 (d, 1H, J H
tion
of
[Ru(η5-C5H5){CdN(CH2CHdCH2)CH(CHdCH2)-
-H
-H
19B
) 17.1, CHdCH18B H trans to H17), 4.64 (dd, 1H, J H
)
19A
-H
CPh2CH2}(CO)(PiPr3)BF4 (5) (150 mg, 121 mmol) in 5 mL of
dichloromethane was stirred for 2 h at room temperature. The
solvent was removed in vacuo, and the residue was treated
with 5 mL of diethyl ether to afford a yellow suspension. The
solution was decanted, and the solid was dried in vacuo. The
solid was crystallized at room temperature from dichlo-
romethane-diethyl ether to give amber crystals. Yield: 120
mg (80%). Anal. Calcd for C36H47NOPRuBF4: C, 59.34; H, 6.50;
N, 1.92. Found: C, 58.98; H, 6.11, N, 2.09. IR (Nujol, cm-1):
ν(CO) 1951 (vs), ν(CdN) and ν(CdC) 1640 (m) and 1599 (w),
ν(BF4) 1053 (br). 1H NMR (300 MHz, CD2Cl2, 293 K plus
COSY): δ 7.46-6.96 (m, 11H, Ph + NCHd), 6.79 (s, 1H, CHd
CPh2), 6.08 (dq, 1H, J H-H ) 13.8, J H-H ) 6.9, dCHCH3), 5.65
(m, 1H, CHdCH2), 5.26 (m, 4H, NCH2), 5.23-5.14 (m, 2H, d
CH2), 4.72 (m, 1H, NCH2), 2.30 (m, 3H, PCHCH3), 1.92 (dd,
3H, J H-H ) 6.9, J H-H ) 1.5, CH3), 1.28 (dd, 9H, J H-H ) 7.1,
J P-H ) 14.6, PCHCH3), 1.26 (dd, 9H, J H-H ) 7.1, J P-H ) 14.1,
PCHCH3). 13C{1H} NMR (75.4 MHz, CD2Cl2, 293 K plus APT
plus HETCOR): δ 247.8 (d, J C-P ) 9.4, Ru-CR), 204.1 (d, J C-P
) 18.2, CO), 141.4 and 140.3 (both s, Cipso), 138.9 (s, CPh2),
138.2 (s, CHdCPh2), 137.1 (NCHd), 130.6, 129.6, 128.9, 128.6,
128.2 (all s, CPh), 128.5 (s, CHdCH2), 121.8 (s, dCH2), 120.9
(s, dCHCH3), 87.4 (s, Cp), 57.7 (s, NCH2), 28.9 (d, J C-P ) 23.3,
PCHCH3), 20.1 and 19.9 (both s, PCHCH3), 15.5 (s, CH3). 31P-
{1H} NMR (121.4 MHz, CD2Cl2, 193 K): δ 63.1 (s).
19A
20
16
17
14.2, J H
) 5.7, NCHCH19A), 4.02 (d, J H
) 8.7,
-H
-H
OCCH16), 3.43 (dd, J H
) 14.2, J H
) 8.7, NCHCH19B),
19A
-H
19B
19B
20
-H
1.87 (m, 3H, PCHCH3), 1.07 (dd, 9H, J H-H ) 7.8, J H-P ) 12.9,
PCHCH3), 1.03 (dd, 9H, J H-H ) 7.5, J H-P ) 13.2, PCHCH3).
13C{1H} NMR (75.4 MHz, C6D6, 293 K plus APT plus HET-
COR): δ 262.2 (d, J P-C ) 11.5, Ru-C1), 259.8 (d, J P-C ) 14.3,
CO), 144.8, 140.5 (both s, Cipso), 137.6 (s, C2HdCPh2), 133.4
(s, C20HdCH2), 132.8 (s, C18HdCH2), 130.7, 129.3, 129.4, 128.8,
128.3, 128.0 (all s, CPh), 129.4 (s, dC3Ph2), 119.8 (s, CHd
C21H2), 119.1 (s, CHdC17H2), 91.9 (s, C16H), 85.9 (s, Cp), 53.1
(s, NC19H2), 28.4 (d, J P-C ) 20.3, PCHCH3), 20.5 and 20.4 (both
s, PCHCH3). 31P{1H} NMR (121.4 MHz, 293 K, C6D6): δ 67.9
(s). MS (FAB+): m/z 643 (M+ + 2H).
