Hemilabile properties of the η3-diphenylvinylphosphine (DPVP) phosphaallyl ligand: Synthesis and reactions of [(η5-C5Me5)Ru(η 3-DPVP)(η1-DPVP)]PF6

Article abstract of DOI:10.1021/om961068j

Pentamethylcyclopentadienyl-ruthenium(II) half-sandwich complexes containing the olefinic phosphine ligand diphenylvinylphosphine (DPVP) are described. The hemilabile properties of the η³-DPVP ligand, a neutral monometallic phosphaallyl, are illustrated by reactions with carbon monoxide and terminal acetylenes. DPVP reacts with [(η⁵-C₅Me₅)-RuCl₂]₂ to give the disubstituted ruthenium(II) compound [(η⁵-C₅Me₅)Ru-(η ³-DPVP)(η¹-DPVP)]-PF₆ (1). 1 reacts with NaNCS to form [(η⁵-C₅Me₅)Ru(η¹-DPVP) ₂(NCS)] (2). 1 reacts with CO, HC≡CPh, HC≡CCH₂CH₂OH, and HC≡CCH₂OH to form [(η⁵-C₅Me₅)Ru(η¹-DPVP) ₂(CO)]PF₆ (3), [(η⁵-C₅Me₅)Ru(η¹-DPVP) ₂{C=C(H)(Ph)}]PF₆ (4), [(η₅-C₅Me₅)Ru(η¹-DPVP) ₂{C(CH₂)₃O}PF₆ (5), and [(η⁵-C₅Me₅)Ru(η¹-DPVP) ₂{C=C(H)(CH₂OH)}]PF₆ (6), respectively. 6 slowly decomposes in aerated solutions to form 3, presumably through an allenylidene intermediate. 6 reacts with excess DPVP and HPF₆ to form the novel, P,P-diphenyltrihydrophospholonium vinylidene compound [(η⁵-C₅Me₅)Ru(η¹-DPVP) ₂{C=C(CH₂)₂PPh₂CH ₂}][PF₆]₂ (7). The characteristic ¹H, ¹³C{¹H}, and ³¹P{¹H} spectroscopic features of all compounds are described. The molecular structures of compounds 1, 4, 5, and 7 have been determined by single crystal X-ray crystallography.

Full text of DOI:10.1021/om961068j

1714
Organometallics 1997, 16, 1714-1723
Hem ila bile P r op er ties of th e η3-Dip h en ylvin ylp h osp h in e
(DP VP ) P h osp h a a llyl Liga n d : Syn th esis a n d Rea ction s
of [(η5-C5Me5)Ru (η3-DP VP )(η1-DP VP )]P F 6
Luis P. Barthel-Rosa,† Kalyani Maitra,† J ean Fischer,‡ and J ohn H. Nelson*,†
Department of Chemistry/ 216, University of NevadasReno, Reno, Nevada 89557-0020,
and Laboratoire de Cristallochimie (URA 424 du CNRS), Universite´ Louis Pasteur,
4 rue Blaise Pascal, F-67070 Strasbourg Cedex, France
Received December 17, 1996X
Pentamethylcyclopentadienyl-ruthenium(II) half-sandwich complexes containing the ole-
finic phosphine ligand diphenylvinylphosphine (DPVP) are described. The hemilabile
properties of the η3-DPVP ligand, a neutral monometallic phosphaallyl, are illustrated by
reactions with carbon monoxide and terminal acetylenes. DPVP reacts with [(η5-C5Me5)-
RuCl2]2 to give the disubstituted ruthenium(II) compound [(η5-C5Me5)Ru(η3-DPVP)(η1-DPVP)]-
PF6 (1). 1 reacts with NaNCS to form [(η5-C5Me5)Ru(η1-DPVP)2(NCS)] (2). 1 reacts with
CO, HCtCPh, HCtCCH2CH2OH, and HCtCCH2OH to form [(η5-C5Me5)Ru(η1-DPVP)2(CO)]PF6
(3), [(η5-C5Me5)Ru(η1-DPVP)2{CdC(H)(Ph)}]PF6 (4), [(η5-C5Me5)Ru(η1-DPVP)2{C(CH2)3O}]PF6
(5), and [(η5-C5Me5)Ru(η1-DPVP)2{CdC(H)(CH2OH)}]PF6 (6), respectively. 6 slowly decom-
poses in aerated solutions to form 3, presumably through an allenylidene intermediate. 6
reacts with excess DPVP and HPF6 to form the novel, P,P-diphenyltrihydrophospholonium
vinylidene compound [(η5-C5Me5)Ru(η1-DPVP)2{CdC(CH2)2PPh2CH2}][PF6]2 (7). The char-
1
acteristic H, 13C{1H}, and 31P{1H} spectroscopic features of all compounds are described.
The molecular structures of compounds 1, 4, 5, and 7 have been determined by single crystal
X-ray crystallography.
In tr od u ction
hemilabile properties.2a-i For example, Werner and co-
workers have demonstrated the hemilabile properties
of the hybrid Pri PCH2CH2OMe ligand when bound to
One of many expanding areas of interest in organo-
metallic chemistry is the use of “hybrid” ligands1 on
transition metal complexes. Hybrid ligands are those
ligands containing two or more chemically different
atoms or groups of atoms suitable for coordination to a
metal center. In addition, hybrid ligands frequently
contain functionalities that display hemilabile2 proper-
ties. Hemilabile atoms or groups of atoms can revers-
ibley create or occupy a vacant coordination site on a
transition metal center. Therefore, hybrid, hemilabile
ligands may enhance selectivity in catalytic systems, or
stabilize reactive intermediates.1-3 Transition metal
complexes containing hemilabile, bidentate phosphines
fall into these categories. Systems such as phosphino-
ether, -amine, and -ester ligands are known to exhibit
2
ruthenium(II) in the complex [RuCl2(η2-Pri PCH2CH2-
2
OMe)2], by displacement of the metal-O bond with CO
and HCtCPh.2b The Pri PCH2CO2Me ligand gave
2
similar results with CO and terminal acetylenes when
bound to ruthenium(II) in the [(η5-C5Me5)RuCl{η2-(P,O)-
Pri PCH2CO2Me}] compound.2g The Pri PCH2CH2OMe
2
2
ligand, when bound to an iridium precatalyst, exhibited
hemilabile properties when used in the hydrogenation
of phenylacetylene.2d Finally, Shell used a hybrid,
hemilabile phosphine ligand bound to nickel for the
commercial oligomerization of ethylene to prepare linear
R-olefins.2i-k
Our investigations with olefinic phosphines, specifi-
cally diphenylvinylphosphine (DPVP), resulted in the
synthesis of [(η5-C5H5)Ru(η3-DPVP)(η1-DPVP)]PF6 (A).4
A contains the η3-DPVP ligand, which is a neutral,
monometallic phosphaallyl ligand. The hemilabile char-
acter of the phosphaallyl ligand illustrated as the metal-
bound vinyl group was readily displaced by carbon
monoxide, nitriles, isonitriles, and phosphines (see
Chart 1). In continuing efforts to explore olefinic
phosphines as hemilabile ligands, we have prepared 1,
[(η5-C5Me5)Ru(η3-DPVP)(η1-DPVP)]PF6, the electron-
rich analog of A. To the best of our knowledge, 1
† University of NevadasReno.
‡ Universite´ Louis Pasteur.
X Abstract published in Advance ACS Abstracts, April 1, 1997.
(1) (a) Lindner, E.; Bader, A. Coord. Chem. Rev. 1991, 108, 27. (b)
Podlahova´, J .; Kratochv´ıl, B.; Langer, V. Inorg. Chem. 1981, 20, 2160.
(2) (a) J effrey, J . C.; Rauchfuss, T. B. Inorg. Chem. 1979, 18, 2658.
(b) Mart´ın, M.; Gevert, O.; Werner H. J . Chem. Soc., Dalton Trans.
1996, 2275, and references therein. (c) Werner, H.; Stark, A.; Schulz,
M.; Wolf, J . Organometallics 1992, 11, 1126. (d) Esteruelas, M. A.;
Lo´pez, A. M.; Oro, L. A.; Pe´rez, A.; Schulz, M.; Werner, H. Organo-
metallics 1993, 12, 1823. (e) Mason, M. R.; Verkade, J . G. Organome-
tallics 1992, 11, 1514. (f) Sassano, C. A.; Mirkin, C. A. J . Am. Chem.
Soc. 1995, 117, 11379. (g) Lindner, E.; Haustein, M.; Fawzi, R.;
Steimann, M.; Wenger, P. Organometallics 1994, 13, 5021. (h) Braun,
T.; Steinert, P.; Werner, H. J . Organomet. Chem. 1995, 488, 169. (i)
Parshall, G. W.; Ittel, S. D. Homogeneous Catalysis: The Applications
and Chemistry of Catalysts by Soluble Transition Metal Complexes,
2nd ed.; Wiley Interscience: New York, 1992; pp 70-72. (j) Keim, W.
Angew. Chem., Int. Ed. Engl. 1990, 29, 235. (k) Andrieu, J .; Braunstein,
P.; Naud, F.; Adams, R. D.; Layland, R. Bull. Soc. Chim. Fr. 1996,
133, 669.
