The cyclopentadienyl-osmium moiety as template for the formation of a dihydronaphthylphosphine by coupling between phenylacetylene and an α-alkenylphosphine

Article abstract of DOI:10.1021/om050487q

Complex Os(η⁵-C₅H₅)(C≡CPh) {[η²-CH₂=C-(CH₃)]PⁱPr ₂} (1) reacts with HBF₄·OEt₂ to give the π-alkyne derivative [Os(η⁵-C₅H₅) (η²-HC≡CPh){η²-CH₂=C(CH ₃)]PⁱPr₂}]BF₄ (2), which is transformed to [Os(η⁵-C₅H₅)(1,2-dihydro-2- methylnaphth-2-yldiisopropylphosphine)]BF₄ (3) as a result of the coupling of the alkyne with the isopropenyl substituent of the starting phosphine. The tridentate coordination mode of the dihydronaphthylphosphine in 3 is proved by X-ray diffraction analysis.

Full text of DOI:10.1021/om050487q

5180
Organometallics 2005, 24, 5180-5183
The Cyclopentadienyl-Osmium Moiety as Template for
the Formation of a Dihydronaphthylphosphine by
Coupling between Phenylacetylene and an
r-Alkenylphosphine
Miguel Baya, Mar´ıa L. Buil, Miguel A. Esteruelas,* 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 June 14, 2005
Summary: Complex Os(η5-C5H5)(CtCPh){[η2-CH2dC-
(CH3)]PiPr2} (1) reacts with HBF4‚OEt2 to give the
π-alkyne derivative [Os(η5-C5H5)(η2-HCtCPh){[η2-CH2d
C(CH3)]PiPr2}]BF4 (2), which is transformed to [Os(η5-
C5H5)(1,2-dihydro-2-methylnaphth-2-yldiisopropylphos-
phine)]BF4 (3) as a result of the coupling of the alkyne
with the isopropenyl substituent of the starting phos-
phine. The tridentate coordination mode of the dihy-
dronaphthylphosphine in 3 is proved by X-ray diffraction
analysis.
Scheme 1
Intermolecular reactions between alkenes and alkynes
promoted by transition metal compounds are of pivotal
importance for the assembly of unsaturated linear
molecules and cyclic products.1 The linear couplings
take place via metallacycle or vinylidene intermediates
or, alternatively, involve hydrometalation or C-H bond
activation processes.2 Most of the cyclization reactions
are [2 + 2] additions, which lead to strained car-
bocycles.3
As a part of our work on the chemistry of the
cyclopentadienyl-osmium unit4 and within a research
program dedicated to the functionalization of trialkyl-
phosphines,5 one year ago, we performed the dehydro-
genation of one of the phosphines of Os(η5-C5H5)Cl(Pi-
Pr3)2.6 Subsequently the resulting isopropenyldiisopropyl-
phosphine of Os(η5-C5H5)Cl{[η2-CH2dC(CH3)]PiPr2} has
been transformed into allylphosphines by reaction with
diazoalkanes via [2 + 2] cycloaddition processes,7 imino-
phosphines by insertion of the carbon-nitrogen triple
bond of benzonitriles into one of the C(sp2)-H bonds of
the isopropenyl group,8 and dienylphosphines via ene-
type reactions between the carbon-carbon double bond
of the R-alkenylphosphine and the carbon-carbon triple
bond of alkyne and alkynol substrates.9
We now show the transformation of isopropenyldiiso-
propylphosphine into a novel dihydronaphthyldiisopro-
pylphosphine (Scheme 1). This unprecedented cycliza-
tion between the isopropenyl substituent of the phosphine
and phenylacetylene takes place via both metallacycle
and vinylidene intermediates. Furthermore, it involves
vinyl- and aryl-CH bond activation and hydrometa-
lation processes.
In contrast to the known high nucleophility of the Câ
atom of the alkynyl groups in late-transition-metal
alkynyl complexes, the addition of 1.8 equiv of HBF4‚
OEt2 to a diethyl ether solution of the alkynyl compound
Os(η5-C5H5)(CtCPh){[η2-CH2dC(CH3)]PiPr2} (1) leads
to the π-phenylacetylene derivative [Os(η5-C5H5)(η2-
HCtCPh){[η2-CH2dC(CH3)]PiPr2}]BF4 (2), which is
isolated as an orange solid in 60% yield.