Sp ectr oscop ic d a ta for 4:28 IR (Nujol, cm-1): ν(CO) 1910
1
(s), ν(CdC) 1639, 1592, and 1505. H NMR (300 MHz, C6D6,
20
21A
293 K): δ 7.44-7.04 (m, 10H, Ph), 6.24 (dddd, 1H, J H
)
-H
20
21B
20
19B
20
19A
16.7, J H
5.55 (ddd, 1H, J H
), 5.35 (dd, 1H, J H
to NCH2), 5.22 (dd, 1H, J H
) 9.7, J H
) 6.7, J H
) 3.9, CH20dCH2),
-H
-H
-H
) 17.3, J H
) J H
) 9.9, CH17d
17
18A
17
18B
17
16
-H
21A
-H
21A
-H
) 16.7, J H
) 1.8, dCH21A, H cis
20
21B
-H
-H
21B
21B
20
21A
21B
) 9.7, J H
) 1.8, dCH
,
)
-H
-H
18A
17
18A
18B
H trans to NCH2), 4.94 (dd, 1H, J H
) 17.3, J H
-H
-H
2.2, dCH18A, H trans to H17), 4.90 (s, 5H, Cp), 4.85 (dd, 1H,
J H
) 9.9, J H
) 2.2, dCH18B, H cis to H17), 4.75
18B
17
18A
18B
-H
-H
P r ep a r a t ion of [R u (η5-C5H 5){C(CHdCP h 2)dNH (CH2-
CHdCH2)}(CO)(P iP r 3)]BF 4 (7). A deep red solution of [Ru-
(η5-C5H5)(dCdCdCPh2)(CO)(PiPr3)]BF4 (1) (200 mg, 0.32 mmol)
in 6 mL of dichloromethane was treated with allylamine (26
(28) All our attempts to achieve a valid elemental analysis deter-
mination for complexes 3 and 4 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.

4-Azoniaheptatrienyl Complexes of Ru
Organometallics, Vol. 22, No. 25, 2003 5283
Ta ble 5. Cr ysta l Da ta a n d Da ta Collection a n d Refin em en t for 3, 4, 5, a n d 9
3
4
5
9
Crystal Data
formula
molecular wt
color and habit
size, mm
symmetry, s group
a, Å
C
36H46NOPRu
C36H46NOPRu
640.78
C36H47BF4NOPRu
728.60
cololess, irregular block
0.18,0.06,0.04
monoclinic, C2/c
28.434(3)
C33H42NOPRu‚1.5 C6H6
717.88
colorless, irregular block
0.20,0.08,0.04
triclinic, P1h
9.674(2)
12.170(3)
15.904(3)
76.879(3)
86.662(3)
640.78
orange, irregular block
0.12,0.04,0.02
monoclinic, P21/c
9.521(4)
15.691(6)
20.348(8)
yellow, plate
0.14,0.14,0.03
triclinic, P1h
9.6984(12)
11.3808(15)
15.840(2)
108.998(2)
95.494(2)
106.465(2)
1550.9(3)
2
b, Å
c, Å
14.2093(15)
20.023(2)
R, deg
â, deg
91.315(7)
122.801(2)
γ, deg
87.046(3)
1819.0(7)
2
V, Å3
3039(2)
4
1.401
6800.1(12)
8
1.423
Z
D
calc, g cm-3
1.372
1.311
Data Collection and Refinement
Bruker Smart APEX
diffractometer
λ(Mo KR), Å
0.71073
graphite oriented
ω scans
monochromator
scan type
µ, mm-1
0.598
3, 50
100.0(2)
29 818
5472 (Rint ) 0.2034)
397/6
0.0585
0.1185
0.586
0.560
0.508
3, 57
100.0(2)
21 506
8342 (Rint ) 0.0637)
435/0
0.0488
0.0991
2θ, range, deg
3, 57
3, 57
temp, K
100.0(2)
18 914
100.0(2)
20 473
no. of data collect
no. of unique data
no. params/restraints
7194 (Rint ) 0.0694)
397/0
7902 (Rint ) 0.1042)
445/0
R1 [F2 > 2σ(F2)]
0.0474
0.0464
a
b
wR2 [all data]
0.0655
0.0559
Sc [all data]
0.780
0.759
0.620
0.828
R1(F) ) ∑||Fo| - |Fc||/∑|Fo|. wR2(F2) ) {∑[w(Fo - Fc2)2]/∑[w(Fo2)2]}1/2
.
c Goof ) S ){∑[Fo - Fc2)2]/(n - p)}1/2, where n is the number
a
b
2
2
of reflections, and p is the number of refined parameters.
µL, 0.35 mmol). The mixture was stirred at room temperature
for 15 min, and the solution became orange. The solvent was
removed in vacuo, and the residue was treated with 6 mL of
diethyl ether at -78 °C to afford a pale yellow suspension.
The solution was decanted, and the solid was washed twice
with diethyl ether and dried in vacuo. Yield: 190 mg (86%).
