The allenylidene complex [Ru(η5-C5H5)(C=C=CPh 2)(CO)(PiPr3)]BF4 as a precursor of novel pyrido[1,2-a]pyrimidinyl and 1,3-thiazinyl complexes

Article abstract of DOI:10.1021/om000415t

The allenylidene complex [Ru(η⁵-C₅H₅)(C=C=CPh ₂)(CO)(PⁱPr₃)]BF4 (1) reacts with 2-aminopyridine to give a mixture of the complexes

Full text of DOI:10.1021/om000415t

Organometallics 2000, 19, 4327-4335
4327
Th e Allen ylid en e Com p lex
[Ru (η5-C5H5)(CdCdCP h 2)(CO)(P iP r 3)]BF 4 a s a P r ecu r sor
of Novel P yr id o[1,2-a ]p yr im id in yl a n d 1,3-Th ia zin yl
Com p lexes
D. J avier Bernad,† Miguel A. Esteruelas,*,† Ana M. Lo´pez,*,† Montserrat Oliva´n,†
Enrique On˜ate,† 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 May 15, 2000
The allenylidene complex [Ru(η5-C5H5)(CdCdCPh2)(CO)(PiPr3)]BF4 (1) reacts with 2-ami-
nopyridine to give a mixture of the complexes [Ru(η5-C5H5){2,2-diphenyl-2H-pyridinium-
[1,2-a]pyrimidin-4-yl}(CO)(PiPr3)]BF4 (2) and [Ru(η5-C5H5){C(CHdCPh2)dNHC(CH)4N}-
(CO)(PiPr3)]BF4 (3). The molar ratio of the isomers in the mixture depends on the reaction
temperature. At temperatures lower than -30 °C, isomer 2 is the main reaction product,
while at 0 °C an inverse relationship is observed. The structure of 2 has been determined
by an X-ray investigation, revealing a Ru-C(bicycle) distance of 2.08(1) Å. Treatment of 2
with sodium methoxide results in the deprotonation of the NH group of the heterocycle to
give the pyrido[1,2-a]pyrimidinyl derivative Ru(η5-C5H5){2,2-diphenyl-2H-pyrido[1,2-a]-
pyrimidin-4-yl}(CO)(PiPr3) (4), which has been also characterized by an X-ray diffraction
analysis. In this case, the study reveals a Ru-C(bicycle) distance of 2.097(5) Å. The
deprotonation of 2 is reversible. Thus, the addition of HBF4‚OEt2 to dichloromethane solutions
of 4 regenerates 2. Similarly, the treatment of 4 with methyl trifluoromethanesulfonate
affords
[Ru(η5-C5H5){1-methyl-2,2-diphenyl-2H-pyridinium[1,2-a]pyrimidin-4-yl}(CO)-
(PiPr3)]CF3SO3 (5). Complex 1 also reacts with thioisonicotinamide. The reaction yields [Ru-
(η5-C5H5){4,4-diphenyl-2-(p-pyridinyl)-4H-1,3-thiazinium-6-yl}(CO)(PiPr3)]BF4 (6), which in
the presence of sodium methoxide affords Ru(η5-C5H5){4,4-diphenyl-2-(p-pyridinyl)-4H-1,3-
thiazin-6-yl}(CO)(PiPr3) (7). The structure of 7 has been determined by an X-ray investigation,
revealing a Ru-C(cycle) distance of 2.067(4) Å. The deprotonation of 6 is also reversible.
Thus, the addition of HBF4‚OEt2 to dichloromethane solutions of 7 regenerates 6. Similarly,
treatment of 7 with methyl trifluoromethanesulfonate gives [Ru(η5-C5H5){3-methyl-4,4-
diphenyl-2-(p-pyridinyl)-4H-1,3-thiazinium-6-yl}(CO)(PiPr3)]CF3SO3 (8).
In tr od u ction
between the HOMO of the metallic fragment and the
LUMO of the allenylidene. Thus, the π-acceptor com-
ponent of the metal-allenylidene bond is stronger than
the σ-donor one. As a result of this bonding situation,
the reactivity of the C3 organic unit strongly depends
on the particular metallic fragment stabilizing the
allenylidene ligand.
Transition-metal allenylidene complexes have at-
tracted a great deal of attention in recent years as a
new type of organometallic intermediate that may have
unusual reactivity in stoichiometric1 and catalytic2
processes.
EHT-MO calculations3 indicate that allenylidenes
coordinate to metal centers as σ-donor and π-acceptor
ligands. The interaction between the HOMO of the
allenylidene and the LUMO of the metallic fragment
produces a lower charge transfer than the interaction
The majority of allenylidene complexes have only
donor ligands which somewhat reduce the electrophi-
licity of the allenylidene. In 1996 we reported the
synthesis of the complex [Ru(η5-C5H5)(CdCdCPh2)-
(CO)(PiPr3)]BF4 (1), containing a carbonyl group.4 The
presence of this ligand may seem trivial; however, its
† Universidad de Zaragoza-CSIC.
‡ Universidad de Ca´diz.
(1) (a) Werner, H. Chem. Commun. 1997, 903. (b) Bruce, M. I. Chem.
Rev. 1998, 98, 2797. (c) Touchard, D.; Dixneuf, P. H. Coord. Chem.
Rev. 1998, 178, 409.
(2) (a) Fu¨rstner, A.; Picquet, M.; Bruneau, C.; Dixneuf, P. H. Chem.
Commun. 1998, 1315. (b) Picquet, M.; Touchard, D.; Bruneau, C.;
Dixneuf, P. H. New J . Chem. 1999, 141. (c) Fu¨rstner, A.; Hill, A. F.;
Liebl, M.; Wilton-Ely, J . D. E. T. Chem. Commun. 1999, 601. (d)
Harlow, K. J .; Hill, A. F.; Wilton-Ely, J . D. E. T. J . Chem. Soc., Dalton
Trans. 1999, 285.
(3) (a) Berke, H.; Huttner, G.; Von Seyerl, J . Z. Naturforsch. 1981,
36B, 1277. (b) Edwards, A. J .; Esteruelas, M. A.; Lahoz, F. J .; Modrego,
J .; Oro, L. A.; Schrickel, J . Organometallics 1996, 15, 3556. (c)
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. (d) Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.;
Modrego, J .; On˜ate, E. Organometallics 1997, 16, 5826.
(4) Esteruelas, M. A.; Go´mez, A. V.; Lahoz, F. J .; Lo´pez, A. M.;
On˜ate, E.; Oro, L. A. Organometallics 1996, 15, 3423.
10.1021/om000415t CCC: $19.00 © 2000 American Chemical Society
Publication on Web 09/14/2000

4328 Organometallics, Vol. 19, No. 21, 2000
Bernad et al.
Sch em e 1
In this paper, we report the synthesis and characteriza-
tion of pyrido[1,2-a]pyrimidinyl- and 1,3-thiazinylru-
thenium complexes, two types of organometallic com-
pounds unknown until now.
Resu lts a n d Discu ssion
1. Rea ction s of [Ru (η5-C5H5)(CdCdCP h 2)(CO)-
(P iP r 3)]BF 4 w ith 2-Am in op yr id in e. Treatment of
dichloromethane solutions of 1 with 1.1 equiv of 2-ami-
nopyridine leads to yellow solutions. After removal of
the solvent, the 31P{1H} NMR spectrum of the residue
in chloroform-d shows two singlets at 62.3 and 62.6
ppm, which corresponds to the pyridinium[1,2-a]pyri-
midinyl and azoniabutadienyl derivatives [Ru(η5-C5H5)-
{2,2-diphenyl-2H-pyridinium[1,2-a]pyrimidin-4-yl}(CO)-
(PiPr3)]BF4 (2) and [Ru(η5-C5H5){C(CHdCPh2)dNH-
Sch em e 2
C(CH)4N}(CO)(PiPr3)]BF4 (3), respectively. The molar
ratio of the isomers in the mixture depends on the
reaction temperature. At temperatures lower than -30
°C, isomer 2 is the main reaction product, while at 0 °C
an inverse relationship is observed (eq 1).