(3) (a) Adams, H.; Bailey, N. A.; Colley, M.; Schofield, P. A.; White,
C. J . Chem. Soc., Dalton Trans. 1994, 1445. (b) J utzi, P.; Kristen, M.
O.; Dahlhaus, J .; Neumann, B.; Stammler, H.-G. Organometallics 1993,
12, 2980. (c) Okuda, J .; Zimmermann, K. H. Angew. Chem., Int. Ed.
Engl. 1991, 30, 430. (d) J utzi, P.; Redeker, T.; Neumann, B.; Stammler,
H.-G. Organometallics 1996, 15, 4153.
(4) J i, H.-L.; Nelson, J . H.; DeCain, A.; Fischer, J .; Solujic´, L.;
Milosavljevic´, E. B. Organometallics 1992, 11, 401.
S0276-7333(96)01068-0 CCC: $14.00 © 1997 American Chemical Society

η3-Diphenylvinylphosphine Phosphaallyl Ligand
Organometallics, Vol. 16, No. 8, 1997 1715
Ch a r t 1. Rea ction s of th e P h osp h a a llyl Liga n d
Ch a r t 2
Ta ble 1. 1H NMR Da ta of 1 a n d A4 for th e η3- a n d
η1-DP VP Liga n d sa
η3-DPVP
η1-DPVP
cmplx
Ha′
Hb′
Hc′
Ha
Hb
Hc
A
δ
4.08
m
4.06 2.41
4.54
ddd
5.61 5.12
ddd ddd
mult
m
m
3J (PH) 15.03b 22.24 21.94 3J (PH) 25.24b 37.57 18.33
3J (PH) 10.52 4.51 10.52
3J (a′b′)c 8.65
3J (a′c′) 6.1
2J (b′c′)
8.65
3J (ac) 18.33
18.33
represents only the second example4 of a neutral,
monometallic phosphaallyl. An abstract of the X-ray
crystal structure of 1 has appeared.5 Herein we report
the synthesis, full details of the crystal structure, and
the reactivity of 1 to probe the hemilabile properties of
this system. Reactions of 1 with sodium thiocyanate,
carbon monoxide, phenylacetylene, propargyl alcohol,
and 3-butyn-1-ol are discussed.
6.1
3J (ab) 12.32 12.32
2.96 2.96 2J (bc)
0.9
0.9
1
δ
3.12
m
3.20 2.62
4.25
ddd
5.35 5.03
ddd ddd
mult
m
m
3J (PH) 13.22b 34.86 16.23 3J (PH) 26.15b 36.06 17.43
3J (PH) 2.10
1.80 6.31
3J (a′b′) 10.37 10.37
3J (a′c′) 0.62
3J (ac) 17.43
17.43
0.62 3J (ab) 12.32 12.32
2J (b′c′)
9.91 9.91 2J (bc)
0.60 0.60
a
NMR spectra measured in CDCl3. All chemical shifts are
reported in ppm downfield from tetramethylsilane. All coupling
constants are reported in hertz. b 2J (PH). c J (HH) coupling where
the symbols a′, b′, c′, a, b, and c represent Ha′, Hb′, Hc′, Ha, Hb,
and Hc, respectively, as defined in Chart 2.
Resu lts a n d Discu ssion
Syn th esis a n d Ch a r a cter iza tion of [(η5-C5Me5)-
Ru (η3-DP VP )(η1-DP VP )]P F 6 (1). The preparation of
1 is accomplished by modification of the procedure
described by Balavoine.6 In acetonitrile, a deep red
contrast, quantitative removal of acetonitrile from A
requires heating at 70-75 °C under high vacuum (0.5
mmHg) for several days.4 The relative ease with which
acetonitrile is removed from 1 is attributed to an
enhanced ruthenium-phosphaallyl π-backbonding in-
teraction as a result of the strong electron-donating
ability of the η5-C5Me5 ligand. The 31P{1H} NMR
spectrum of 1 in chloroform-d shows two doublets
7
solution of [(η5-C5Me5)RuCl2]2 is treated with excess
powdered zinc and the solution gradually turns yellow/
brown. After 2 h, the excess zinc is removed by
filtration and the solution is treated with DPVP for 8
hours at room temperature. The resulting solution is
then treated with sodium hexafluorophosphate to pro-
duce 1 in 72% yield after recrystallization (eq 1). 1 is a
corresponding to the two inequivalent phosphines at
44.8 and 14.3 ppm with a coupling constant of J PP
2
)
48.5 Hz. On the basis of the assignment of the 31P{1H}
NMR spectrum of A, the η1-DPVP and η3-DPVP phos-
phorus nuclei resonate at 44.8 and 14.3 ppm, respec-
tively. This assignment was confirmed by selective
1H{31P} NMR spectroscopy. In addition, the phosphorus
chemical shifts of 1 are similar to those of A, which
shows two doublets at 42.3 and 24.2 ppm (2J PP ) 43.9
1
Hz), respectively.4 The H NMR spectrum of 1 shows
(1)
three multiplets corresponding to the η1-DPVP hydro-
gens at 5.35, 5.03, and 4.25 ppm for Hb, Hc, and Ha
protons, respectively (see Chart 2). The η3-DPVP phos-
phaallyl hydrogens resonate at 3.20, 2.62, and 3.12 ppm
for Hb′, Hc′ and Ha′ respectively, and appear as complex
1
multiplets. All aspects of the H NMR spectral data for
bright yellow, crystalline material that is air stable both
in the solid state and in aerated solutions. Similar to
what is observed for A, 1 reversibly binds acetonitrile;
however, in contrast to A, 1 reacts with acetonitrile
more slowly. Another notable difference between the
two compounds is that coordinated acetonitrile is quan-
titatively removed from 1 on a rotary evaporator (∼10
mmHg) under mild conditions (∼40 °C, 15 min). In
1 are comparable to those of A,4 and Table 1 summarizes
1
selected H NMR data for both compounds. Moreover,
the η3-DPVP ligand is bound in the exo orientation both
in solution and in the solid state, as confirmed by a 1D-
NOE difference experiment and X-ray crystallography.
A view of the geometry of the cation of 1 is shown in
Figure 1. Selected bond distances and angles are listed
in Table 2. Crystallographic data and details of struc-
ture determination are given in Table 6. The analysis
reveals a distorted octahedral geometry at ruthenium;
the η5-C5Me5 moiety occupies three facial coordination
(5) Barthel-Rosa, L. P.; Nelson, J . H.; Catalano, V. J .; Fischer, J .
Phosphorus, Sulfur, Silicon 1996, 109-110, 169-172.
(6) Balavoine, G. G. A.; Boyer, T. Organometallics 1992, 11, 456.
(7) Koelle, U.; Kossakowski, J . Inorg. Synth. 1992, 29, 225-228.

1716 Organometallics, Vol. 16, No. 8, 1997
Barthel-Rosa et al.
η3-DPVP and η1-DPVP ligands, respectively. The coor-
dinated C13-C14 bond distance in 1 (1.51 Å) is signifi-
cantly longer than the analogous coordinated C-C bond
in A (1.399 Å). The longer coordinated C-C bond
distance in 1 compared to that of A is attributed to the
more electron-rich ruthenium center in 1 as a result of
the strong electron-donating properties of the η5-C5Me5
ligand. The Ru1-C13 and Ru1-C14 bond distances of
2.17(2) and 2.25(2) Å in 1 are virtually identical to the
respective metal-carbon bond distances of 2.176(3) and
2.244(4) Å for A. The similar metal-carbon bond
distances of the η3-DPVP ligands in 1 and A are not
surprising, since those distances have little dependence
on the electron density at ruthenium. Overall, the
crystallographic data for 1 confirms the phosphaallyl
nature of the η3-DPVP ligand.
Rea ction s of 1. Treatment of a dichloromethane/
methanol solution of 1 with a large excess of NaNCS at
room temperature results in the formation of 2, [(η5-C5-
Me5)Ru(η1-DPVP)2(NCS)] (eq 2). The η3-DPVP phos-
F igu r e 1. Structural drawing of one cation of [(η5-C5Me5)-
Ru(η3-DPVP)(η1-DPVP)]PF6 (1) showing the atom number-
ing scheme (30% probability ellipsoids). Hydrogen atoms
have been omitted for clarity.
Ta ble 2. Selected Bon d Dista n ces a n d An gles
for Ca tion 1 of
[(η5-C5Me5)Ru (η3-DP VP )(η1-DP VP )]P F 6 (1)
Bond Distances (Å)
Ru1-P1
Ru1-P2
P1-C13
P2-C27
C13-C14
C27-C28
Ru1-C13
2.288(4)
2.355(5)
1.71(2)
1.84(2)
1.51(3)
1.24(2)
2.17(2)
Ru1-C14
Ru1-C29
Ru1-C30
Ru1-C31
Ru1-C32
Ru1-C33
Ru1-Cp*a
2.25(2)
2.30(2)
2.23(2)
2.20(2)
2.26(2)
2.31(2)
1.90
phaallyl ligand is displaced by the incoming thiocyanate
ion, which is confirmed by 31P{1H} NMR spectroscopy
as the two doublets at 44 and 14 ppm disappear and a
singlet appears at 39.0 ppm. The 1H NMR spectrum
in chloroform-d shows complex multiplets at 5.69 and
5.19 ppm for the uncoordinated vinyl hydrogens, which
is typical for disubstituted metal-DPVP complexes.4,8
Second-order effects arising from coupling to both
phosphorus nuclei give rise to the complex nature of the
vinyl resonances. The resonance for the η5-C5Me5
hydrogens appears as a triplet at 1.33 ppm (4J PH ) 1.5
Bond Angles (deg)
P1-Ru1-P2
P1-Ru1-C13
P1-Ru1-C14
Ru1-P1-C13
Ru1-P2-C27
P1-C13-C14
P2-C27-C28
91.1(2)
44.9(5)
75.0(4)
63.9(6)
117.6(6)
118(1)
C1-P1-C7
104.6(6)
104.0(8)
110.0(8)
100.3(8)
112.9(8)
101.2(7)
C15-P2-C21
C1-P1-C13
C15-P2-C27
C7-P1-C13
C21-P2-C27
129(2)
a
Cp* denotes the centroid of the C29-C33 ring.