Anal. Calcd for C33H43BF4NOPRu: C, 57.56; H, 6.29; N, 2.03.
Found: C, 57.53; H, 6.46; N, 2.31. IR (Nujol, cm-1): ν(NH)
3316 (m), ν(CO) 1936 (vs), ν(CdN) and ν(CdC) 1613 (m) and
K, C6D6): δ 7.63-7.04 (m, 10H, Ph), 6.85 (s, 1H, CHdCPh2),
3 2
6.25 (m, 1H, CHdCH2), 5.31 (dd, J H-H ) 17.1, J H-H ) 2.1,
3
2
1H, dCH2, H cis to NCH2), 5.12 (dd, J H-H ) 9.3, J H-H ) 2.1,
1H, dCH2, H trans to NCH2), 4.58 (s, 5H, Cp), 4.47 (br d, 1H,
J H-H ) 15.6, NCH2), 4.25 (br d, 1H, J H-H ) 15.6, NCH2), 2.12
(m, 3H, PCHCH3), 1.10 (dd, 9H, J H-H ) 7.2, J P-H ) 13.5,
PCHCH3), 0.96 (dd, 9H, J H-H ) 6.9, J P-H ) 12.6, PCHCH3).
13C{1H} NMR (75.4 MHz, 293 K, C6D6, plus APT): δ 208.5 (d,
J P-C ) 16.1, CO), 195.4 (d, J P-C ) 11.5, Ru-CR), 144.7, (s, 2
1545 (w), ν(BF4) 1100 (br). 1H NMR (300 MHz, 293 K, CDCl3):
δ 9.92 (br, 1H, NH), 7.50-7.11 (m, 10H, Ph), 6.55 (s, 1H, CHd
C
ipso Ph), 141.6 (s, dCPh2), 141.2 (s, CHdCPh2), 139.0 (s, CHd
CH2), 130.7, 127.6, 128.7, 128.5, 128.1, 127.5, and 126.8 (all s,
Ph), 113.8 (s, dCH2), 87.2 (s, Cp), 60.9 (s, NCH2), 27.5 (d, J P-C
) 27.5, PCHCH3), 19.9, 19.4 (both s, PCHCH3). 31P{1H} NMR
(121.4 MHz, 293 K, C6D6): δ 68.9 (s).