The presence of the π-alkyne ligand in 2 is supported
by the 1H and 13C{1H} NMR spectra of this compound.
The carbon-carbon triple bond gives rise, in the IR
* To whom correspondence should be addressed. E-mail: maester@
unizar.es.
(1) Naota T.; Takaya, H.; Murahashi, S.-I. Chem. Rev. 1998, 98,
2599.
1
spectrum, to a ν(CtC) band at 1729 cm-1. In the H
(2) Trost, B. M.; Toste, F. D.; Pinkerton, A. B. Chem. Rev. 2001,
101, 2067.
(3) De´rien, S.; Monnier, F.; Dixneuf, P. H. Top. Organomet. Chem.
2004, 11, 1.
(4) Esteruelas, M. A.; Lo´pez, A. M. Organometallics 2005, 24, 3584.
(5) (a) Edwards, A. J.; Esteruelas, M. A.; Lahoz, F. J.; Lo´pez, A. M.;
On˜ate, E.; Oro, L. A.; Tolosa, J. I. Organometallics 1997, 16, 1316. (b)
Esteruelas, M. A.; Lledo´s, A.; Maseras, F.; Oliva´n, M.; On˜ate, E.;
Tajada, M. A.; Toma`s, J. Organometallics 2003, 22, 2087. (c) Barrio,
P.; Esteruelas, M. A.; On˜ate, E. Organometallics 2003, 22, 2472.
(6) Baya, M.; Buil, M. L.; Esteruelas, M. A.; On˜ate, E. Organome-
tallics 2004, 23, 1416.
NMR spectrum in dichloromethane-d2, the HC(sp)-
hydrogen atom displays a singlet at 4.09 ppm, whereas
the resonances corresponding to H2C(sp2)-hydrogen
atoms of the phosphine are observed at 4.06 and 2.81
ppm as double doublets with H-P coupling constants
of 30.2 and 8.7 Hz, respectively, and a H-H coupling
constant of 3.0 Hz. In the 13C{1H} NMR spectrum the
C(sp) resonances of the alkyne appear at 124.5 and
120.8 ppm as singlets, while the C(sp2) resonances of
(7) Esteruelas, M. A.; Gonza´lez, A. I.; Lo´pez, A. M.; On˜ate, E.
Organometallics 2004, 23, 4858.
(8) Baya, M.; Esteruelas, M. A.; Gonza´lez, A. I.; Lo´pez, A. M.; On˜ate,
E. Organometallics 2005, 24, 1225.
(9) Baya, M.; Buil, M. L.; Esteruelas, M. A.; On˜ate, E. Organome-
tallics 2005, 24, 2030.
10.1021/om050487q CCC: $30.25 © 2005 American Chemical Society
Publication on Web 09/13/2005

Notes
Organometallics, Vol. 24, No. 21, 2005 5181
∆l parameters11 have values of 0.12 and -0.02 Å,
respectively.