π-acidic nature enhances the reactivity associated with
the allenylidene spine.3d,4,5 Thus, in contrast to other
allenylidene complexes of the iron triad, the diphenyl-
allenylidene ligand of 1 adds the N-H bond of secondary
and primary amines at the CR-Câ double bond to afford
azoniabutadienyl derivatives of the types[Ru(η5-C5H5)-
{C(CHdCPh2)dNR2}(CO)(PiPr3)]BF4 and [Ru(η5-C5H5)-
{C(CHdCPh2)dNHR}(CO)(PiPr3)]BF4,respectively.Treat-
ment of the tertiary azoniabutadienyl complexes with
sodium methoxide produces the deprotonation of the
CHdCPh2 group of the unsaturated η1-carbon donor
ligand and the formation of the corresponding aminoal-
lenyl derivatives, while under the same conditions the
deprotonation of the secondary azoniabutadienyl com-
pounds occurs at the nitrogen atom, and as a result,
azabutadienyl derivatives are formed (Scheme 1).5f
In reactions with secondary amines containing a
second nitrogen atom, the diphenylallenylidene ligand
of 1 is active not only at the CR-Câ double bond but
also at the Cγ atom. Thus, the addition of pyrazoles to
solutions of 1 leads to pyrazolo[1,2-a]pyrazolyl com-
plexes, which yield functionalized alkynyl derivatives
by treatment with sodium methoxide (Scheme 2).5b
Interest in the behavior of the diphenylallenylidene
ligand of 1 in the presence of primary amines containing
a second heteroatom led us to investigate the reactivity
of 1 toward 2-aminopyridine and thioisonicotinamide.
At first glance, the formation of 2 could be rationalized
as the addition of one of the two NH bonds of the amine
to the Câ-Cγ double bond of the allenylidene ligand of
1 and the subsequent coordination of the nitrogen atom
of the pyridine group to the CR atom. The formation of
3 can be rationalized as the addition of one of the two
NH bonds of the amine to the CR-Câ double bond of
the allenylidene ligand of 1, in agreement with the
reactions collected in Scheme 1. The orientations ob-
served for the additions (NfCR or Cγ and HfCâ) agree
well with EHT-MO calculations on transition-metal
allenylidene complexes, indicating that the CR and Cγ
atoms are electrophilic centers, while the Câ atom is a
nucleophile.3
According to the data collected in eq 1, one could think
that the addition of primary amines containing a second
nitrogen atom occurs not only at the CR-Câ double bond
of the allenylidene but also at the Câ-Cγ double bond.
The first addition should be favored at low temperature,
while the second one should be favored at high temper-
(5) (a) Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.; On˜ate, E.; Ruiz,
N. Organometallics 1998, 17, 2297. (b) Esteruelas, M. A.; Go´mez, A.
V.; Lo´pez, A. M.; On˜ate, E. Organometallics 1998, 17, 3567. (c)
Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.; Puerta, M. C.; Valerga,
P. Organometallics 1998, 17, 4959. (d) Esteruelas, M. A.; Go´mez, A.
V.; Lo´pez, A. M.; Modrego, J .; On˜ate, E. Organometallics 1998, 17,
5434. (e) Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.; On˜ate, E.; Ruiz,
N. Organometallics 1999, 18, 1606. (f) Bernad, D. J .; Esteruelas, M.
A.; Lo´pez, A. M.; Modrego, J .; Puerta, M. C.; Valerga, P. Organome-
tallics 1999, 18, 4995. (g) Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A.
M.; Oliva´n, M.; On˜ate, E.; Ruiz, N. Organometallics 2000, 19, 4.

[Ru(η5-C5H5)(CdCdCPh2)(CO)(PiPr3)]BF4
Organometallics, Vol. 19, No. 21, 2000 4329
Ta ble 1. Selected Bon d Dista n ces (Å) a n d An gles (d eg) for th e Com p lexes
[Ru (η5-C5H5){2,2-d ip h en yl-2H-p yr id in iu m [1,2-a ]p yr im id in -4-yl}(CO)(P iP r 3)]BF 4 (2) a n d
Ru (η5-C5H5){2,2-d ip h en yl-2H-p yr id o[1,2-a ]p yr im id in -4-yl}(CO)(P iP r 3) (4)
2
4
2
4
Rua-P
2.356(3)
2.26(1)
2.25(1)
2.25(1)
2.26(1)
2.23(1)
1.84(1)
2.08(1)
1.16(1)
1.45(1)
1.37(1)
2.3520(14)
2.266(6)
2.276(7)
2.251(6)
2.222(6)
2.242(7)
1.835(5)
2.097(5)
1.152(5)
1.442(6)
1.421(6)
N(1)-C(26)
N(2)-C(9)
1.38(1)
1.45(1)
1.35(1)
1.36(1)
1.46(1)
1.55(2)
1.57(1)
1.43(2)
1.33(2)
1.38(2)
1.34(2)
1.376(6)
1.467(6)
1.284(6)
1.332(6)
1.515(6)
1.539(6)
1.557(6)
1.439(6)
1.324(7)
1.420(7)
1.349(7)
Ru-C(1)
Ru-C(2)
Ru-C(3)
Ru-C(4)
Ru-C(5)
Ru-C(6)
Ru-C(7)
C(6)-O
N(2)-C(22)
C(7)-C(8)
C(8)-C(9)
C(9)-C(10)
C(9)-C(16)
C(22)-C(23)
C(23)-C(24)
C(24)-C(25)
C(25)-C(26)
N(1)-C(7)
N(1)-C(22)
M(1)b-Ru-P
130.3(2)
125.5(4)
117.9(2)
86.2(4)
129.8(2)
126.2(3)
118.3(3)
85.57(16)
91.18(13)
95.9(2)
122.9(3)
123.4(4)
113.6(4)
115.8(4)
123.3(4)
122.9(5)
109.9(4)
109.3(8)
N(2)-C(9)-C(16)
N(2)-C(22)-C(23)
C(7)-N(1)-C(22)
C(7)-N(1)-C(26)
C(7)-C(8)-C(9)
C(8)-C(9)-C(10)
C(8)-C(9)-C(16)
C(9)-N(2)-C(22)
C(10)-C(9)-C(16)
C(22)-C(23)-C(24)
C(23)-C(24)-C(25)
C(24)-C(25)-C(26)
C(26)-N(1)-C(22)
109.8(8)
122(1)
108.2(4)
120.9(5)
118.2(4)
122.4(4)
123.9(5)
114.2(4)
106.0(4)
117.1(4)
110.0(4)
121.7(5)
120.7(5)
118.3(5)
119.1(4)
M(1)-Ru-C(6)
M(1)-Ru-C(7)
P-Ru-C(6)
119.6(9)
121.1(9)
126.9(10)
115.0(9)
108.6(8)
121.0(9)
108.1(9)
119(1)
P-Ru-C(7)
92.4(3)
C(6)-Ru-C(7)
Ru-C(7)-N(1)
Ru-C(7)-C(8)
N(1)-C(7)-C(8)
N(1)-C(22)-C(23)
N(1)-C(22)-N(2)
N(1)-C(26)-C(25)
N(2)-C(9)-C(8)
N(2)-C(9)-C(10)
94.6(5)
122.7(7)
124.1(8)
113.1(9)
118(1)
119.3(10)
120(1)
106.0(9)
109.3(8)
119(1)
120(1)
119.3(9)
a
b
Ru, P, and O in this table stand for Ru(1), P(1), and O(1) in Figure 1. M(1) is the centroid of the C(1)-C(5) Cp carbon atoms.
the azoniabutadienyl ligand. At first glance, it could be
argued that this is due to the large steric hindrance
experienced by the phenyl and pyridinyl groups. How-
ever, we have previously observed that complex 1 reacts
with pyridine-2-thiol to give [Ru(η5-C5H5){CdCHC-
(Ph)2N(CH)4CS}(CO)(PiPr3)]BF4 containing a N(pyridi-
nyl)-CPh2 bond.5b Therefore, the instability of the
product resulting from the intramolecular cyclization of
3 should be related to the electronic structure of its
condensed heterocycles.