3
CPh2), 5.91 (m, 1H, CHdCH2), 5.28 (d, J H-H ) 17.1, 1H, d
3
CH2, H cis to NCH2), 5.27 (d, J H-H ) 10.2, 1H, H trans to
NCH2), 4.91 (s, 5H, Cp), 4.37 (m, 2H, NCH2), 2.26 (m, 3H,
PCHCH3), 1.30 (dd, 9H, J H-H ) 6.9, J P-H ) 14.4, PCHCH3),
1.29 (dd, 9H, J H-H ) 6.9, J P-H ) 13.8, PCHCH3). 13C{1H} NMR
(75.4 MHz, 293 K, CDCl3): δ 243.3 (d, J P-C ) 10.6, Ru-CR),
204.6 (d, J P-C ) 17.1, CO), 141.3 (s, dCPh2), 141.0 and 138.7
(both s, Cipso Ph), 133.8 (s, CHdCPh2), 130.4, 130.1, 128.5,
128.4, 128.3 (all s, Ph), 129.0 (s, CHdCH2), 121.3 (s, dCH2),
86.9 (s, Cp), 55.1 (s, NCH2), 28.8 (d, J P-C ) 23.9, PCHCH3),
19.9 and 19.4 (both s, PCHCH3). 31P{1H} NMR (121.4 MHz,
293 K, CDCl3): δ 63.1 (s).
P r ep a r a tion of Ru (η5-C5H5){C(CHdCP h 2)dNCHd
CHCH3}(CO)(P iP r 3) (9). A yellow solution of Ru(η5-C5H5)-
{C(CHdCPh2)dNCH2CHdCH2}(CO)(PiPr3) (8) (125 mg, 0.21
mmol) in 5 mL of toluene was heated at 70 °C for 48 h. The
solution was evaporated to dryness. The residue was treated
with 3 mL of pentane and stored at -78 °C for 24 h to afford
pale yellow microcrystals. The solution was decanted, and the
crystals were washed twice with cold pentane and dried in
vacuo to afford a yellow oil. 1H NMR (300 MHz, 293 K,
CDCl3): δ 7.66-7.05 (m, 10H, Ph), 7.38 (d, 1H, J H-H ) 13.2,
NCH2d), 7.03 (s, 1H, CH5dCPh2), 5.89 (dq, 1H, J H-H ) 13.2,
J H-H ) 6.9, dCH3CH3), 4.59 (s, 5H, Cp), 2.11 (m, 3H,
P r ep a r a tion of Ru (η5-C5H5){C(CHdCP h 2)dNCH2CHd
CH2}(CO)(P iP r 3) (8). A pale yellow solution of [Ru(η5-C5H5)-
{C(CHdCPh2)dNH(CH2CHdCH2)}(CO)(PiPr3)]BF4 (7) (285
mg, 0.41 mmol) in 10 mL of tetrahydrofuran was treated with
sodium methoxide (45 mg, 0.82 mmol). The mixture was
stirred at room temperature for 40 min, and the color changed
to dark yellow. The solvent was removed in vacuo. Dichlo-
romethane was added, and the suspension was filtered to
remove potassium tetrafluoroborate. Solvent was evaporated
to dryness, and the residue was treated with 6 mL of pentane
at -78 °C to afford a yellow suspension. The solution was
decanted, and the solid was washed twice with cold pentane
and dried in vacuo. Yield: 172 mg (70%). Anal. Calcd for
PCHCH3), 1.70 (d, 3H, J H-H ) 6.9, CH3), 1.11 (dd, 9H, J H-H
7.2, J P-H ) 13.5, PCHCH3), 0.97 (dd, 9H, J H-H ) 6.9, J P-H
)
)
12.9, PCHCH3). 13C{1H} NMR (75.4 MHz, 293 K, C6D6, plus
APT): δ 208.1 (d, J P-C ) 19.8, CO), 206.1 (d, J P-C ) 12.9, Ru-
C1), 144.4 (s, dC6Ph2), 142.3 (s, NC2Hd), 141.5 (s, Cipso), 140.6
(s, C5HdCPh2), 137.4 (s, Cipso), 130.8, 128.8, 128.5, 128.1, 126.9
(all s, Ph), 118.5 (s, dC3HCH3), 87.3 (s, Cp), 27.9 (d, J P-C
)
22.1, PCHCH3), 20.2 and 19.7 (both s, PCHCH3), 15.5 (s, CH3).
31P{1H} NMR (121.4 MHz, 293 K, C6D6): δ 69.2 (s). MS
(FAB+): m/z 602 (M+ + H).
Str u ctu r a l An a lysis of Com p lexes 3, 4, 5, a n d 9. X-ray
data were collected for all complexes at low temperature on a
Bruker Smart APEX CCD diffractometer at 100.0(2) K equipped
C
33H42NOPRu: C, 65.98; H, 7.05; N, 2.33. Found: C, 65.80;
H, 7.29, N, 2.14. IR (Nujol, cm-1): ν(CO) 1919 (vs), ν(CdN)
1
and ν(CdC) 1599 (w) and 1541 (m). H NMR (300 MHz, 293

5284 Organometallics, Vol. 22, No. 25, 2003
Buil et al.
with a normal focus, 2.4 kW sealed tube source (molybdenum
radiation, λ ) 0.71073 Å) operating at 50 kV and 40 mA. Data
were collected over the complete sphere by a combination of
four sets (3, 4, and 9) or over the hemisphere by a combination
of three sets (5). Each frame exposure time was 10 or 30 s
covering 0.3° in ω. Data were corrected for absorption by using
a multiscan method applied with the SADABS29 program. The
structures for all compounds were solved by the Patterson
method. Refinement, by full-matrix least squares on F2 with
SHELXL97,30 was similar for all complexes, including isotropic
and subsequently anisotropic displacement parameters for all
non-hydrogen atoms. The hydrogen atoms were observed or
calculated and refined freely or using a restricted riding model,
respectively.
Ack n ow led gm en t. We are grateful for financial
support from the MCYT of Spain (Projects PPQ2000-
0488-P4-02 and BQU2002-00606). M.L.B. thanks the
Ministerio de Ciencia y Tecnolog´ıa (CICYT) of Spain for
a Ramo´n y Cajal project.
Su p p or tin g In for m a tion Ava ila ble: Tables of atomic
coordinates and equivalent isotropic displacement coefficients,
anisotropic thermal parameters, experimental details of the
X-ray studies, and bond distances and angles for 3, 4, 5, and
9. This material is available free of charge via the Internet at
http://pubs.acs.org.
(29) Blessing, R. H. Acta Crystallogr. 1995, A51, 33-38. SADABS,
Area-detector absorption correction; Bruker-AXS: Madison, WI, 1996.
(30) SHELXTL Package v. 6.10; Bruker-AXS: Madison, WI, 2000.
Sheldrick, G. M. SHELXS-86 and SHELXL-97; University of Go¨ttin-
gen: Go¨ttingen, Germany, 1997.
OM030518M