The coordination fashion of the diene moiety in 3
agrees well with that found in the 1,4-diphenylbutadi-
ene derivative [OsH(η4-C4H4Ph2){[η2-CH2dC(CH3)]Pi-
n
Pr2}(PiPr2 Pr)]BF4 (θ ) 80.0(4)°, ∆d ) 0.15, ∆l ) -0.05
Å).5c However, it differs from that observed in the
osmium(0) complex Os(η4-C4H5Ph)(CO)(PiPr3)2, where
on the basis of θ (83.0(1)°), ∆d (0.064(3) Å), and ∆l
(0.036(5) Å) parameters, a coordination intermediate
between the resonance forms η4-π and σ2-π has been
proposed.13
Complex 3 is a new example of an η2-aromatic
compound.14 The coordination of C(3) and C(4) to the
osmium atom produces a slight alteration in the aro-
matic ring. Thus, the bond lengths C(3)-C(8), C(7)-
C(6), and C(5)-C(4) (1.440(9), 1.430(10), and 1.431(9)
Å, respectively) are considerably longer than the dis-
tances C(8)-C(7) and C(6)-C(5) (1.345(9) and 1.355-
(10) Å, respectively), which have more double-bond
character. A similar phenomenon has been observed for
the benzoallyl complex Os(η5-C5H5)(η3-CHPhC6H5)-
(PiPr3).15
The Os-P distance of 2.317(2) Å is about 0.01 Å
longer than the Os-P bond length in the isoprope-
nylphosphine derivative [Os(η5-C5H5){η2-(Z)-PhCHd
CHPh}{[η2-CH2dC(CH3)]PiPr2}]PF6 (2.3093(10) Å),6
about 0.02 Å longer than that found in the dienylphos-
phine compound Os(η5-C5H5)Cl{[η2-(E)-PhCdCHCH2C-
(dCH2)]PiPr2} (2.2990(12) Å),9 and about 0.05 Å longer
Figure 1. Molecular diagram of the cation of [Os(η5-C5H5)-
(1,2-dihydro-2-methylnapht-2-yldiisopropylphosphine)]B-
Ph4 (3). Selected bond lengths (Å) and angles (deg): Os-
C(1) ) 2.244(8), Os-C(2) ) 2.180(8), Os-C(3) ) 2.197(7),
Os-C(4) ) 2.369 (7), Os-P ) 2.317(2), C(1)-C(2) ) 1.416-
(10), C(3)-C(4) ) 1.392(9), C(2)-C(3) ) 1.423(9); C(9)-
C(10)-C(1) ) 107.0(6), C(2)-C(1)-C(10) ) 124.8(7), C(1)-
C(2)-C(3) 117.2(7), C(4)-C(3)-C(2) ) 116.9(7); C(3)-
C(4)-C(9) ) 115.4(6); C(4)-C(9)-C(10) ) 109.4(6).
the olefin are observed at 52.7 and 31.4 ppm as doublets
with C-P coupling constants of 17.3 and 5.7 Hz,
respectively. The 31P{1H} NMR spectrum shows a
singlet at 21.9 ppm.
In dichloromethane, complex 2 is converted to the
dihydronaphthyldiisopropylphosphine derivative [Os(η5-
C5H5)(1,2-dihydro-2-methylnapht-2-yldiisopropylphos-
phine)]BF4 (3), which is isolated as a brown solid in 60%
yield.
The tridentate coordination mode of the phosphine
was proved by an X-ray diffraction analysis experiment
on a single crystal of the BPh4 salt of 3. This salt was
prepared by treatment of the BF4 salt with NaBPh4 in
dichloromethane. Figure 1 shows a view of the structure
of the cation.
The geometry around the osmium center can be
described as a very distorted octahedron, with the
cyclopentadienyl ligand occupying the three sites of a
face, whereas the phosphorus atom and the double
bonds C(1)-C(2) and C(3)-C(4) of the phosphine are
situated in the sites of the opposite face.