1
Hz). Both the 31P{1H} and H NMR spectroscopic data
sites, with one η1-DPVP and one η3-DPVP completing
the coordination sphere. There are no unusual interi-
onic contacts. There are two molecules in the asym-
metric unit, and the cations have an enantiomeric
relationship. The metrical parameters for the two
cations are very similar, and the discussion that follows
is for only one of them. Complete data are given in the
Supporting Information. For 1, the η3-DPVP ligand has
a Ru1-P1 bond distance of 2.288(4) Å, and the η1-DPVP
ligand has a longer Ru1-P2 bond distance of 2.355(5)
Å while the P1-Ru1-P2 bond angle is 91.1(2)˚. Both
Ru-P distances in 1 are very similar to the analogous
distances of 2.276(1) and 2.315(1) Å for A, which has a
P-Ru-P bond angle of 93.34(3)˚.4 For 1, the η3-DPVP
phosphaallyl ligand has a P1-C13 bond distance of
1.71(2) Å, which is shorter than the P2-C27 bond
distance of 1.84(2) Å for the η1-DPVP vinylphosphine
ligand. The same trends are observed for A, which has
P-C bond distances of 1.761(4) and 1.810(3) Å for the
η3-DPVP and η1-DPVP ligands, respectively. For 1, the
coordinated C13-C14 bond of the η3-DPVP ligand has
a distance of 1.51(3) Å, which is significantly longer than
the C27-C28 bond distance of 1.24(2) Å for the η1-DPVP
ligand. The same trends are observed for A, which has
C-C bond distances of 1.399(5) and 1.306(5) Å for the
indicate that 2 contains a mirror plane of symmetry in
solution with two η1-DPVP ligands. The IR spectrum
of 2 in Nujol shows characteristic ν(N-CS) at 2095 cm-1
and ν(NCS) at 800 cm-1, indicating that the thiocyanate
ligand is bound through the nitrogen atom.9 The most
notable feature of the 13C{1H} NMR spectrum in chlo-
roform-d is the presence of the NCS carbon resonance
as a triplet at 127.17 ppm (3J PC ) 1.9 Hz). Both the IR
and 13C{1H) NMR data are characteristic of an N-bound
NCS- moiety.9 Treatment of 1 with NaN3 under similar
conditions led to the formation of many products, as
indicated by 31P{1H} NMR spectroscopy, with reso-
nances of approximately equal intensity at 38.7, 37.3,
31.1, and 24.4 ppm. In addition, these solutions are air
sensitive and decompose rapidly. No further attempts
were made to purify the compound(s) formed in the
NaN3 reaction.
(8) Barthel-Rosa, L. P.; Catalano, V. J .; Maitra, K.; Nelson, J . H.
Organometallics 1996, 15, 3924.
(9) (a) MacDougall, J . J .; Nelson, J . H.; Fultz, W. C.; Burmeister, J .
L.; Holt, E. M.; Alcock, N. W. Inorg. Chim. Acta 1982, 63, 75. (b) Nelson,
J . H.; MacDougall, J . J .; Alcock, N. W.; Mathey, F. Inorg. Chem. 1982,
21, 1200. (c) Fultz, W. C.; Burmeister, J . L.; MacDougall, J . J .; Nelson,
J . H. Inorg. Chem. 1980, 19, 1085. (d) For S-bound ruthenium NCS-
complex, see: Homanen, P.; Haukka, M.; Pakkanen, T. A.; Pursiainen,
J .; Laitinen, R. H. Organometallics 1996, 15, 4081.

η3-Diphenylvinylphosphine Phosphaallyl Ligand
Organometallics, Vol. 16, No. 8, 1997 1717
Treatment of 1 with CO in refluxing 1,2-dichloro-
ethane results in the formation of the bright yellow 3,
[(η5-C5Me5)Ru(η1-DPVP)2(CO)]PF6, in high yield after
116 h (eq 3). The 31P{1H} NMR spectrum in chloro-
1
form-d shows a singlet at 35.3 ppm while the H NMR
spectrums shows the characteristic second-order unco-
ordinated vinyl hydrogen resonances at 5.93, 5.45, and
5.29 ppm. The 13C{1H} NMR spectrum shows the
characteristic triplet at 204.25 ppm (2J CP ) 17.2 Hz) for
the carbonyl carbon. For [(η5-C5H5)Ru(η1-DPVP)2(CO)]-
PF6, the CO carbon resonance occurs at 202.68 ppm
(2J PC ) 17.3 Hz) in nitromethane-d3.4 Substitution of
CO onto 1 to form 3 required a much longer reaction
time (116 h) when compared to the η5-C5H5 analog A (8
h), under similar conditions. The long reaction time for
the conversion of 1 into 3 is attributed to a stronger
ruthenium η3-DPVP phosphaallyl interaction as a result
of the electron-donating properties of the η5-C5Me5
ligand compared to η5-C5H5.
Other illustrative examples of the hemilabile proper-
ties of the η3-DPVP phosphaallyl ligand are the reac-
tions with terminal acetylenes. Treatment of 1 with
phenylacetylene in refluxing methanol affords the vi-
nylidene 4, [(η5-C5Me5)Ru(η1-DPVP)2{CdC(H)(Ph)}]PF6
(eq 4). The 31P{1H} NMR spectrum in chloroform-d
F igu r e 2. Structural drawing of the cation of [(η5-C5Me5)-
Ru(η1-DPVP)2{CdC(H)(Ph)}]PF6 (4) showing the atom
numbering scheme (40% probability ellipsoids). Hydrogen
atoms and phenyl carbon atoms of the η1-DPVP ligands
have been omitted for clarity.
Ta ble 3. Selected Bon d Dista n ces a n d An gles for
[(η5-C5Me5)Ru (η1-DP VP )2{CdC(H)(P h )}]P F 6 (4)
Bond Distances (Å)
Ru1-P1
Ru1-P2
Ru1-C15
C15-C16
C16-C17
P1-C11
P2-C13
C11-C12
2.346(4)
2.355(3)
1.824(13)
1.33(2)
1.47(2)
1.797(12)
1.83(2)
C13-C14
Ru1-C1
Ru1-C2
Ru1-C3
Ru1-C4
Ru1-C5
Ru1-Cp*a
1.29(2)
2.330(14)
2.336(13)
2.263(14)
2.271(13)
2.268(13)
1.954
1.29(2)
Bond Angles (deg)
P1-Ru1-P2
92.5(2)
86.7(4)
89.8(4)
172.5(11)
128.4(13)
C11-P1-Ru1
C13-P2-Ru1
C12-C11-P1
C14-C13-P2
113.9(5)
115.1(5)
126.7(13)
128(2)
C15-Ru1-P1
C15-Ru1-P2
C16-C15-Ru1
C15-C16-C17
a
Cp* denotes the centroid of the C(1-5) ring.
distorted octahedral geometry at ruthenium. The Ru1-
C15 bond length is 1.824(13) Å while the C15-C16
length is 1.33(2) Å, which are typical values for vi-
nylideneruthenium complexes.10,11 The vinylidene ligand
is nearly linear with a C16-C15-Ru1 bond angle of
172.5(11)° which is only slightly smaller than the angle
of 174(1)° reported for [(η5-C5Me5)Ru(PPhMe2)2{CdC-
(H)(Ph)}]PF6.10 In 4, the vinylidene plane defined by
Ru1-C15-C16-C17 makes an angle of 87.6° with the
plane bisecting the P1-Ru-P2 angle, which is typical
for half-sandwich vinylidene complexes.11,12 Kostic and
Fenske calculated that maximal π-stabilization arises
when the p orbitals of the CR carbon and the metal 2a′′
orbital interact with one another,13 a consistent with the
observed orientation of the vinlyidene fragment in 4.
However, there exists a second, lower energy π interac-
tion between the π* orbital of the organic group and the
shows a singlet at 38.0 ppm while the 1H NMR spectrum
shows the characteristic second-order uncoordinated
vinyl hydrogen resonances at 5.79, 5.65, and 5.01 ppm.
The unique vinylidene hydrogen resonance appears as
a broad triplet at 5.26 ppm (4J HP ) 2.2 Hz). The 13C-
{1H} NMR spectrum shows the characteristic RudCR
carbon resonance at 353.6 ppm, but the phosphorus-
carbon coupling is not resolved. The NMR data for 4
compare with the values reported for [(η5-C5Me5)Ru-
(PPhMe2)2{CdC(H)(Ph)}]PF6, which shows the unique
vinylidene hydrogen resonance as a triplet at 5.42 ppm
(4J HP ) 2.2 Hz) and the RudCR carbon resonance at
354.3 ppm.10 In addition, the spectroscopic data for 1
are typical for transition metal vinylidene complexes.11
4 was also characterized by X-ray crystallography.