Isomer 2 was obtained as pure yellow crystals in
66% yield, by crystallization in dichloromethane-
diethyl ether of the crude product obtained from the
reaction of 1 with 2-aminopyridine at -55 °C, and
characterized by an X-ray crystallographic study. A view
of the molecular geometry of the cation of 2 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 occupy-
ing one face of the octahedron, and the angles formed
by the triisopropylphosphine, the carbonyl group, and
the heterocycle are close to 90°.
The unsaturated η1-carbon ligand can be described
as a 2,2-diphenyl-2H-pyridinium[1,2-a]pyrimidin-4-yl
F igu r e 1. Molecular diagram of the cation of 2, [Ru(η5-
C5H5){2,2-diphenyl-2H-pyridinium[1,2-a]pyrimidin-4-yl}-
(CO)(PiPr3)]+. Thermal ellipsoids are shown at 50% prob-
ability.
ature. This trivial conclusion is probably incorrect. It
should be noted that 2-aminopyridine also exists in the
imino tautomeric form and that this tautomeric equi-
librium is highly dependent on the temperature.6 On
this basis, the formation of 2 can be rationalized as the
addition of the endocyclic NH bond of the imino form
at the CR-Câ double bond of the allenylidene ligand and
the subsequent coordination of the exocyclic nitrogen
atom to the Cγ atom.
group. The C(7)-C(8)-C(9)-N(2)-C(22)-N(1) ring has
a twisted conformation. If the C(8) and C(22) atoms are
situated in the ideal least-squares plane through the
six atoms of the ring (the deviations from this plane (Å)
are 0.03(1) (C(8)) and -0.01(1) (C(22))), the C(7) and
N(2) atoms lie 0.158(9) and 0.193(9) Å above, respec-
tively, while the C(9) and N(1) atoms lie 0.25(1) and
0.143(8) Å below, respectively. In contrast, the ring
In addition, it should be noted that the pyridinic
nitrogen atom of 3 is not coordinated to the Cγ atom of
(6) (a) Katritzky, A. R.; Lagowski, J . M. Adv. Heterocycl. Chem. 1963,
1, 341. (b) Elguero, J .; Marzin, C.; Katritzky, A. R.; Linda, P. In The
Tautomerism of Heterocycles: Advances in Heterocyclic Chemistry;
Academic Press: New York, 1976; Supplement 1, Chapter 2.
N(1)-C(22)-C(23)-C(24)-C(25)-C(26) is almost
planar. The deviations from the best plane (Å) are
0.033(8) (N(1)), -0.04(1) (C(22)), 0.00(1) (C(23)),

4330 Organometallics, Vol. 19, No. 21, 2000
Bernad et al.
0.07(2) (C(24)), -0.03(1) (C(25)), and -0.02(1) (C(26)).
The dihedral angle formed by the least-squares planes
through the atoms of both cycles is 13.6°.
The Ru-C(7) distance (2.08(1) Å) lies within the range
2.03(1)7-2.141(3) Å,8 where a Ru-C(sp2) single bond
has been proposed to exist. In accordance with the sp2
hybridization for C(7), the angles Ru-C(7)-N(1) and
Ru-C(7)-C(8) are 122.7(7) and 124.1(8)°, respectively.
The structural parameters obtained for the C(7)-
C(8)-C(9)-N(2)-C(22)-N(1) ring support the electronic
structure proposed in eq 1. The C(7)-C(8) distance of
1.36(1) Å is in agreement with the sample mean of
carbon-carbon bond lengths for double bonds (1.32(1)
Å),9 whereas the C(8)-C(9) bond length (1.46(1) Å) is
statistically identical with the sample mean of the
C(sp2)-C(sp3) single-bond distance (1.48(3) Å).9 The
C(7)-N(1) and C(9)-N(2) bond lengths are identical
(1.45(1) Å) and agree well with C-N single bonds.
However, the N(1)-C(22) (1.37(1) Å) and N(2)-C(22)
(1.35(1) Å) distances are intermediate between those
found for C-N double bonds in Schiff bases, hydrazones,
and related compounds (about 1.29 Å) and those ex-
pected for a C-N single bond, suggesting electron
delocalization over N(1), C(22), and N(2).
F igu r e 2. Molecular diagram of the complex Ru(η5-C5H5)-
{2,2-diphenyl-2H-pyrido[1,2-a]pyrimidin-4-yl}(CO)(PiPr3)
(4). Thermal ellipsoids are shown at 50% probability.
As a consequence of the participation of N(2) in the
N(1)-C(22)-N(2) electron delocalization, the N(2)H
hydrogen atom of 2 is relatively acidic. Thus, treatment
of tetrahydrofuran suspensions of 2 with sodium meth-
oxide leads to the pyrido[1,2-a]pyrimidinyl complex
Ru(η5-C5H5){2,2-diphenyl-2H-pyrido[1,2-a]pyrimidin-4-
yl}(CO)(PiPr3) (4), as a result of the deprotonation of
the N(2) atom of 2 (eq 2).
The structural parameters obtained for the N(1)-
C(22)-C(23)-C(24)-C(25)-C(26) ring are also in ac-
cordance with the electronic structure proposed in eq 1
for this cycle. The N(1)-C(26) distance (1.38(1) Å) is
similar to the N(1)-C(22) one, indicating electron de-
localization over C(26), N(1), and C(22). Furthermore,
the C(26)-C(25) (1.34(2) Å), C(25)-C(24) (1.38(2) Å),
and C(24)-C(23) (1.33(2) Å) distances suggest that the
electron delocalization also reaches to C(25), C(24), and
C(23). The C(23)-C(22) bond length of 1.43(2) Å indi-
cates a C(23)-C(22) single bond.
In agreement with the presence of a hydrogen atom
bonded to N(2) in the complex, the IR spectrum of 2 in
Nujol shows a ν(NH) band at 3328 cm-1. In the 1H NMR
spectrum, the NH resonance appears at 8.56 ppm as a
singlet. In addition, it should be mentioned that there
exists another singlet at 5.50 ppm, corresponding to the
C(8)-H resonance. In the 13C{1H} NMR spectrum, the
most noticeable feature is the presence of a doublet at
145.8 ppm, with a J (CP) value of 12.0 Hz, due to the
C(7) resonance.
Complex 4 was isolated as yellow crystals in 60%
yield and, as for 2, characterized by an X-ray crystal-
lographic study. Figure 2 gives a view of the molecular
geometry. Selected bond distances and angles are listed
in Table 1.
Similarly to 2, the geometry around the ruthenium
center of 4 is close to octahedral, with the cyclopenta-
dienyl ligand occupying one face of the octahedron, and
the angles formed by the triisopropylphosphine, carbo-
nyl group, and the bicycle are close to 90°.
The conformation of the cycle containing the two
nitrogen atoms is twisted, as in 2, with the related
atoms lying in positions similar to those previously
mentioned for the case of 2, whereas the cycle containing
only one heteroatom is almost planar. The dihedral
angle formed by the least-squares planes through the
atoms of both cycles is 17.7°.
The Ru-C(7) distance of 2.097(5) Å compares well
with the bond length in 2 and agrees with a Ru-C(sp2)
single bond. The angles Ru-C(7)-C(8) ) 123.4(4)° and
Ru-C(7)-N(1) ) 122.9(3)° support the sp2 hybridization
for C(7).
Complex 3 was characterized by IR and H, 31P{1H},
1
and 13C{1H} NMR spectroscopy. In the IR spectrum in
Nujol, the most noticeable absorption is a ν(NH) band,
1
which appears at 3283 cm-1. In the H NMR spectrum,
the NH resonance is observed as a broad singlet at 11.22
ppm. The 13C{1H} NMR spectrum strongly supports the
presence of an azoniabutadienyl ligand in 3, showing
the RuC resonance at 255.1 ppm, as a doublet with a
J (CP) of 8.4 Hz. The chemical shift and J (CP) values of
this resonance agree well with those reported for
previously synthesized azoniabutadienyl complexes.5f
(7) Torres, M. R.; Vegas, A.; Santos, A.; Ros, J . J . Organomet. Chem.