The C(1)-C(2)-C(3)-C(4) moiety of the phosphine
coordinates to the metal center as expected for a
butadiene ligand.10 Coordination of both double bonds
is asymmetrical. The Os-C(terminal) distances (Os-
C(1) ) 2.244(8) Å and Os-C(4) ) 2.3697(7) Å) are
significantly longer than the Os-C(central) bond lengths
(Os-C(2) ) 2.180(8) Å and Os-C(3) ) 2.197(7) Å). On
the other hand, both C(terminal)-C(central) distances
(C(1)-C(2) ) 1.416(10) Å and C(3)-C(4) ) 1.392(9) Å)
are shorter than the C(central)-C(central) bond length
(C(2)-C(3) ) 1.423(9) Å). These structural parameters
strongly support a η4-π-coordination for the diene
moiety. In agreement with this coordination mode, the
dihedral angle between the C(1)-Os-C(4) and C(1)-
C(2)-C(3)-C(4) planes (θ) is 80.5(4)°, and the ∆d and
than those in the complexes iminophosphine Os(η5-
C5H5)Cl{NHdC(Ph)CHdC(CH3)PiPr2} (2.2686(12) Å)8
and R-allylphosphine [OsH(η5-C5H5){[η3-CHPhCHC-
(CH3)]PiPr2}]PF6 (2.2634(9) Å).7
The 1H and 13C{1H} NMR spectra of 3 are consistent
1
with the structure shown in Figure 1. In the H NMR
spectrum in dichloromethane-d2, the resonances corre-
sponding to the olefinic protons HC(1) and HC(2) appear
at 3.82 and 6.15 ppm, respectively. The H2C(9) group
displays two signals, at 1.95 and 1.17 ppm; the latter is
masked by a CH3 resonance. In the 13C{1H} NMR
spectrum, the ring junction carbon atoms C(3) and C(4)
give rise to singlets at 165.1 and 164.16 ppm, while the
olefinic C(2) and C(1) atoms display doublets at 66.4 and
49.4 ppm, with C-P coupling constants of 8.5 and 23.1
Hz, respectively. The resonances due to C(9) and C(10)
are observed at 33.2 and 52.7 ppm, also as doublets but
with C-P coupling constants of 6.1 and 34.8 Hz,
respectively. The 31P{1H} NMR spectrum shows a
singlet at -43.2 ppm, shifted 65.1 ppm to higher field
in comparison with the resonance of 2.
The addition of DBF4‚D2O to a dichloromethane
solution of 1 leads to the instantaneous formation of the
monodeuterated π-alkyne derivative [Os(η5-C5H5)(η2-
DCtCPh){[η2-CH2dC(CH3)]PiPr2}]BF4 (2-d1). Like 2, in
(11) ∆d ) {d[Os-C(1)] + d[Os-C(4)]}/2 - {d[Os-C(2)] + d[Os-
C(3)]}/2 and ∆l ) {l[C(1)-C(2)] + l[C(3)-C(4)]}/2 - l[C(2)-C(3)]. See
ref 12.
(12) Yasuda, H.; Nakamura, A. Angew. Chem., Int. Ed. Engl. 1987,
26, 723.
(13) Bohanna, C.; Esteruelas, M. A.; Lahoz, F. J.; On˜ate, E.; Oro,
L. A.; Sola, E. Organometallics 1995, 14, 4825.
(14) Keane, J. M.; Harman, W. D. Organometallics 2005, 24, 1786.
(15) Esteruelas, M. A.; Gonza´lez, A. I.; Lo´pez, A. M.; On˜ate, E.
Organometallics 2003, 22, 414.
(10) McArdle, P.; Skelton, J.; Manning, A. R. J. Organomet. Chem.
1997, 538, 9.

5182 Organometallics, Vol. 24, No. 21, 2005
Notes
Scheme 2
Scheme 4
Scheme 3
could afford a hydride-phenylvinylidene intermediate b,
which, according to our previous observations, should
be in equilibrium with the corresponding iPr2P-alkenyl-
hydride-osmacyclopentadiene species d. The reductive
elimination of isopropenyldiisopropylphosphine in the
latter and the subsequent insertion of the isopropenyl
group of the phosphine into the Os-aryl bond of the
osmacyclopentadiene moiety should lead to an osmacy-
cloheptadiene intermediate f. This species could gener-
ate the dihydronaphthylphosphine by reductive coupling
of the Os-C(sp2) and Os-C(sp3) bonds of the metalla-
cycle.