A view of the structure of the cation of 4 is shown in
Figure 2. Selected bond distances and angles are listed
in Table 3. The analysis reveals a distorted octahedral
geometry about ruthenium with one η5-C5Me5 moiety
that occupies three facial coordination sites, two η1-
DPVP ligands and the CdC(H)(Ph) vinylidene moiety
completing the coordination sphere. The interligand
bond angles of 92.5(2)° for P1-Ru1-P2, 86.7(4)° for
C15-Ru1-P1 and 89.8(4)° for C15-Ru1-P2 reflect the
(10) Lagadec, R. L.; Roman, E.; Toupet, L.; Mu¨ller, U.; Dixneuf, P.
H. Organometallics 1994, 13, 5030.
(11) Bruce, M. I. Chem. Rev. 1991, 91, 197.
(12) Davies, S. G.; McNally, J . P.; Smallridge, A. J . Adv. Organomet.
Chem. 1990, 30, 1.
(13) (a) Kostic, N. M.; Fenske, R. F. Organometallics 1982, 1, 974.
(b) Schilling, B. E. R.; Hoffman, R.; Lichtenberger, D. L. J . Am Chem.
Soc. 1979, 101, 585. (c) Consiglio, G.; Morandini, F. Inorg. Chim. Acta
1987, 127, 79. (d) Consiglio, G.; Bangerter, F.; Darpin, C.; Morandini,
F.; Lucchini, V. Organometallics 1984, 3, 1446.

1718 Organometallics, Vol. 16, No. 8, 1997
Barthel-Rosa et al.
metal fragment 3a′ orbital, which predicts facile rotation
about the metal-CR (MdCR) bond.12 The barrier to
rotation about metal-vinylidene (MdCR) bonds has
been calculated to be on the order of 15 kJ /mol.13b This
barrier was measured to be around 38-43 kJ /mol for a
series of ruthenium(II) vinylidene compounds of the
type, [(η5-C5H5)-Ru(Ph2PCHRCHR′PPh2){CdC(H)-
(R′′)]+.11-13c,d
Treatment of 1 with 3-butyn-1-ol in refluxing dichlo-
romethane affords the cyclic Fischer carbene complex
5, [(η5-C5Me5)Ru(η1-DPVP)2{C(CH2)3O}]PF6 (eq 5). The
F igu r e 3. Structural drawing of the cation of [(η5-C5Me5)-
Ru(η1-DPVP)2{C(CH2)3OP}]PF6 (5) showing the atom num-
bering scheme (40% probability ellipsoids). Hydrogen atoms
omitted for clarity.
31P{1H} NMR spectrum in dichloromethane shows that
the first step in the reaction is isomerization of the
alkene to form the metal-vinylidene,12 which appears
as a singlet at 38 ppm. No attempt was made to isolate
the intermediate vinylidene compound. Upon heating,
intramolecular attack of the hydroxyl group at the
RudCR carbon, concomitant with a proton shift, results
in the formation of the final product 5. The synthesis
of cyclic carbenes by metal-mediated activation of 3-bu-
tyn-1-ol has been used to make close analogs of 5
Ta ble 4. Selected Bon d Dista n ces a n d An gles for
[(η5-C5Me5)Ru (η1-DP VP )2{C(CH2)3O}]P F 6 (5)
Bond Distances (Å)
Ru1-P1
Ru1-P2
Ru1-C39
O1-C39
O1-C42
C41-C42
C40-C41
C39-C40
P1-C11
2.3270(13)
2.3382(13)
1.942(5)
1.329(6)
1.462(6)
1.454(9)
1.520(8)
1.492(7)
1.825(5)
P2-C31
C11-C12
C31-C32
Ru1-C1
Ru1-C2
Ru1-C3
Ru1-C4
Ru1-C5
Ru1-Cp*a
1.813(5)
1.318(7)
1.303(7)
2.283(5)
2.272(5)
2.341(5)
2.328(5)
2.298(5)
1.960
including the following: [(η5-C5H5)Ru(PMe3)2{C(CH2)3-
O}]+,14 [(η5-C5H5)Ru(PPh3)2{C(CH2)3O}]+, [(η5-C9H7)Os-
(PPh3)2{C(CH2)3O}]+,15 and [(η6-C6Me6)Ru(PMe3)(Cl){C-
Bond Angles (deg)
P1-Ru1-P2
94.41(5)
90.1(2)
87.38(14)
123.2(3)
129.8(4)
O1-C39-C40
C39-C40-C41
C42-C41-C40
C41-C42-O1
C39-O1-C42
107.0(4)
103.8(5)
103.1(5)
104.3(5)
112.6(4)
C39-Ru1-P1
C39-Ru1-P2
O1-C39-Ru1
C40-C39-Ru1
(CH2)3O}]+.16 The notable features of the 1H NMR
spectrum of 5 (in chloroform-d) include two triplets at
4.31 and 3.35 ppm (3J HH ) 7.0 Hz) and a broad multiplet
at 2.11 ppm for the hydrogens of the three methylene
groups in the carbene ring. The 1H NMR spectral
features of 5 compare to those of [(η5-C5H5)Ru(PPh3)2-
a
Cp* denotes the centroid of the C(1-5) ring.
4. The analysis reveals a distorted octahedral coordina-
tion geometry about ruthenium with one facial η5-C5-
Me5 moiety, two η1-DPVP ligands, and the cyclic carbene
moiety completing the coordination sphere. The inter-
ligand bond angles of 94.41(5)° for P1-Ru1-P2, 90.1-
(2)° for C39-Ru1-P1 and 87.38(14)° for C39-Ru1-P2
reflect the distorted octahedral geometry at ruthenium.
There are two molecules in the asymmetric unit that
differ only in the conformations of the cyclic carbene
ring. Both molecules have esentially the same geo-
metrical shape; therefore, only the distances and angles
of one of them will be discussed. The Ru1-C39 distance
in 5 is 1.942(5) Å, which compares with the ruthenium
carbene carbon bond length of 1.946(8) Å in the analo-
{C(CH2)3O}]+,14 which shows two triplets at 3.93 and
3.74 ppm and a quintet at 1.77 ppm (3J HH ) 8 Hz) for
the methylene protons of the carbene ring. The 31P-
{1H} NMR spectrum of 5 in chloroform-d consists of a
singlet at 45.1 ppm while the 13C{1H} NMR spectrum
shows the carbene carbon (RudCR) resonance at 299.5
ppm; however, the triplet structure due to phosphorus
coupling was not completely resolved. The methylene
carbons of the carbene ring resonate as singlets at 80.86,
55.81, and 23.41 ppm. The 13C{1H} NMR spectrum of
[(η5-C5H5)Ru(PPh3)2{C(CH2)3O}]+ 14shows the resonance
for the carbene carbon as a triplet at 300.5 ppm (2J (PC)
) 14 Hz) while the carbene ring carbons appear at 81.6,
60.8, and 22.6 ppm, all of which are typical values for
these types of ruthenium carbenes.14-16
gous ruthenium compound [(η5-C5H5)(CO)(PPh3)Ru{C-
a
(CHPh)(CH2)2O}]+,17
and falls between the metal
carbene bond distances of 2.086(8), 1.889(8), and 2.00-
5 was characterized by X-ray crystallography, and a
view of the structure of the cation is shown in Figure 3.
Selected bond distances and angles are listed in Table
(2) Å for [(η5-C5H5)(CO)2(I)Mo{C(CH2)3O}],17b [(CO)4Mn-
t
(µ-I)Pt{C(CH2)3O}(PBu2 Me)],17c and [(CH3)(PMe2Ph)2Pt-
(14) Bruce, M. I.; Swincer, A. G.; Thomson, B. J .; Wallis, R. C. Aust.
J . Chem. 1980, 33, 2605.
(15) Gamasa, M. P.; Gimeno, J .; Gonzalez-Cueva, M.; Lastra, E. J .
Chem. Soc., Dalton Trans. 1996, 2547.
(16) Bozec, H. L.; Ouzzine, K.; Dixneuf, P. H. Organometallics 1991,
10, 2768.
(17) (a) Nombel, P.; Lugan, N.; Mathieu, R. J . Organomet. Chem.
1995, 503, C22. (b) Bailey, N. A.; Chell, P. L.; Manuel, C. P.;
Mukhopadhyay, A.; Rogers, D.; Tabbron, H. E.; Winter, M. J . J . Chem.
Soc., Dalton Trans. 1983, 2397. (c) Berry, M., Martin-Gil, J .; Howard,
J . A. K.; Stone, F. G. A. J . Chem. Soc., Dalton Trans. 1980, 1625. (d)
Stepanick, R. F.; Payne, N. C. J . Organomet. Chem. 1974, 72, 453.