1987, 326, 413.
(8) Bohanna, C.; Esteruelas, M. A.; Lahoz, F. J .; On˜ate, E.; Oro, L.
A. Organometallics 1995, 14, 4685.
(9) Orpen, A. G.; Brammer, L.; Allen, F. H.; Kennard, O.; Watson,
D. G.; Taylor, R. J . Chem. Soc., Dalton Trans. 1989, S1.
The structural parameters obtained for the bicycle
reveal the high electronic perturbation undergone by
both cycles, as a result of the deprotonation. In contrast
to 2, the cycle of 4 containing the two nitrogen atoms

[Ru(η5-C5H5)(CdCdCPh2)(CO)(PiPr3)]BF4
Organometallics, Vol. 19, No. 21, 2000 4331
does not show any zone of electron delocalization. The
deprotonation of N(2) gives rise to a CdN double bond
between N(2) and the ring junction carbon atom (N(2)-
C(22) distance 1.284(6) Å) and the loss of electron
delocalization in the bond between this atom and N(1)
(N(1)-C(22) distance 1.421(6) Å). The effect of the
deprotonation in the cycle containing only one nitrogen
atom is the reduction of the electron delocalization from
N(1)-C(26)-C(25)-C(24)-C(23) in 2 to N(1)-C(26)-
C(25) in 4 and the formation of the C(24)-C(23) double
bond in 4 (C(23)-C(24) distance 1.324(7) Å).
The most noticeable feature in the IR spectrum of 4
is the absence of any ν(NH) band. In the 1H NMR
spectrum, the resonance corresponding to the RuCdCH
proton appears at 4.94 ppm as a singlet. The 13C{1H}
NMR spectrum shows the resonance due to the RuCd
carbon atom at 140.2 ppm, as a doublet with a J (CP)
value of 13.7 Hz.
The reaction shown in eq 2 is reversible. Thus,
addition of 1.1 equiv of HBF4‚OEt2 to dichloromethane
solutions of 4 regenerates 2 as a consequence of the
protonation of N(2). Similarly, treatment of 4 with
methyl trifluoromethanesulfonate affords the N-meth-
ylpyridinium[1,2-a]pyrimidinyl complex [Ru(η5-C5H5)-
{1-methyl-2,2-diphenyl-2H-pyridinium[1,2-a]pyrimidin-
4-yl}(CO)(PiPr3)]CF3SO3 (5), which was isolated as a
yellow solid in 65% yield (eq 3).
4-substituted or 2-substituted pyridinium[1,2-a]pyrim-
idines.14
In addition, it should be noted that the pyrazolo[1,2-
a]pyrazolyl compounds shown in Scheme 2 and 2 (eq 2)
behave differently in the presence of sodium methoxide.
While the former compounds undergo ring opening as
a consequence of the deprotonation of the RuCdCH
proton, the deprotonation of 2 occurs at the N(2)
nitrogen atom without ring opening. This difference in
behavior appears to suggest that, in contrast to the
heterocycles formed by addition of secondary amines
with a second nitrogen atom to the allenylidene of 1,
the heterocycles resulting from the addition of primary
amines with a second nitrogen atom are stable in basic
medium. The reason for the stability of the latter seems
to be the presence of a hydrogen atom in the nonring
junction nitrogen atom. The behavior of both types of
heterocycles toward the deprotonation can be related
with the behavior of tertiary and secondary azoniab-
utadienyl complexes. The pyrazolo[1,2-a]pyrazolyl and
tertiary azoniabutadienyl compounds, which are derived
from secondary amines, undergo deprotonation at the
RuCdCH carbon atom, while pyridinium[1,2-a]pyrim-
idinyl and secondary azoniabutadienyl complexes, which
come from primary amines, undergo deprotonation at
the nitrogen atom.
2. Rea ction s of [Ru (η5-C5H5)(CdCdCP h 2)(CO)-
(P iP r 3)]BF 4 w ith Th ioison icotin a m id e. Treatment
of dichloromethane solutions of 1 with 1.1 equiv of
thioisonicotinamide, under reflux, affords after 3 h the
1,3-thiazinium-6-yl-ruthenium complex [Ru(η5-C5H5)-
{4,4-diphenyl-2-(p-pyridinyl)-4H-1,3-thiazinium-6-yl}-
(CO)(PiPr3)]BF4 (6), which was isolated as an orange
solid in 86% yield, according to eq 4.
The presence of the [CF3SO3]- anion in 5 is supported
by its IR spectrum, which contains the characteristic
stretching bands of the free anion10 at 1277, 1262, 1144,
and 1030 cm-1. In the 1H NMR spectrum, the most
noticeable resonances are two singlets at 5.42 and 2.96,
with a 1:3 intensity ratio, corresponding to the RuCd
CH proton and methyl group, respectively. The 13C{1H}
NMR spectrum shows the resonance due to the RuCd
carbon atom at 145.3 ppm, as a broad signal.
From a methodogical point of view, it should be
mentioned that in organic chemistry, the reaction of
2-aminopyridine with 1,3-bifunctional compounds is a
useful synthetic method for the preparation of pyrido-
[1,2-a]pyrimidines.11 Thus, aromatic salts of pyrido[1,2-
a]pyrimidines have been prepared from 1,3-dioxo com-
pounds12 or their acetal and ketal equivalents12c,13 in
acidic media. The reactions of â-oxo acetals and â-chlo-
rovinyl aldehydes with 6-unsubstituted 2-aminopy-
ridines give 4-substituted salts, whereas 2-substituted
salts are formed from 6-substituted 2-aminopyridines.12a
The reactions with â-chlorovinyl ketones afford either
The formation of 6 with the nitrogen atom bonded to
the Ph2C carbon atom can be rationalized, formally, as
the addition of one of the two NH bonds of the thioamide
at the Câ-Cγ double bond of the allenylidene ligand of
1, followed by the coordination of the sulfur atom to the
CR atom of the resulting vinylidene. However, it should
be taken into account that primary and secondary
thioamides have the tautomeric forms shown in eq 5.15
(10) Lawrence, G. A. Chem. Rev. 1986, 86, 17.
Furthermore, the addition of HXR (X ) O, S, NR′)
molecules to the CR-Câ double bond of the allenylidene
ligand of 1 is a well-known process,4,5f while there are
(11) Hermecz, I.; Vasva´ri-Debreczy, L.; Ma´tyus, P. In Compehensive
Heterocyclic Chemistry II, A Review of the Literature 1982-1995; J ones,
G., Ed.; Pergamon: Oxford, U.K., 1996; Vol. 8, Chapter 8.23.
(12) (a) Sawyer, J . R. H.; Wibberley, D. G. J . Chem. Soc., Perkin
Trans. 1 1973, 1138. (b) Potts, K. T. Dugas, R.; Surapaneni, C. R. J .
Heterocycl. Chem. 1973, 10, 821. (c) Dennin, F.; Blondeau, D.; Sliwa,
H. Tetrahedron Lett., 1991, 32, 4307.
(14) Fischer, G. W. Z. Chem. 1978, 18, 121; Chem. Abstr. 1978, 89,
23666.
(13) (a) Pollak, A.; Stanovnik, B.; Tisler, M. J . Org. Chem. 1971,
36, 2457. (b) Tamura, S.; Ono, M. Chem. Pharm. Bull. 1978, 26, 3167.
(15) Walter, W.; Voss, J . In The Chemistry of Amides; Patai, S., Ed.;
Interscience: London, 1970; Chapter 8.

4332 Organometallics, Vol. 19, No. 21, 2000
Bernad et al.