We note that, in contrast to this osmium system, the
indenyl-â-alkenylphosphine-ruthenium(II) [Ru(η5-C7H9)-
{[η2-CH2dCHCH2]PPh2}(PPh3)]+ reacts with terminal
alkynes and alkynols to afford vinylidene and allenyli-
dene intermediates, respectively, which are transformed
to bicyclic alkylidene compounds by intramolecular [2
+ 2] cycloadition processes between the olefinic sub-
stituent of the phosphine and the CR-Câ bonds of the
cumulene ligands.17
In conclusion, the cyclopentadienyl-osmium unit pro-
motes a novel cyclization reaction between phenylacety-
lene and the isopropenyl group of isopropenyldiisopro-
pylphosphine, which affords a 1,2-dihydro-2-methyl-
naphth-2-yldiisopropylphosphine-osmium complex. The
new phosphine is generated from two regioselective
C-C couplings: the terminal carbon atom of the alkyne
with the CR atom of the isopropenyl group of the starting
phosphine, and an ortho carbon atom of the phenyl
group of the alkyne with the Câ atom of the olefin
substituent of isopropenyldiisopropylphosphine. In ad-
dition to these C-C couplings the cyclization involves
CH bond activation reactions on the phenyl group of the
alkyne and the isopropenyl substituent of the starting
phosphine, as intermediate elementary steps of the
overall process.
dichloromethane, complex 2-d1 is converted to the
dihydronaphthylphosphine compound 3-d1, containing
a deuterium atom at C(2) (Scheme 2). The transforma-
tion involves a 1,2-deuterium shift in the alkyne of 2-d1.
This suggests the participation of a vinylidene inter-
mediate in the cyclization process. The positions of the
deuterium atoms in 2-d1 and 3-d1 are strongly sup-
ported by the 2H NMR spectra, which show broad
singlets at 4.1 and 6.2 ppm, respectively.
To know the destination of the hydrogen atom of the
ortho-CH bond of the phenyl ring activated during the
formation of 3 and 3-d1, we have also investigated the
reaction of Os(η5-C5H5)(CtCC6D5){[η2-CH2dC(CH3)]Pi-
Pr2} (1-d5) with HBF4‚OEt2 (Scheme 3). The addition
of 1.0 equiv of HBF4‚OEt2 to a dichloromethane solution
of 1-d5 gives [Os(η5-C5H5)(η2-HCtCC6D5){[η2-CH2d-
C(CH3)]PiPr2}]BF4 (2-d5). Similarly to 2 and 2-d1,
complex 2-d5 leads to 3-d5, containing a deuterium atom
at C(9). The presence of a deuterium at this carbon atom
is strongly supported by the 2H NMR spectrum of 3-d5,
which contains a broad singlet at 1.2 ppm.
Scheme 4 shows a sequence of reactions, which
rationalizes the presence of deuterium at C(2) of 3-d1
and at C(9) of 3-d5. Previously, we have proved that, in
solution, cyclopentadienyl-osmium-hydride-phenylvi-
nylidene species coexist in equilibrium with hydride-
osmacyclopentadiene derivatives, resulting from the
migratory insertion of the vinylidene into the Os-H
bond and subsequent ortho-CH bond activation of the
phenyl ring.16 The π-alkyne-vinylidene tautomerization
in 2, 2-d1, or 2-d5, followed by a C(sp2)-H bond
activation of the isopropenyl group of the phosphine,
(17) (a) AÄ lvarez, P.; Lastra, E.; Gimeno, J.; Bassetti, M.; Falvello,
L. R. J. Am. Chem. Soc. 2003, 125, 2386. (b) Bran˜a, P.; Gimeno, J.;
Sordo, J. A. J. Org. Chem. 2004, 69, 2544. (c) Bassetti, M.; AÄ lvarez,
P.; Gimeno, J.; Lastra, E. Organometallics 2004, 23, 5127. (d) D´ıez,
J.; Gamasa, M. P.; Gimeno, J.; Lastra, E.; Villar, A. Organometallics
2005, 24, 1410.
(16) (a) Baya, M.; Esteruelas, M. A.; On˜ate, E. Organometallics 2001,
20, 4875. (b) Baya, M.; Esteruelas, M. A. Organometallics 2002, 21,
2332. (c) Baya, M.; Esteruelas, M. A.; On˜ate, E. Organometallics 2002,
21, 5681.

Notes
Organometallics, Vol. 24, No. 21, 2005 5183
mg, 0.37 mmol) in 0.6 mL of dichloromethane was heated at
40 °C for 16 h. After that period of time, the solvent was
concentrated to dryness. Addition of diethyl ether (7 mL)
caused the formation of a brown solid. The solution was
decanted and the solid washed with diethyl ether (2 × 3 mL)
and dried in vacuo. Yield: 134 mg (60%). Anal. Calcd for
C22H30BF4OsP: C, 41.36; H, 4.89. Found: C, 41.11; H, 4.38.