η3-Diphenylvinylphosphine Phosphaallyl Ligand
Organometallics, Vol. 16, No. 8, 1997 1719
Sch em e 1. P r op osed Mech a n ism for th e
Tr a n sfor m a tion of In ter m ed ia te 6a in to 3
{C(CH2)3O}],17d respectively. The C(39)-O(1) bond
distance of 1.329(6) Å in 5 is very similar to the carbene
carbon-oxygen bond distances of 1.312(9),17a 1.337-
(11),17b 1.32(1),17c and 1.26(2) Å,17d respectively, for the
compounds listed above. The C40-C41 and C41-C42
bond distances of 1.520(8) and 1.454(9) Å are typical for
Csp3-Csp3 bond lengths. For 5, the carbene ring adopts
an envelope conformation and the deviations from the
mean plane of the carbene ring defined by Ru1, C39,
C40, and O1 are as follows: Ru1 -0.0012 Å, C39 0.0041
Å, C40 -0.0014 Å, C41 0.4963 Å, C42 0.0523 Å, and O1
-0.0014 Å. Deviations from planarity for these types
of five-membered cyclic carbenes are not unusual, and
the structures in the reported complexes above vary
from nearly planar17c to a deviation of -0.406 Å for the
ring carbon â to the oxygen atom , O-CH2-CâH2.17b
Treatment of 1 with propargyl alcohol in chloroform
results in the formation of the vinylidene 6, [(η5-C5-
Me5)Ru(η1-DPVP)2{CdC(H)(CH2OH)}]PF6 (eq 6). The
in color. All attempts to isolate and purify the inter-
mediate complex 6a were not successful and ultimately
resulted only in the isolation of the yellow carbonyl 3
(vide supra). The formation of 3 from solutions of 6/6a
suggests at least one possible decomposition pathway
in which adventitious water attacks the RudCR carbon
of the allenylidene to form an R,â-unsaturated hydroxy-
carbene, followed by hydrogen transfer to ruthenium
with subsequent â-hydride elimination to give 3 and
ethylene (Scheme 1). Although the intermediates pro-
posed in Scheme 1 have not been directly observed, the
nucleophilic addition of water at the RudCR carbon of
allenylidenes to form hydroxycarbenes is known.19
a
Moreover, the hydration of vinylidenes into alkylcarbo-
nyl compounds is well-known12,19b,c and has recently
been studied in detail.21 Therefore, the mechanism
proposed for the transformation of 6 to 3 in Scheme 1
seems reasonable; however, a more meticulous inves-
tigation into this transformation is warranted.
reaction requires 72 h to go to completion at room
temperature. The 31P{1H} NMR spectrum of the reac-
tion mixture (in chloroform) shows a resonance for 6 as
a singlet at 38.6 ppm. Pure 6 is sparingly soluble in
chloroform-d; therefore, 1H and 13C{1H} NMR data were
1
obtained in acetone-d6. The H NMR spectrum shows
Refluxing a solution of 6 in methanol over a period of
several days resulted in the unexpected precipitation
of a rose-colored solid. Recrystallization of the precipi-
tate afforded X-ray quality crystals and a structural
analysis was performed (vide infra). The structure was
shown to be that of 7, [(η5-C5Me5)Ru(η1-DPVP)2-
the unique vinylidene hydrogen resonance as a triplet
3
of triplets at 4.88 ppm with coupling constants of J HH
4
) 8.0 Hz and J HP ) 2.2 Hz. The OH resonance appears
as a triplet at 4.19 ppm (3J HH ) 5.8 Hz), by virtue of
the coupling to the CH2 group. However, after 24 h at
room temperature, the CH2-OH coupling constant is
washed out. The 13C{1H} NMR spectrum shows the
vinylidene carbon (RudCR) as a triplet at 351.0 ppm
(2J CP ) 15.7 Hz) while the RudCdCâ carbon resonates
{CdC(CH2)2PPh2CH2}][PF6]2 (Figure 4; Scheme 2).
Compound 7 contains a novel heterocyclic, disubstituted
vinylidene (CdCR∼R′), where R∼R′ is a P,P-diphenyl-
trihydrophospholonium ring. Compound 7 “scavenged”
DPVP from the solution, which then behaved as a
nucleophile and attacked the allenylidene Cγ carbon of
the intermediate 6a with concomitant ring closure to
form a five-membered heterocycle. In the presence of
excess DPVP and HPF6, 6 readily reacts to form 7 as
outlined in Scheme 2.
A very similar reaction was reported12 for [(η5-C5H5)-
Ru(PPh3)2(Cl)], a close analog of 1. [(η5-C5H5)Ru-
(PPh3)2(Cl)] was shown to react with propargyl alcohol
and NH4PF6 to form the primary allenylidene complex
[(η5-C5H5)(PPh3)2Ru{CdCdCH2}]+, which then scav-
1
as a triplet at 112.8 ppm (3J CP ) 1.2 Hz). The H and
13C{1H} NMR spectral data for 6 are typical for vi-
nylidenes11 and very similar to the values reported for
the close analog [(η5-C5Me5)(PPhMe2)2Ru{CdC(H)(CH2-
OH)}]PF6,10 which shows the unique vinylidene hydro-
gen as a triplet of triplets at 4.63 ppm (3J HH ) 8.0 Hz,
4J PH ) 2.2 Hz) and the triplet for the vinylidene RudCR
at 346.4 ppm (2J CP ) 15.2 Hz).
6 is a yellow-orange solid and forms orange solutions
in acetonitrile, acetone, dichloromethane, and methanol.
Upon standing for long periods of time, (>1 week),
solutions of 6 gradually turn intensely violet. The violet
color suggests that 6 gradually dehydrates to form the
allenylidene complex, [(η5-C5Me5)Ru(η1-DPVP)2{CdCd
CH2}]PF6 (6a ), since solutions of many ruthenium
allenylidene complexes18a-c including the close analog,
[(η6-C6Me6)Ru(Cl)(PMe3){CdCdCPh2}]PF6,18a are violet
(19) (a) Esteruelas, M. A.; Go´mez, A. V.; Lahoz, F. J .; Lo´pez, A. M.;
On˜ate, E.; Oro, L. A. Organometallics 1996, 15, 3423. (b) Gamasa, M.
P.; Gimeno, J .; Lastra, E.; Lanfranchi, M.; Tiripicchio, A. J . Organomet.
Chem. 1992, 430, C39. (c) Bruce, M. I.; Swincer, A. G. Aust. J . Chem.
1980, 33, 1471.
(20) Bianchini, C.; Casares, J . A.; Peruzzini, M.; Romerosa, A.;
Zanobini, F. J . Am. Chem. Soc. 1996, 118, 4585.
(21) (a) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Borge, J .; Garc´ıa-
Granda, S. J . Chem. Soc., Chem. Commun. 1994, 2495. (b) Cadierno,
V.; Gamasa, M. P.; Gimeno, J .; Lastra, E. J . Organomet. Chem. 1994,
474, C27. (c) Berke, H.; Huttner, G.; Seyerl, J . Z. Naturforsch. 1981,
36B, 1277.
(18) (a) Bozec, H. L.; Ouzzine, K.; Dixneuf, P. H.; J . Chem. Soc.,
Chem. Commun. 1989, 219. (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) Pilette, D.; Ouzzine,
K.; Le Bozec, H.; Dixneuf, P. H.; Rickard, C. E. F.; Roper, W. R.
Organometallics 1992, 11, 809.

1720 Organometallics, Vol. 16, No. 8, 1997
Barthel-Rosa et al.
Ta ble 5. Selected Bon d Dista n ces a n d An gles for
[(η5-C5Me5)Ru (η1-DP VP )2{CdC(CH2)2P P h 2CH2}][P F 6]2
(7)
Bond Distances (Å)
Ru1-P1
Ru1-P2
Ru1-C39
C39-C40
C40-C41
C41-C42
P3-C42
P3-C43
C40-C43
2.345(3)
2.357(3)
1.816(12)
1.33(2)
P3-C44
P3-C50
C11-C12
C25-C26
Ru1-C1
Ru1-C2
Ru1-C3
Ru1-C4
Ru1-C5
Ru1-Cp*a
1.788(13)
1.807(13)
1.275(14)
1.32(2)
2.279(12)
2.273(13)
2.334(12)
2.328(11)
2.283(12)
1.957
1.54(2)
1.522(14)
1.782(12)
1.831(11)
1.53(2)
Bond Angles (deg)
P1-Ru1-P2
93.47(13)
88.2(4)
92.4(4)
175.5(11)
122.2(13)
124.2(12)
110.1(11)
104.7(8)
C42-P3-C43
C43-C40-C41
C42-P3-C44
C42-P3-C50
C44-P3-C43
C44-P3-C50
C50-P3-C43
95.5(5)
C39-Ru1-P1
C39-Ru1-P2
C401-C39-Ru1
C39-C40-C41
C39-C40-C43
C42-C41-C40
C41-C42-P3
113.6(11)
111.3(6)
110.0(6)
109.5(6)
112.2(6)
116.3(6)
F igu r e 4. Structural drawing of the cation [(η5-C5-
Me5)Ru(η1-DPVP)2{CdC(CH2)2PPh2CH2}][PF6]2 (7) show-
ing the atom numbering scheme (30% probability ellip-
soids). Hydrogen atoms and phenyl carbon atoms of the
η1-DPVP ligands have been omitted for clarity.
a
Cp* denotes the centroid of the C(1-5) ring.