Ta ble 2. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) for th e Com p lex Ru (η5-C5H5){4,4-d ip h en yl-
2-(p-p yr id in yl)-4H-1,3-th ia zin -6-yl}(CO)(P iP r 3) (7)
Ru-P
2.3056(14)
2.226(4)
2.256(4)
2.251(4)
2.234(4)
2.212(4)
1.813(4)
2.067(4)
1.146(5)
1.762(4)
S-C(19)
1.757(4)
1.464(4)
1.259(5)
1.318(7)
1.313(6)
1.313(5)
1.512(5)
1.521(5)
1.528(5)
1.474(5)
Ru-C(1)
Ru-C(2)
Ru-C(3)
Ru-C(4)
Ru-C(5)
Ru-C(6)
Ru-C(16)
C(6)-O
N(1)-C(18)
N(1)-C(19)
N(2)-C(22)
N(2)-C(23)
C(16)-C(17)
C(17)-C(18)
C(18)-C(25)
C(18)-C(31)
C(19)-C(20)
S-C(16)
M(1)a-Ru-P
M(1)-Ru-C(6)
M(1)-Ru-C(16)
P-Ru-C(6)
128.49(15) C(16)-C(17)-C(18) 124.5(3)
125.08(19) N(1)-C(18)-C(17) 110.4(3)
119.16(17) C(17)-C(18)-C(25) 108.9(3)
88.05(13) C(17)-C(18)-C(31) 112.0(3)
95.11(10) C(25)-C(18)-C(31) 110.5(3)
F igu r e 3. Molecular diagram of the complex Ru(η5-C5H5)-
{4,4-diphenyl-2-(p-pyridinyl)-4H-1,3-thiazin-6-yl}(CO)(Pi-
Pr3) (7). Thermal ellipsoids are shown at 50% probability.
P-Ru-C(16)
C(6)-Ru-C(16)
91.02(15) C(18)-N(1)-C(19)
N(1)-C(19)-S
114.63(18) N(1)-C(19)-C(20)
116.1(3) S-C(19)-C(20)
118.2(3)
124.9(3)
117.5(3)
117.4(3)
Ru-C(16)-C(17) 128.6(3)
Ru-C(16)-S
S-C(16)-C(17)
no precedents for the addition of primary amines to the
Câ-Cγ double bond. Therefore, the addition of the S-H
bond of the imidothiol form b to the CR-Câ double bond
of the allenylidene ligand of 1, followed by the coordina-
tion of the nitrogen atom to the Cγ atom of the resulting
thiocarbene intermediate, seems to be the most reason-
able way to explain the formation of 6.
Moreover, since the formation of an isomer of 6
containing the nitrogen atom bonded to the RuC carbon
atom is not observed, eq 4 suggests that the addition of
SH bonds to the CR-Câ double bond of the allenylidene
ligand of 1 is favored with regard to the addition of NH
bonds.
a
M(1) is the centroid of the C(1)-C(5) Cp carbon atoms.
Similarly to 2 and 4, the geometry around the
ruthenium center in 7 is close to octahedral with the
cyclopentadienyl ligand occupying one face of the octa-
hedron. The angles formed by the triisopropylphosphine,
the carbonyl group, and the thiazinyl ligand are close
to 90°.
The thiazine skeleton maintains a boat conformation
with the C(16), C(17), N(1), and C(19) atoms lying in a
plane (the deviations from this plane are -0.013(3),
0.014(3), -0.012(3), and 0.015(4) Å, respectively) and
the C(18) and S atoms situated 0.536(3) and 0.4734(9)
Å above the plane, respectively.
The most noticeable feature in the IR spectrum of 6
in Nujol is the presence of a ν(NH) band at 3249 cm-1
.
1
The Ru-C(16) distance of 2.067(4) Å compares well
with the Ru-C(7) distances in 2 and 4 and supports a
Ru-C(sp2) single bond. The angles Ru-C(16)-C(17) )
128.6(3)° and Ru-C(16)-S ) 114.63(14)° support the
sp2 hybridization for C(16).
In the H NMR spectrum, the NH resonance appears
at 8.95 ppm, as a broad signal, whereas the resonance
due to the RuCdCH proton is observed as a singlet at
5.70 ppm. The 13C{1H} NMR spectrum shows the RuC
resonance at 130.9 as a doublet with a J (CP) value of
14.2 Hz.
The structural parameters within the thiazine ring
agree well with those found in organic thiazines.16 The
C(16)-C(17) (1.313(5) Å) and C(19)-Ν(1) (1.259(5) Å)
bond lengths support the double-bond character of these
bonds, whereas the C(16)-S (1.762(4) Å), S-C(19)
(1.757(4) Å), N(1)-C(18) (1.464(4) Å), and C(17)-C(18)
(1.512(5) Å) distances indicate single bonds between
these atoms.
Similarly to 2, the nitrogen atom of 6 undergoes
deprotonation in basic medium. Thus, the treatment of
tetrahydrofuran suspensions of 6 with sodium methox-
ide leads to the thiazinyl derivative Ru(η5-C5H5)-
{4,4-diphenyl-2-(p-pyridinyl)-4H-1,3-thiazin-6-yl}(CO)-
(PiPr3) (7), which was isolated as a yellow solid in 60%
yield, according to eq 6.
In agreement with the structure shown in Figure 3,
1
the H NMR spectrum of 7 contains a singlet at 6.08
ppm due to the C(17)-H resonance, and the 13C{1H}
NMR spectrum shows a doublet at 132.2 ppm, with a
J (CP) value of 13.8 Hz, corresponding to C(16).
The deprotonation of 6 is reversible. Thus, the addi-
tion of 1.1 equiv of HBF4‚OEt2 to dichloromethane
solutions of 7 regenerates 6. Similarly, the treatment
of dichloromethane solutions of 7 with 1.1 equiv of
methyl trifluoromethanesulfonate yields the N-meth-
ylthiazinium derivative [Ru(η5-C5H5){3-methyl-4,4-
(16) (a) Yokoyama, M.; Nakamura, M.; Ohteki, H.; Imamoto, T.;
Yamaguchi, K. J . Org. Chem. 1982, 47, 1090. (b) Bakasse, M.; Duguay,
G.; Quiniou, H.; Toupet, L. Tetrahedron 1988, 44, 139. (c) Tea, C. G.;
Prade`re, J . P.; Bujoli, B.; Quiniou, H.; Toupet, L. Bull. Soc. Chim. Fr.
1987, 149. (d) Quiniou, H.; Guilloton, O. Adv. Heterocycl. Chem. 1990,
50, 85.
Complex 7 was characterized by an X-ray crystal-
lographic study. Figure 3 shows a view of the molecular
geometry. Selected bond distances and angles are col-
lected in Table 2.

[Ru(η5-C5H5)(CdCdCPh2)(CO)(PiPr3)]BF4
Organometallics, Vol. 19, No. 21, 2000 4333
diphenyl-2-(p-pyridinyl)-4H-1,3-thiazinium-6-yl}(CO)-
(PiPr3)]CF3SO3 (8), which was isolated as an orange
solid in 76% yield (eq 7).
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)(PiPr3)]BF4 (1)
was prepared by the published method.10
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.
P r ep a r a tion of [Ru (η5-C5H5){2,2-d ip h en yl-2H-p yr id in -
iu m [1,2-a ]p yr im id in -4-yl}(CO)(P iP r 3)]BF 4 (2) a n d [Ru (η5-
C5H5){C(CHdCP h 2)dNHC(CH)4N}(CO)(P iP r 3)]BF 4 (3). A
dark red solution of 1 (295 mg, 0.47 mmol) in 5 mL of
dichloromethane at -55 °C was treated with 2-aminopyridine
(49 mg, 0.52 mmol), and the mixture was stirred for 10 min.
The solution became yellow and the solvent was removed in
vacuo, giving a yellow residue. The 31P{1H} NMR (CDCl3)
spectrum of this residue shows the presence of complexes 2
and 3 in a molar ratio of 4:1. The residue was washed with
diethyl ether to afford a yellow solid, which was crystallized,
at room temperature, from dichloromethane/diethyl ether to
give yellow crystals of complex 2. Yield: 251 mg (66%). Anal.
Calcd for C35H42BF4N2OPRu‚CH2Cl2: C, 51.87; H, 5.22; N,
3.46. Found: C, 51.89; H, 5.22; N, 3.63.
The IR spectrum of 8, in Nujol, shows the character-
istic stretching bands of the [CF3SO3]- anion at 1275,
1
1260, 1161, and 1030 cm-1. In the H NMR spectrum,
the most noticeable resonances are two singlets at 5.79
and 4.55 ppm, with a 1:3 intensity ratio, corresponding
to the RuCdCH proton and methyl group, respectively.