IR (Nujol, cm-1): ν(BF4) 1060. 1H NMR (400 MHz, CD2Cl2,
293 K): δ 7.77-6.80 (m, 4H, Ph); 6.15 (dd, 1H, JH-H ) 6.0,
Experimental Section
General Procedures. 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 Os(η5-C5H5)-
(CtCPh){[η2-CH2dC(CH3)]PiPr2} (1)9 and DBF4‚D2O16c were
prepared by the published methods. Complex Os(η5-C5H5)(Ct
CC6D5){[η2-CH2dC(CH3)]PiPr2} (1-d5) was prepared analo-
gously to 1 using lithium phenylacetylide-d5 instead of PhCt
CLi.
JH-P ) 2.0, H2); 4.92 (s, 5H, η5-C5H5); 3.82 (ddd, 1H, JH-H
)
6.0, JH-P ) JH-H′ ) 2.0, H1); 3.03 (m, 1H, one of the PCH);
2.55 (m, 1H, one of the PCH); 1.95 (ddd, 1H, JH-P ) 5.6, JH-H
1H, 31P{1H}, and 13C{1H} NMR spectra were recorded on
either a Bruker Avance 300 MHz or a Bruker Avance 400 MHz
instrument. Chemical shifts (expressed in parts per million)
are referenced to residual solvent peaks (1H, 13C{1H}) or
external H3PO4 (31P{1H}). Coupling constants, J, are given in
hertz. Infrared spectra were run on a Perkin-Elmer 1730
spectrometer (Nujol mulls on polyethylene sheets). C, H, and
N analyses were carried out in a Perkin-Elmer 2400 CHNS/O
analyzer. Mass spectral analyses were performed with a VG
Austospec instrument. In LSIMS+ mode, ions were produced
with the standard Cs+ gun at ca. 30 kV, and 3-nitrobenzyl
alcohol (NBA) was used in the matrix.
) 4.4, JH-H ) 2.0, one of the H in CH2); 1.55 (dd, 3H, JH-P
16.0, JH-H ) 7.2, one of the PCHCH3); 1.49 (dd, 3H, JH-P
15.6, JH-H ) 8.0, one of the PCHCH3); 1.47 (dd, 3H, JH-P
16.8, JH-H ) 7.6, one of the PCHCH3); 1.46 (dd, 3H, JH-P
)
)
)
)
13.8, JH-H ) 7.4, one of the PCHCH3); 1.17 (d, 4H, JH-P ) 14.0,
CH3 + 1H of the CH2). 13C{1H} NMR (100.5 MHz, CD2Cl2, 293
K, plus APT, plus HSQC, plus HMBC): δ 165.1 and 164.6
(both s, C3 and C4); 139.8, 129.2, 127.0, and 121.6 (all s, C5,
C6, C7, and C8); 80.0 (s, η5-C5H5); 66.4 (d, JC-P ) 8.5, C2); 52.7
(d, JC-P ) 34.8, C10); 49.4 (d, JC-P ) 23.1, C1); 33.2 (d, JC-P
6.1, C9); 30.2 (d, JC-P ) 14.0, one of the PCH); 25.9 (d, JC-P
)
)
Preparation of [Os(η5-C5H5)(η2-HCtCPh){[η2-CH2dC-
(CH3)]PiPr2}]BF4 (2). A solution of Os(η5-C5H5)(CtCPh){[η2-
CH2dC(CH3)]PiPr2} (1) (155 mg, 0.29 mmol) in 6 mL of diethyl
ether was treated with HBF4‚Et2O (74 µL, 0.53 mmol). An
orange solid was formed immediately. The mixture was stirred
for 10 min, and the solution was decanted. The solid was
washed with diethyl ether (2 × 2 mL) and dried in vacuo.