Sch em e 2. P ossible Mech a n ism for th e F or m a tion
of 7 fr om In ter m ed ia te 6a
show three methylene resonances at 4.40, 3.83, and 3.27
ppm. The downfield resonance at 4.40 ppm appears as
a doublet (2J PH ) 11.0 Hz) corresponding to the CH2
group bound directly to the vinylidene RudCdCâ carbon
and the phospholonium phosphorus. The resonance at
3.83 ppm appears as a doublet of triplets (3J PH ) 15.0
Hz, 3J HH ) 7.5 Hz) and represents the other CH2 group
bound to the RudCdCâ carbon. Finally, the remaining
CH2 group appears at 3.27 ppm as a doublet of triplets
3
(2J PH ) 10.5 Hz, J HH ) 7.5 Hz). The 13C{1H} NMR
spectrum shows the RudCR carbon resonance as a
triplet at 341.1 ppm (2J PC ) 13.8 Hz) while the reso-
nances for the three CH2 carbons of the trihydrophos-
pholonium ring appear as doublets at 24.8 (1J PC ) 4.1
Hz), 24.3 (2J PC ) 1.7 Hz) and 23.3 ppm (1J PC ) 2.1 Hz),
respectively.
enged PPh3 to form the phosphonium salt, [(η5-C5H5)-
Ru(PPh3)2{CtC(CH2PPh3)}]PF6.12 The phosphonium
salt was readliy protonated with HPF6 to form the
dicationic vinylidene compound [(η5-C5H5)Ru(PPh3)2-
{CdC(H)(CH2PPh3)}][PF6]2. MO calculations on the
model compound, [(η5-C5H5)(CO)2Mn{CdCdCH2}], have
shown that the allenylidene CR and Cγ carbons are
electrophilic while the Câ carbon is nucleophilic.11,13b
Likewise, it is well-known that phosphines such as
PMe3,21a,b PPh3,21c and PEt321c will add to allenylidenes
at Cγ ;11,12,21 however, the use of DPVP for this purpose
has no precedent. Allenylidenes are also known to
undergo C-C coupling reactions,21a,22 sometimes to form
carbocycles,22b,c but to the best of our knowledge the
reaction between an olefinic phosphine and an alle-
nylidene to form a heterocyclic vinylidene is unprec-
edented. In contrast to the reaction of 6 with a
phosphine, the closely related ruthenium analog, [(η5-
C5Me5)(PPhMe2)2Ru{CdC(H)(CH2OH)}]PF6, reportedly
did not react with PPh3 via an allenylidene intermediate
to form the corresponding phosphonium salt.10
A view of the geometry of the cation of 7 is shown in
Figure 4. Selected bond distances and angles are listed
in Table 5. The analysis reveals a distorted octahedral
geometry at ruthenium with one facial η5-C5Me5 moiety,
two η1-DPVP ligands, and the vinylidene phospholo-
nium moiety completing the coordination sphere. The
interligand bond angles of 93.47(13)° for P1-Ru1-P2,
88.2(4)° for C39-Ru1-P1, and 92.4(4)° for C39-Ru1-
P2 reflect the distorted octahedral geometry at ruthe-
nium. The Ru1-C39 bond length in 7 is 1.816(12) Å
and the C39-C40 bond distance is 1.33(2) Å, which are
typical vinylidene bond lengths.11 The C40-C41 and
C40-C43 bond lengths are 1.54(2) and 1.53(2) Å,
a-c
respectively, and are typical23
for alkylvinylidene
(dCâsC) bond lengths, which range from 1.485(11) Å23c
for [(η5-C5H5)Ru(PMe3)2{CdC(H)(CH3)}]PF6 to 1.55 Å23a
for [(η5-C5H5)(Ph2P(CH2)2PPh2)Ru{CdC(Ph)(C7H7)]PF6.
The P3-C43 and P3-C42 bond lengths in 7 are 1.831-
(11) and 1.782(12) Å, respectively, which are typical
phosphorus-carbon bond distances. Analysis of the
bond angles at P3 indicate that the coordination geom-
etry is that of a distorted tetrahedron (see Table 5). The
trihydrophospholonium ring adopts an envelope confor-
The 31P{1H} NMR spectrum of 7 in acetonitrile-d3
shows a broad singlet at 35.7 ppm and a sharp singlet
at 42.9 ppm in a 2:1 ratio corresponding to the two η1-
DPVP ligands and the phospholonium phosphorus,
respectively. The 1H NMR data in nitromethane-d3
(22) (a) Wiedemann, R.; Steinert, P.; Gevert, O.; Werner, H. J . Am.
Chem. Soc. 1996, 118, 2495. (b) Bruce, M. I.; Hinterding, P.; Tiekink,
E. R. T.; Skelton, B. W.; White, A. H. J . Organomet. Chem. 1993, 450,
209. (c) Selegue, J . P. J . Am. Chem. Soc. 1983, 105, 5921. (d) Antonova,
A. B.; Ioganson, A. A. Russ. Chem. Rev. 1989, 58, 693. (e) Braun, T.;
Meuer, P.; Werner, H. Organometallics 1996, 15, 4075.
(23) (a) Bruce, M. I.; Dean, C.; Duffy, D. N.; Humphrey, M. G.;
Koutsantonis, G. A. J . Organomet. Chem. 1985, 295, C40. (b) Bruce,
M. I.; Humphrey, M. G.; Snow, M. R.; Tiekink, E. R. T. J . Organomet.
Chem. 1986, 314, 213. (c) Bruce, M. I.; Wong, F. S.; Skelton, B. W.;
White, A. H. J . Chem. Soc., Dalton Trans. 1982, 2203.

η3-Diphenylvinylphosphine Phosphaallyl Ligand
Organometallics, Vol. 16, No. 8, 1997 1721
mmol), and 100 mL of freshly distilled CH3CN. The dark red
mixture was stirred vigorously for 2 h and gradually turned
from red to green to yellow/brown. The excess zinc was
removed by filtration under nitrogen and washed with 2 × 5
mL portions of CH3CN. The yellow/brown filtrate was charged
with diphenylvinylphosphine (3.64 mL, 18.3 mmol), and the
solution was stirred at room temperature for 8 h. To this
mixture was added a solution of NaPF6 (1.7 g, 10.1 mmol) in
35 mL of MeOH. A precipitate formed upon addition of the
salt solution. The reaction mixture was stirred for 45 min,
after which all solvents were removed in vacuo. The resulting
brown residue was dissolved in a minimal amount of CH2Cl2
and filtered, and the solvent was removed in vacuo. The
yellow/brown residue was flash chromatographed over Celite/
silica gel with 1250 mL of CH2Cl2 to give a yellow solution.
The solvent was removed in vacuo, and the yellow amorphous
solid was dried under high vacuum for 24 h to give 4.7 g of 1
in 72% yield. The product was recrystallized from boiling
absolute EtOH before use in subsequent reactions. Mp: 190-
191 °C. Anal. Calcd for C38H41F6P3Ru: C, 56.65; H, 5.13.
Found: C, 56.59; H, 5.02. 1H NMR (CDCl3): δ 6.9-7.9 (m,
20H, Ph), 5.35 (ddd, 3J (PHb) ) 36.06 Hz, 3J (HaHb) ) 12.32 Hz,
mation and the deviations from the mean plane defined
by C39, C40, C41, and C43 are as follows: C39 -0.0016
Å, C40 0.0042 Å, C41 -0.0013 Å, C42 -0.1201 Å, P3
-0.8452 Å, and C43 -0.0013 Å. The vinylidene is
nearly linear with a Ru1-C39-C40 bond angle of 175.5-
(11)°. In 7, the vinylidene plane defined by Ru1-C39-
C40-C41 makes an angle of 82.1° with the plane
bisecting the P1-Ru-P2 angle, as expected.11,12 The
formation of 7 suggests that primary allenylidenes can
be used in the synthesis of novel heterocycles.
Su m m a r y
The synthesis, characterization, and properties of the
phosphaallyl 1 are presented for the first time. Com-
pound 1 contains the bidentate, olefinic phosphine η3-
DPVP ligand, which displays hemilabile properties as
illustrated by displacement of the olefin with CO and
terminal acetylenes. Compound 7 represents a novel
cyclization product between an olefinic phosphine and
a primary allenylidene. Compound 1 may be useful as
a catalyst for carbon-carbon bond formation involving
the coupling of terminal acetylenes with alkenes. Stud-
ies in this area are currently in progress.
3
3
2J (HbHc) ) 0.6 Hz, 1H, Hb), 5.03 (ddd, J (PHc) ) J (HaHc) )
17.43 Hz, 2J (HbHc) ) 0.6 Hz, 1H, Hc), 4.25 (ddd, 2J (PHa) )
26.15 Hz, 3J (HaHc) ) 17.43 Hz, 3J (HaHb) ) 12.32 Hz, 1H, Ha),
3
3
3
3.20 (m, J (PHb′) ) 34.86 Hz, J (PHb′) ) 1.80 Hz, J (Ha′Hb′) )
10.37 Hz, 2J (Hb′Hc′) ) 9.91 Hz, 1H, Hb′), 3.12 (m, 2J (PHa′) )
13.22 Hz, 3J (PHa′) ) 2.10 Hz, 3J (Ha′Hb′) ) 10.37 Hz, 3J (Ha′Hc′)
Exp er im en ta l Section
3
3
) 0.62 Hz, 1H, Ha′), 2.62 (m, J (PHc′) ) 16.23 Hz, J (PHc′) )
6.31 Hz, 2J (Hb′Hc′) ) 9.91 Hz, 3J (Ha′Hc′) ) 0.62 Hz, 1H, Hc′),
A. Rea gen ts a n d P h ysica l Mea su r em en ts. All chemi-
cals were reagent grade and were used as received from
commercial sources (Aldrich or Fisher Scientific) or synthe-
sized as described below. Diphenylvinylphosphine was pur-
chased from Organometallics. HPF6 (60 wt % solution in
water) was purchased from Aldrich and used as received.