The 13C{1H} NMR spectrum contains a resonance due
to the RuCd carbon atom, which appears at 132.3 ppm
as a doublet with a J (CP) value of 13.8 Hz.
Sp ectr oscop ic Da ta for 2.
As a consequence of the discovery of the cephalospor-
ins and the enormous developments occurring in the
chemistry of these antibiotics since the 1940s, the 1,3-
thiazine nucleus has became one of the most important
six-membered heterocycles.16d The syntheses of 1,3-
thiazines have been classified in four types ([3 + 3], [4
+ 2], [5 + 1], and [6 + 0]) according to the composition
of the assembling units.17 The reaction shown in eq 4
is a novel [3 + 3] synthesis, where an allenylidene
derivative is used as the C3 reagent for the first time.
IR (Nujol, cm-1): ν(NH) 3328 (m), ν(CO) 1935 (s), ν(CdN,
CdC, Ph) 1646 (m), 1592 (s), 1516 (m), ν(BF4) 1093 (br). 1H
NMR (300 MHz, 20 °C, CDCl3, plus COSY): δ 8.68 (d, 1H,
J (H6H7) ) 6.9, H6), 8.56 (s, 1H, NH), 7.28-7.12 (m, 12H, H8,
H9, and Ph), 6.60 (ddd, 1H, J (H6H7) ) J (H7H8) ) 6.9, J (H7H9)
) 2.1, H7), 5.50 (s, 1H, H3), 5.30 (s, 5H, Cp), 2.13 (m, 3H,
PCHCH3), 0.89 (dd, 9H, J (HH) ) 6.9, J (PH) ) 14.7, PCHCH3),
0.86 (dd, 9H, J (PH) ) 6.9, J (PH) ) 13.8, PCHCH3). 31P{1H}
NMR (121.4 MHz, 20 °C, CDCl3): δ 62.3 (s). 13C{1H} NMR
(75.4 MHz, 20 °C, CDCl3, plus DEPT): δ 206.5 (d, J (PC) )
21.1, CO), 151.3 (s, C9a), 145.8 (d, J (PC) ) 12.0, C4), 145.2,
144.7 (both s, Cipso-Ph), 141.0, 140.3, 115.5, 112.2 (all s, C6-
C9), 134.4 (br s, C3), 128.9, 128.6, 127.9, 127.2, 126.5 (all s,
Ph), 85.7 (s, Cp), 62.3 (s, C2), 25.5 (d, J (PC) ) 21.7, PCHCH3),
19.6, 18.8 (both s, PCHCH3). MS (FAB+): m/z 639 (M+).
Sp ectr oscop ic Da ta for 3. IR (Nujol, cm-1): ν(NH) 3283
(m), ν(CO) 1952 (s), ν(CdN) 1592 (m), ν(BF4) 1090 (br). 1H
NMR (300 MHz, 20 °C, CDCl3): δ 11.22 (br s, 1H, NH), 8.17
(d, J (HH) ) 4.8, 1H, py), 7.74 (m, 1H, py) 7.54-6.90 (m, 13H,
Ph + 2H, py + dCH), 5.04 (s, 5H, Cp), 2.31 (m, 3H, PCHCH3),
1.29 (dd, 9H, J (HH) ) 6.9, J (PH) ) 14.4, PCHCH3), 1.26 (dd,
9H, J (PH) ) 6.6, J (PH) ) 13.5, PCHCH3). 31P{1H} NMR (121.4
MHz, 20 °C, CDCl3): δ 62.6 (s). 13C{1H} NMR (75.4 MHz, 20
°C, CDCl3): δ 255.1 (d, J (PC) ) 8.4, RuC), 203.8 (d, J (PC) )
16.1, CO), 148.0, 139.1, 130.2, 128.2, 128.0, 122.9, 117.4 (all
s, Ph + py + CHdCPh2), 87.5 (s, Cp), 29.1 (d, J (PC) ) 23.4,
PCHCH3), 19.8, 19.5 (both s, PCHCH3). All attempts to obtain
complex 3 analytically pure from the reaction mixture of 2 and
3 by either fractional crystallization or column chromatogra-
phy were unsuccessful.
Con clu d in g Rem a r k s
This study has revealed the existence of two new
types of η1-carbon unsaturated ligands and the ability
of the unsaturated chain of the allenylidene ligand of
[Ru(η5-C5H5)(CdCdCPh2)(CO)(PiPr3)]BF4 to act as a C3
reagent in condensation reactions with 2-aminopyridine
and thioisonicotinamide.
Reactions of [Ru(η5-C5H5)(CdCdCPh2)(CO)(PiPr3)]-
BF4 with the above-mentioned organic molecules
leads to the derivatives [Ru(η5-C5H5){2,2-diphenyl-2H-
pyridinium[1,2-a]pyrimidin-4-yl}(CO)(PiPr3)]BF4 and
[Ru(η5-C5H5){4,4-diphenyl-2-(p-pyridinyl)-4H-1,3-thiaz-
inium-6-yl}(CO)(PiPr3)]BF4, which react with sodium
methoxide to give the corresponding pyrido[1,2-a]pyri-
midinyl and 1,3-thiazinyl complexes and, in contrast to
the previously reported pyrazolo[1,2-a]pyrazolyl related
compounds, do not undergo ring opening.
In conclusion, the allenylidene ligand of [Ru(η5-C5H5)-
(CdCdCPh2)(CO)(PiPr3)]BF4 undergoes 1,2,3-dihetero-
cyclization reactions with primary amines containing a
second heteroatom and thioamides, similar to those with
secondary amines with a second heteroatom. However,
the resulting cycles from the primary amines are stable
in basic medium, as a consequence of the presence of a
NH bond in one of the heterocycles, which can be
deprotonated, preventing the ring opening.
P r ep a r a tion of Ru (η5-C5H5){2,2-d ip h en yl-2H-p yr id o-
[1,2-a ]p yr im id in -4-yl}(CO)(P iP r 3) (4). A yellow suspension
of 2 (160 mg, 0.22 mmol) in 10 mL of tetrahydrofuran was
treated with sodium methoxide (24 mg, 0.44 mmol) and stirred
for 1 h. The solvent was removed in vacuo. Toluene (10 mL)
was added, and the suspension was filtered to eliminate
sodium tetrafluoroborate. Solvent was evaporated, and the
residue was washed with pentane to afford a yellow solid.
(17) Sainsbury, M. In Comprehensive Heterocyclic Chemistry II, A
Review of the Literature 1982-1995; Boulton, A. J ., Ed.; Pergamon:
Oxford, U.K., 1996; Vol. 6, Chapter 6.07.

4334 Organometallics, Vol. 19, No. 21, 2000
Bernad et al.