Yield: 105 mg (60%). Anal. Calcd for C22H30BF4OsP: C, 41.36;
H, 4.89. Found: C, 41.84; H, 5.19. IR (Nujol, cm-1): ν(CtC)
1729; ν(BF4) 1064. 1H NMR (300 MHz, CD2Cl2, 293 K): δ 7.33-
7.07 (5H, Ph); 5.92 (s, 5H, η5-C5H5); 4.09 (s, 1H, HCt); 4.06
31.7, one of the PCH); 23.6 (d, JC-P ) 3.6, C11); 21.7; 19.2, 19.1,
and 18.5 (all s, CH3). 31P{1H} NMR (161.4 MHz, CD2Cl2, 293
K): δ -43.2 (s). MS (LSIMS+): m/z 517 (M+).
Complexes 3-d1 and 3-d5 were prepared similarly starting
from 2-d1 and 2-d5, respectively.
Crystal data for 3: C46H50BOsP, Mw 834.84, yellow, ir-
regular block (0.06 × 0.06 × 0.02 mm), triclinic, space group
P1h, a ) 10.1242(17) Å, b ) 12.635(2) Å, c ) 14.459(2) Å, R )
88.271(4)°, â ) 80.540(3)°, γ ) 89.024(3)°, V ) 1823.4(5) Å3, Z
) 2, Dcalc ) 1.521 g cm-3, F(000) ) 844, T ) 100.0(2) K; µ )
3.573 mm-1. 13 118 measured reflections (2θ ) 3-57°, ω scans
0.3°), 8380 unique (Rint ) 0.0541); min./max. transm factors
) 0.801/0.882. Final agreement factors were R1 ) 0.0581 (6231
observed reflections, I > 2σ(I)) and wR2 ) 0.0977; data/
restraints/parameters ) 8380/0/459; GoF ) 0.831. Largest
peak and hole ) 1.762 and -1.733 e/Å3.
(dd, 1H, JH-P ) 30.2, JH-H ) 3.0, PCdCHtrans P); 2.81 (dd,
to
1H, JH-P ) 8.7, JH-H ) 3.0, PCdCHcis to P); 2.61 (m, 1H, one of
the PCH); 2.32 (d, 3H, JHP ) 8.2, PC(CH3)d); 2.02 (m, 1H,
one of the PCH); 1.73-1.43 (12H, PCHCH3). 13C{1H} NMR
(75.4 MHz, CD2Cl2, 293 K, plus APT, plus HSQC): δ 142.0 (s,
Cipso Ph); 129.4, 127.5, and 126.8 (all s, Ph); 124.5 (s, tCPh);
120.8 (s, HCt); 90.5 (s, η5-C5H5); 52.7 (d, JC-P ) 17.3, PC));
31.4 (d, JC-P ) 5.7, CH2); 30.7 (d, JC-P ) 31.6, one of the PCH);
22.6 (d, JC-P ) 31.0, one of the PCH); 21.5 (d, JC-P ) 6.0, CH3);
19.9 and 17.7 (both s, CH3). 31P{1H} NMR (121.4 MHz, CD2-
Cl2, 293 K): δ 21.9 (br). MS (LSIMS+): m/z 517 (M+); 413 (M+
- PhCtCH).
Acknowledgment. Financial support from the
MCYT of Spain (Project BQU2002-00606, PPQ2000-
0488-P4-02) is acknowledged. M.L.B. thanks the Span-
ish MCYT/Universidad de Zaragoza for funding through
the “Ramo´n y Cajal” program.
Complex 2-d1 was prepared similarly by using DBF4‚D2O
instead of HBF4‚OEt2, whereas 2-d5 was obtained from 1-d5
and HBF4‚OEt2.
Supporting Information Available: Crystallographic
data and bond lengths and angles. This material is available
free of charge via the Internet at http://pubs.acs.org.
Preparation of [Os(η5-C5H5)(1,2-dihydro-2-methyl-
naphth-2-yldiisopropylphosphine)]BF4 (3). A solution of
[Os(η5-C5H5)(η2-HCtCPh){[η2-CH2dC(CH3)]PiPr2}]BF4 (2) (200
OM050487Q