Solvents were dried by standard procedures and stored over
Linde type 4Å molecular sieves. All syntheses were conducted
1.29 (apparent t, J (PH) ) 4J (P′H) ) 1.5 Hz, 15H, CH3). 13C-
4
{1H} NMR (CDCl3): δ 136.20 (d, 2J (PC) ) 12.47 Hz, Co),
133.17(d, 2J (PC) ) 9.82 Hz, Co), 132.06 (d, 2J (PC) ) 10.66 Hz,
Co), 132.01 (d, 2J (PC) ) 12.09 Hz, Co), 131.63 (d, 1J (PC) ) 45.85
Hz, CR), 131.28 (s, Cp), 103.54 (s, Cp), 129.75 (d, 3J (PC) ) 11.56
Hz, Cm), 129.53 (d, 3J (PC) ) 11.56 Hz, Cm), 129.48 (dd, 1J (PC)
) 68.40 Hz, 3J (PC) ) 4.08 Hz, Ci), 129.02 (d, 2J (PC) ) 4.9 Hz,
Câ), 128.60 (d, 3J (PC) ) 9.22 Hz, Cm), 128.50 (d, 3J (PC) ) 10.05
24
in Schlenk glassware under a nitrogen atmosphere. HC5Me5
1
1
Hz, Cm), 128.44 (d, J (PC) ) 54.57 Hz, Ci), 127.75 (dd, J (PC)
7
and [(η5-C5Me5)RuCl2]2 were synthesized by literature proce-
3
) 43.99 Hz, J (PC) ) 4.75 Hz, Ci), 96.45 (s, C5Me5), 47.87 (d,
dures. Elemental analyses were performed by Galbraith
Laboratories, Knoxville, TN. Melting points were obtained
using a Mel-Temp melting point apparatus and are uncor-
rected. 1H, 1H{31P}, and 13C{1H} NMR spectra were recorded
at 499.8, 499.8, and 125.7 MHz, respectively, on a Varian
Unity Plus 500 FT-NMR spectrometer. Proton and carbon
chemical shifts are relative to internal Me4Si or solvent
resonances. 31P{1H} NMR spectra were recorded at 121.65
MHz on a General Electric GN 300 FT-NMR spectrometer.
Phosphorus chemical shifts are relative to external 85% H3-
PO4(aq) with positive values being downfield of the respective
reference. Unless otherwise stated, all chromatography was
performed using the following general procedure: A 60 mL
sintered glass fritted funnel was used as the column and
attached to a 1000 mL Erlenmeyer flask equipped with a side
arm. A 2.5 cm layer of silica gel (grade 12, 28-300 mesh,
Aldrich) was covered with Celite (Aldrich, 0.5 cm layer) and
firmly packed with a spatula and suction. The crude reaction
product was dissolved in a minimal amount of a volatile
solvent (usually CH2Cl2) and loaded onto the column, and the
solvent was removed with suction. All subsequent solvents
were eluted with suction.
2J (PC) ) 7.2 Hz, Câ′), 37.55 (d, J (PC) ) 33.8 Hz, CR′), 9.01 (t,
1
3J (PC) ) J (P′C) ) 11.2 Hz, CH3). 31P{1H} NMR (CDCl3): δ
3
44.85 (d, J (PP) ) 48.5 Hz, η1-DPVP), 14.29 (d, J (PP) ) 48.5
2
2
Hz, η3-DPVP), -144.1 (septet, J (PF) ) 712.8 Hz, PF6-).
1
P r ep a r a tion of [(η5-C5Me5)Ru (η1-DP VP )2(NCS)] (2). A
25 mL Schlenk flask was charged with 1 (0.15 g, 0.19 mmol),
10 mL of CH2Cl2, and a solution of NaNCS (0.13 g, 1.6 mmol)
in 10 mL of MeOH. The solution was stirred vigorously for
20 h and gradually turned from yellow to red. The solvents
were removed in vacuo, and the residue was dissolved in a
minimal amount of CH2Cl2 and filtered. The filtrate was
evaporated, and the product was extracted with 4 × 20 mL of
Et2O. The Et2O washings were combined, evaporated to
dryness, and dried to give 0.09 g of 2 in 67% yield. The product
is mildly air sensitive in solution. Mp: 225 °C dec. Anal.
Calcd for C39H41NP2RuS: C, 65.16; H, 5.57. Found: C, 65.02;
H, 5.38. 1H NMR (CDCl3): δ 7.56-6.96 (m, 20 H, Ph), 5.69
4
(m, 4H, Ha,b), 5.19 (m, 2H, Hc), 1.33 (t, J (PH) ) 1.5 Hz, 15H,
1
3
CH3). 13C{1H} NMR (CDCl3): δ 136.56 (D, | J (PC) + J (PC)|
) 41.4 Hz, Ci), 134.84 (T, | J (PC) + 4J (PC)| ) 11.8 Hz, Co),
2
133.78 (D, | J (PC) + 3J (PC)| ) 36.6 Hz, CR), 133.51 (D, | J (PC)
1
1
3
2
4
+ J (PC)| ) 42.5 Hz, Ci), 132.99 (T, | J (PC) + J (PC)| ) 9.7
B. Syn th eses. P r epar ation of [(η5-C5Me5)Ru (η3-DP VP )-
(η1-DP VP )]P F 6 (1). A 250 mL, three-neck round-bottom flask
was fitted with a septum, gas inlet adapter, and a U-tube
adapter. A glass frit funnel was attached to both the U-tube
and a second 250 mL round-bottom flask equipped with two
necks. The entire apparatus was flame-dried under vacuum
and flushed with nitrogen. The first flask was charged with
[(η5-C5Me5)RuCl2]2 (2.5 g, 4.1 mmol), powdered zinc (6.6 g, 101
Hz, Co), 131.80 (D, | J (PC) + 4J (PC)| ) 2.8 Hz, Câ), 129.85 (s,
2
Cp), 128.85 (s, Cp), 127.68 (T, | J (PC) + 5J (PC)| ) 9.6 Hz, Cm),
3
127.48 (T, | J (PC) + 5J (PC)| ) 9.1 Hz, Cm), 127.2 (t, J (PC) )
1.9 Hz, NCS), 90.16 (t, 2J (PC) ) 2.1 Hz, C5Me5), 9.53 (s, CH3).
31P{1H} NMR (CDCl3): δ 39.0 (s).
3
3
P r ep a r a tion of [(η5-C5Me5)Ru (η1-DP VP )2(CO)]P F 6 (3).
A 50 mL flask was charged with 1 (0.15 g, 0.19 mmol) and 20
mL of 1,2-dichloroethane. A Tygon tube, fitted to a gas inlet
adapter, was inserted into the solution. This solution was then
heated to reflux under a CO atmosphere for 116 h. The solvent
(24) Fendrick, C. M; Schertz, L. D.; Mintz, E. A.; Marks, T. J . Inorg.
Synth. 1992, 29, 193.

1722 Organometallics, Vol. 16, No. 8, 1997
Ta ble 6. Cr ysta llogr a p h ic Da ta for 1, 4, 5, a n d 7
Barthel-Rosa et al.
1
4
5
7
empirical formula
fw
cryst dimens (mm)
cryst syst
space group
a (Å)
C38H41F6P3Ru
805.7
0.15 × 0.30 × 0.40
orthorhombic
Pca21
17.291(5)
14.313(4)
29.640(8)
90
90
90
7335(6)
8
1.459
C46H47F6P3Ru
907.82
0.18 × 0.2 × 0.3
orthorhombic
Pbca
15.275(2)
22.723(3)
24.834(2)
90
90
90
8620(2)
8
1.399
C42H47F6OP3Ru
875.78
C55H57F12P5Ru
1201.93
0.10 × 0.17 × 0.42
monoclinic
P21/c
10.359(2)
27.270(5)
19.081(3)
90
0.46 × 0.25 × 0.84
triclinic
P1h
13.119(2)
15.605(2)
20.538(3)
106.424(11)
93.550(12)
90.923(12)
4022.8(10)
4
b (Å)
c (Å)
R (deg)
â (Å)
90.606(14)
90
5390(2)
γ (Å)
V (Å3)
Z
4
dcalcd (g/cm3)
1.446
0.569
Mo KR
298
1.481
0.518
Mo KR
298
µ (mm-1
)
0.6027
Mo KR
293
0.532
Mo KR
298
radiation (λ ) 0.710 73 Å)
temp (K)
scan type
2θ range (deg)
no. of reflcns collcd
no. of indepdnt reflcns
abs corr
ω/2θ
ω
ω
ω
4-50
3.58-45
3.62-45
3.68-45
7093
7093
6845
12 080
10415 (Rint ) 0.0187)
ψ-scans
0.9742 and 0.7831
10415/0/1001
0.0409, 0.0947
1.308
0.00040(11)
0.54/-0.46
8870
5637 (Rint ) 0.1018)
ψ-scans
0.7447 and 0.7317
5635/0/505
0.082, 0.1087
0.989
7049 (Rint ) 0.0934)
ψ-scans
0.7723 and 0.7158
7046/0/695
0.0849, 0.1029
1.014
ψ-scans
1 and 0.95
3822/1/864
0.040, 0.052a
1.079
max and min transmission
data/restraints/params
R1,b wR2c [I > 2σ(I)]
goodness of fit (F2)d
extinction coeff
0
0
0
largest diff peak and hole (e Å-3
)
0.87/-0.58
0.38/-0.41
0.44/-0.40
a
b
2
d
2
[I > 3σ(I)]. R1(F) ) ∑||Fo| - |Fc||/∑|Fo|. c wR2(F2) ) [∑[w (Fo - Fc2)2]/∑[w(Fo2)2]0.5
.