Ta ble 3. Cr ysta l Da ta a n d Da ta Collection a n d Refin em en t Deta ils for
[Ru (η5-C5H5){2,2-d ip h en yl-2H-p yr id in iu m [1,2-a ]p yr im id in -4-yl}(CO)(P iP r 3)]BF 4 (2),
Ru (η5-C5H5){2,2-d ip h en yl-2H-p yr id o[1,2-a ]p yr im id in -4-yl}(CO)(P iP r 3) (4), a n d
Ru (η5-C5H5){4,4-d ip h en yl-2-(p-p yr id in yl)-4H-1,3-th ia zin -6-yl}(CO)(P iP r 3) (7)
2
4
7
Crystal Data
C35H41N2OPRu
formula
mol wt
C
35H42BF4N2OPRu‚CH2Cl2
C36H41N2OPRuS‚1/2C7H8
727.88
810.52
637.74
color and habit
symmetry, space group
a, Å
b, Å
yellow prism
monoclinic, P21
10.207(3)
17.975(9)
10.305(5)
98.11(3)
yellow prism
monoclinic, P21/n
11.726(2)
17.719(3)
15.393(3)
103.18(2)
3114(1); 4
1.360
yellow prism
monoclinic, P21/c
14.688(9)
13.419(5)
17.696(8)
102.65(3)
3403(3); 4
1.421
c, Å
â, deg
V, Å3; Z
1871(1); 2
1.438
D
calcd, g cm-3
Data Collection and Refinement
diffractometer
λ(Mo KR), Å
monochromator
µ, mm-1
AFC6S-Rigaku
0.710 73
graphite oriented
0.646
Bruker Siemens STOE AED-2
0.710 73
graphite oriented
0.58
Bruker Siemens-P4
0.710 73
graphite oriented
0.604
scan type
ω/2θ
ω/2θ
ω/2θ
2θ range, deg
temp, K
3 e 2θ e 50
3 e 2θ e 50
3 e 2θ e 50
298.0(2)
298.0(2)
173.0(2)
no.of data collect
no. of unique data
no. of obsd data
no. of params refined
R1a
3427
6747
7219
5430 (Rint ) 0.0451)
5880 (Rint ) 0.0204)
2733
393
0.0537 (F > 3σ(F))
371
419
0.0528 (F2 > 2σ(F2))
0.0984
0.0390 (F2 > 2σ(F2))
0.1082
wR2b (all data)
GOF
2.364
0.995
1.009
R1(F) ) ∑||Fo| - |Fc||/∑|Fo|. wR2(F2) ) {∑[w(Fo - Fc2)2]/∑[w(Fo2)2]}1/2
.
a
b
2
Yield: 84 mg (60%). Anal. Calcd for C35H41N2OPRu: C, 65.91;
C6-C9), 142.0, 139.5 (both s, Cipso-Ph), 135.0 (s, C3), 128.9, 128.8,
128.5, 128.1, 127.7 (all s, Ph), 120.9 (q, J (CF) ) 322, CF3), 85.9
(s, Cp), 69.2 (s, C2), 36.24 (s, NCH3), 25.3 (d, J (PC) ) 19.8,
PCHCH3), 19.4, 18.7 (both s, PCHCH3). MS (FAB+): m/z 653
(M+).
H, 6.48; N, 4.39. Found: C, 65.98; H, 6.39; N, 4.52. IR (Nujol,
cm-1): ν(CO) 1918 (s), ν(CdN, CdC, Ph) 1639 (m), 1592 (s),
1530 (m). 1H NMR (300 MHz, 20 °C, C6D6, plus COSY): δ 7.86
(d, 1H, J (H6H7) ) 6.9, H6), 7.80-7.00 (m, 10H, Ph), 6.78 (d,
1H, J (H8H9) ) 9.0, H9), 6.32 (ddd, 1H, J (H8H9) ) 9.0, J (H7H8)
) 6.9, J (H6H8) ) 1.5, H8), 5.53 (dd, 1H, J (H6H7) ) J (H7H8) )
6.9, H7), 4.94 (s, 1H, H3), 4.88 (s, 5H, Cp), 2.00 (m, 3H,
PCHCH3), 0.77 (dd, 9H, J (PH) ) 6.6, J (PH) ) 13.5, PCHCH3),
0.64 (dd, 9H, J (HH) ) 7.2, J (PH) ) 12.9, PCHCH3). 31P{1H}
NMR (121.4 MHz, 20 °C, C6D6): δ 65.6 (s). 13C{1H} NMR (75.4
MHz, 20 °C, C6D6, plus HETCOR): δ 207.9 (d, J (PC) ) 21.7,
CO), 152.5 (s, C9a), 151.9, 150.6 (both s, Cipso-Ph), 140.2 (d, J (PC)
) 13.7, C4), 138.9 (s, C6), 130.5 (s, C8), 129.3 (s, C3), 128.6,
128.5, 128.4, 127.6, 126.0, 125.1 (all s, Ph), 123.1 (s, C9), 101.6
(s, C7), 85.8 (s, Cp), 66.2 (s, C2), 26.0 (d, J (PC) ) 23, PCHCH3),
19.9, 19.3 (both s, PCHCH3). MS (FAB+): m/z 639 (M++ H).
P r ep a r a tion of [Ru (η5-C5H5){4,4-d ip h en yl-2-(p-p yr id i-
n yl)-4H-1,3-th ia zin iu m -6-yl}(CO)(P iP r 3)]BF 4 (6).
A dark red solution of 1 (395 mg, 0.63 mmol) in 12 mL of
dichloromethane was treated with thioisonicotinamide (96 mg,
0.69 mmol), and the mixture was refluxed for 3 h. The solvent
was removed in vacuo, and the residue was washed with
diethyl ether to afford an orange solid. Yield: 410 mg (86%).
Anal. Calcd for C36H42BF4N2OPRuS: C, 56.18; H, 5.50; N, 3.64;
S, 4.17. Found: C, 56.10; H, 5.57; N, 3.59; S, 4.25. IR (Nujol,
cm-1): ν(NH) 3249 (w), ν(CO) 1909 (s), ν(CdN, CdC, Ph) 1638
(m), 1620 (m), 1575 (m). 1H NMR (300 MHz, 20 °C, CDCl3): δ
8.95 (br, 1H, NH), 8.68 (d, 2H, J (HH) ) 6.5, py), 8.08 (d, 2H,
J (HH) ) 6.5, py), 7.31-710 (m, 10H, Ph), 5.70 (s, 1H, dCH),
5.19 (s, 5H, Cp), 2.20 (m, 3H, PCHCH3), 1.04 (dd, 9H, J (HH)
) 7.2, J (PH) ) 14.4, PCHCH3), 1.02 (dd, 9H, J (HH) ) 7.2,
J (PH) ) 13.8, PCHCH3). 31P{1H} NMR (121.4 MHz, 20 °C,
CDCl3): δ 66.4 (s). 13C{1H} NMR (75.4 MHz, 20 °C, CDCl3): δ
207.0 (d, J (PC) ) 19.3, CO), 158.5 (s, SCN), 148.6 (s, Cp-py),
148.1 (s, Co-py), 147.9, 147.7 (both s, Cipso-Ph), 130.9 (d, J (PC)
) 14.2, RuC), 128.2 (s, dCH), 127.9, 127.8, 127.7, 126.3, 126.2
(all s, Ph),121.9 (s, Cm-py), 85.7 (s, Cp), 70.8 (s, CPh2), 26.8 (d,
J (PC) ) 23.5, PCHCH3), 19.9, 19.4 (both s, PCHCH3). MS
(FAB+): m/z 683 (M+).
Rea ction of 4 w ith HBF 4. A solution of 4 (12.8 mg, 0.02
mmol) in 0.5 mL of dichloromethane-d2 was treated with 2.8
µL (0.02 mmol) of HBF4‚OEt2. The 1H and 31P{1H} NMR
spectra recorded after 2 min showed only the presence of 2.
P r ep a r a tion of [Ru (η5-C5H5){1-m eth yl-2,2-d ip h en yl--
2H-p yr id in iu m [1,2-a ]p yr im id in -4-yl}(CO)(P iP r 3)]CF 3SO3
(5). A yellow solution of 4 (145 mg, 0.22 mmol) in 5 mL of
dichloromethane was treated with methyl trifluoromethane-
sulfonate (27 µL, 0.24 mmol), and the mixture was stirred for
5 min. The solvent was removed in vacuo, and the residue was
washed with diethyl ether to afford a yellow solid. Yield: 104
mg (65%). Anal. Calcd for C37H44F3N2O4PRuS: C, 55.42; H,
5.53; N, 3.49; S, 4.00. Found: C, 55.74; H, 5.68; N, 3.23; S,
4.19. IR (Nujol, cm-1): ν(CO) 1927 (s), ν(CdN, CdC, Ph) 1630
(m), 1585 (m), 1500 (m), ν(SO3) and ν(CF3) 1277 (vs), 1262 (vs),
1
1144 (s), 1030 (s). H NMR (300 MHz, 20 °C, CDCl3): δ 9.14
(br s, 1H, H6), 7.82 (m, 1H, py), 7.39-7.10 (m, 12H, Ph + 2H,
py), 6.97 (m, 1H, py), 5.42 (br s, 1H, H3), 5.25 (s, 5H, Cp), 2.96
(s, 3H, NCH3), 2.12 (m, 3H, PCHCH3), 0.90 (m, 18H, PCHCH3).
31P{1H} NMR (121.4 MHz, 20 °C, CDCl3): δ 62.8 (s). 13C{1H}
NMR (75.4 MHz, 20 °C, CDCl3): δ 206.3 (d, J (PC) ) 21.6, CO),
151.4 (s, C9a), 145.3 (br, C4), 143.4, 142.9, 112.7, 112.2 (all s,
P r ep a r a tion of Ru (η5-C5H5){4,4-d ip h en yl-2-(p-p yr id i-
n yl)-4H-1,3-th ia zin -6-yl}(CO)(P iP r 3) (7). An orange sus-
pension of 6 (410 mg, 0.54 mmol) in 15 mL of tetrahydrofuran
was treated with sodium methoxide (58 mg, 1.08 mmol) and

[Ru(η5-C5H5)(CdCdCPh2)(CO)(PiPr3)]BF4
Organometallics, Vol. 19, No. 21, 2000 4335
stirred for 1 h. The solvent was removed in vacuo. Toluene
(10 mL) was added, and the suspension was filtered to
eliminate sodium tetrafluoroborate. The solution was concen-
trated to ca. 1 mL, and 10 mL of pentane was added to afford
a yellow solid, which was washed with pentane. Yield: 175
mg (60%). Anal. Calcd for C36H41N2OPRuS: C, 63.42; H, 6.06;
N, 4.11; S, 4.70. Found: C, 63.28; H, 5.95; N, 4.01; S, 4.93. IR
(Nujol, cm-1): ν(CO) 1920 (s), ν(CdN, CdC, Ph) 1580 (m), 1580
CO), 157.8 (br, SCN), 152.5 (br, Cp-py), 147.8, 147.4 (both br,
C
ipso-Ph), 145.9 (s, Co-py), 132.3 (d, J (PC) ) 13.8, RuC), 129.7
(s, dCH), 128.2, 128.1, 127.9, 127.0, 126.9 (all s, Ph),125.2 (s,
m-py), 121.0 (q, J (CF) ) 321, CF3), 86.0 (s, Cp), 71.7 (s, CPh2),
C
48.5 (s, NCH3), 27.3 (d, J (PC) ) 23.5, PCHCH3), 19.9, 19.4
(both s, PCHCH3). MS (FAB+): m/z 697 (M+).
Cr ysta l Da ta for 2, 4, a n d 7. Crystals suitable for X-ray
diffraction analysis were mounted onto a glass fiber and
transferred to AFC6S-Rigaku (2; T ) 298.0(2) K), Bruker-
Siemens-STOE AED-2 (4; T ) 298.0(2) K), and Bruker-
Siemens P4 (7; T ) 173.0(2) K) automatic diffractometers (Mo
KR radiation, graphite monochromator, λ ) 0.710 73 Å).
Accurate unit cell parameters were determined by least-
squares fitting from the settings of high-angle reflections. Data
were collected by the ω/2θ scan method. Lorentz and polariza-
tion corrections were applied. Decay were monitored by
measuring three standard reflections throughout data collec-
tion. Shift corrections for decay and absorption (semiempirical
ψ-scan method) were also applied.
The structures were solved by Patterson methods and
refined by full-matrix least squares on F (2)18 or F2 (4 and 7).19
Non-hydrogen atoms were anisotropically refined, and the
hydrogen atoms were observed or included at idealized posi-
tions. For 2 and 7, crystallization solvent molecules (dichlo-
romethane and disordered toluene, respectively) were also
detected, included in the refinement, and refined isotropically.
Crystal data and details of the data collection and refinenent
are given in Table 3.
1
(m), 1575 (m), 1550 (m). H NMR (300 MHz, 20 °C, C6D6): δ
8.60 (d, 2H, J (HH) ) 4.5, py), 7.85 (d, 2H, J (HH) ) 4.5, py),
7.73 (m, 4H, Ph), 7.28-7.00 (m, 6H, Ph), 6.08 (s, 1H, dCH),
4.88 (s, 5H, Cp), 1.95 (m, 3H, PCHCH3), 0.83 (dd, 9H, J (HH)
) 7.2, J (PH) ) 14.1, PCHCH3), 0.76 (dd, 9H, J (HH) ) 6.2,
J (PH) ) 13.2, PCHCH3). 31P{1H} NMR (121.4 MHz, 20 °C,
C6D6): δ 67.1 (s). 13C{1H} NMR (75.4 MHz, 20 °C, CD2Cl2): δ
207.6 (d, J (PC) ) 19.3, CO), 159.3 (s, SCN), 150.4 (s, Co-py),
149.6, 148.8 (both s, Cipso-Ph), 145.8 (s, Cp-py), 132.2 (d, J (PC)
) 13.8, RuC), 130.7 (s, dCH), 128.3, 128.1, 127.9, 126.4, 126.3
(all s, Ph),121.3 (s, Cm-py), 86.2 (s, Cp), 70.9 (s, CPh2), 27.4 (d,
J (PC) ) 23.0, PCHCH3), 20.3, 19.8 (both s, PCHCH3). MS
(FAB+): m/z 683 (M+ + H).
Rea ction of 7 w ith HBF 4. A solution of 7 (13.4 mg, 0.02
mmol) in 0.5 mL of dichloromethane-d2 was treated with 2.8
µL (0.02 mmol) of HBF4‚OEt2. The 1H and 31P{1H} NMR
spectra recorded after 2 min showed only the presence of 6.
P r ep a r a tion of [Ru (η5-C5H5){3-m eth yl-4,4-d ip h en yl-2-
(p -p y r i d i n y l)-4H -1,3-t h i a z i n i u m -6-y l}(C O )(P i P r 3 )]-
CF 3SO3 (8). A yellow-brown solution of 7 (78 mg, 0.11 mmol)
in 5 mL of dichloromethane was treated with methyl trifluo-
romethanesulfonate (15 µL, 0.13 mmol), and it was stirred for
5 min. The red solution obtained was concentrated to ca. 2
mL, and addition of 12 mL of diethyl ether caused the
precipitation of an orange solid. Yield: 75 mg (76%). Anal.
Calcd for C38H44F3N2O4PRuS2: C, 53.95; H, 5.24; N, 3.31; S,
7.58. Found: C, 53.90; H, 5.21; N, 3.40; S, 7.63. IR (Nujol,
cm-1): ν(CO) 1925 (s), ν(CdN, CdC, Ph) 1645 (m), 1562 (m),
Ack n ow led gm en t. We aknowledge financial sup-
port from the DGES of Spain (Project PB98-1591).
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 2, 4, and 7.
This material is available free of charge via the Internet at
http://pubs.acs.org.
1
ν(SO3) and ν(CF3) 1275 (vs), 1260 (vs), 1161 (s), 1030 (s). H
NMR (300 MHz, 20 °C, CDCl3): δ 8.93 (d, 2H, J (HH) ) 6.8,
py), 8.55 (d, 2H, J (HH) ) 6.8, py), 7.38-7.24 (m, 10H, Ph),
5.79 (s, 1H, dCH), 5.31 (s, 5H, Cp), 4.55 (s, 3H, NCH3), 2.29
(m, 3H, PCHCH3), 1.15 (dd, 9H, J (HH) ) 7.5, J (PH) ) 14.4,
PCHCH3), 1.13 (dd, 9H, J (HH) ) 6.9, J (PH) ) 13.8, PCHCH3).
31P{1H} NMR (121.4 MHz, 20 °C, CD2Cl2): δ 65.2 (s). 13C{1H}
NMR (75.4 MHz, 20 °C, CD2Cl2): δ 207.2 (d, J (PC) ) 19.3,
OM000415T
(18) Sheldrick, G. M. SHELX-97; University of Go¨ttingen, Go¨ttingen,
Germany, 1997.
(19) TEXSAN Single-Crystal Structure Analysis Software, version
5.0; Molecular Structure Corp., The Woodlands, TX, 1989.