GOF ) S ) [∑[w(Fo - Fc2)2]/(n - p)]0.5
.
was removed in vacuo, and the yellow residue was treated with
3 × 5 mL portions of Et2O. The product was dried in high
vacuum (0.1 mmHg) at 68 °C for 24 h to give 0.15 g of 3 in
94% yield. Mp: 182-183 °C. Anal. Calcd for C39H41F6OP3-
Ru: C, 56.18; H, 4.96. Found: C, 56.08; H, 5.04. 1H NMR
(CDCl3): δ 6.76-7.76 (m, 20H, Ph), 5.93 (m, 2H, Hb), 5.45 (br
m, 2H, Ha), 5.29 (m, 2H, Hc), 1.59 (t, 4(PH) ) 1.7 Hz, 15H,
was refluxed for 28 h. The mixture was then concentrated to
a volume of about 10 mL, Et2O (15 mL) was layered on top of
the CH2Cl2 solution, and the mixture was stored at -25 °C
for 48 h. The resulting yellow crystals were collected on a glass
frit, washed with 3 × 5 mL portions of Et2O, and dried to give
0.14 g of 5 in 63% yield. Anal. Calcd for C42H47F6OP3Ru: C,
57.60; H, 5.41. Found: C, 57.54; H, 5.32. 1H NMR (CDCl3):
2
CH3). 13C{1H} NMR (CDCl3): δ 204.25 (t, J (PC) ) 17.2 Hz,
2
4
2
CO), 134.23 (T, | J (PC) + J (PC)| ) 11.9 Hz, Co), 132.33 (D,
O
1
2
| J (PC) + 3J (PC)| ) 47.0 Hz, CR), 132.31 (T, | J (PC) + 4J (PC)|
3
1
) 9.7 Hz, Co), 130.86 (D, | J (PC) + 4J (PC)| ) 5.7 Hz, Câ), 130.84
2
4
5
(s, Cp), 130.62 (s, Cp), 129.59 (D, | J (PC) + 3J (PC)| ) 43.9 Hz,
1
Ci), 128.96 (D, | J (PC) + 3J (PC)| ) 50.9 Hz, Ci), 128.91 (T,
1
3
3
| J (PC) + 5J (PC)| ) 10.6 Hz, Cm), 128.52 (T, | J (PC) + 5J (PC)|
) 10.1 Hz, Cm), 100.1 (t, 2J (PC) ) 1.4 Hz, C5Me5), 9.72 (s, CH3).
31P{1H} NMR (CDCl3): δ 35.3 (s), -144.1 (septet, 1J (PF) )
712.8 Hz, PF6-).
δ 6.61-7.59 (m, 20H, Ph), 5.67 (br m, 4H, Hb,c), 4.93 (br m,
3
3
2H, Ha), 4.31 (t, J (HH) ) 7.0 Hz, 2H, C(3)H), 3.35 (t, J (HH)
) 7.0 Hz, 2H, C(5)H), 2.11 (br m, 2H, C(4)H), 1.48 (br m, 15H,
CH3). 13C{1H} NMR (CDCl3): δ 299.50 (m, RudCRd), 135.23
(br m), 133.78 (br), 133.11 (br), 131.37 (s), 130.01 (br), 128.27
P r epar ation of [(η5-C5Me5)Ru (η1-DP VP )2{CdC(H)(P h )}]-
P F 6 (4). A 25 mL Schlenk flask was charged with 1 (0.20 g,
0.25 mmol), 20 mL of MeOH, and HCtCPh (0.04 mL, 0.36
mmol). The solution was refluxed under N2 for 16 h and
rapidly turned from yellow to red. The reaction solution was
then cooled to -25 °C for 48 h, from which an orange solid
precipitated. The precipitate was collected on a glass frit,
washed with 3 × 5 mL portions of Et2O, and dried to give 0.12
g of 4 in 53% yield. Compound 4 can be recrystallized from
hot methanol. Mp: 174-176 °C. Anal. Calcd for C46H47F6P3-
Ru: C, 60.86; H, 5.22. Found: C, 60.73; H, 5.09. 1H NMR
(CDCl3): δ 6.68-7.64 (m, 25H, Ph), 5.79 (m, 2H, Hb), 5.65 (br
3
5
(T, | J (PC) + J (PC)| ) 10.0 Hz, Cm), 127.08 (br), 126.64 (br),
99.32 (br, C5Me5), 80.86 (s, C3), 55.81 (s, C5), 23.41 (s, C4),
10.04 (s, CH3). 31P{1H} NMR (CDCl3): δ 45.1 (s), -144.4
1
(septet, J (PF) ) 712.8 Hz).
P r ep a r a t ion of [(η5-C5Me5)R u (η1-DP VP )2{CdC(H )-
(CH2OH)}]P F 6 (6). A 25 mL Schlenk flask was charged with
1 (0.25 g, 0.31 mmol), 12 mL of CHCl3, and HCtCCH2OH
(0.035 mL, 0.60 mmol). The solution was stirred at room
temperature for 72 h and a yellow solid gradually precipitated
out of solution. The yellow precipitate was isolated on a glass
frit, washed with 2 × 5 mL portions of hexanes, and dried to
give 0.16 g of 6 in 60% yield. Anal. Calcd for C41H45F6OP3-
Ru: C, 57.14; H, 5.26. Found: C, 57.07; H, 5.14. 1H NMR
{(CD3)2CdO}: δ 7.78-6.78 (m, 20H, Ph), 5.95 (m, 2H, Hb), 5.79
(br m, 2H, Hc), 5.17 (m 2H, Ha), 4.88 (tt, 3J (HH) ) 8.0 Hz,
4J (PH) ) 2.2 Hz, 1H, dCdCH), 4.49 (dd, 3J (HH) ) 8.0 Hz,
3J (HH) ) 5.8 Hz, 2H, CH2), 4.19 (t, 3J (HH) ) 5.8 Hz, 1H, OH),
1.63 (t, 4J (PH) ) 1.5 Hz, 15H, CH3). 13C{1H} NMR {(CD3)2-
CdO}: δ 351.00 (t, 2J (PC) ) 15.7 Hz, RudCRd), 135.69 (T,
4
m, 2H, Ha), 5.26 (t, J (PH) ) 2.2 Hz, 1H, dCdCH), 5.01 (m,
4
2H, Hc), 1.62 (t, J (PH) ) 1.5 Hz, 15H, CH3). 13C{1H} NMR
(CDCl3): δ 353.6 (m, RudCRd), 134.4-126.99 (m, PCdC, Ph),
115.41 (s, RudCdCâ), 103.83 (br s, C5Me5), 9.96 (s, CH3). 31P-
{1H} NMR (CDCl3): δ 38.0 (s), -144.2 (septet, 1J (PF) ) 712.7
Hz, PF6-).
P r epar ation of (5) [(η5-C5Me5)Ru (η1-DP VP )2{C(CH2)3O}]-
P F 6 (5). A 50 mL Schlenk flask was charged with 1 (0.20 g,
0.25 mmol), 20 mL of CH2Cl2, and HCtCCH2CH2OH (0.04 mL,
0.53 mmol). The solution was stirred at room temperature
for 15 h. The 31P{1H} NMR spectrum of this solution contains
a singlet at 38.0 ppm for the vinylidene adduct. This solution
2
2
| J (PC) + 4J (PC)| ) 11.8 Hz, Co), 133.99 (T, | J (PC) + 4J (PC)|
) 9.7 Hz, Co), 132.90 (s, Cp), 131.75 (s, Cp), 131.60 (m, Ci),
131.24 (m, Ci), 130.77 (D, | J (PC) + 3J (PC)| ) 51.5 Hz, CR,
1
3
5
DPVP), 130.64 (s, Câ, DPVP), 129.72 (T, | J (PC) + J (PC)| )
10.3 Hz, Cm), 129.29 (T, | J (PC) + 5J (PC)| ) 10.2 Hz, Cm),
3

η3-Diphenylvinylphosphine Phosphaallyl Ligand
Organometallics, Vol. 16, No. 8, 1997 1723
112.08 (t, 3J (PC) ) 1.2 Hz, RudCdCâ), 104.06 (t, 2J (PC) ) 1.4
Hz, C5Me5), 53.93 (s, CH2), 10.04 (s, CH3). 31P{1H} NMR (CH2-
were refined at calculated positions with a riding model in
which the C-H vector was fixed at 0.95 Å with isotropic
temperature factors such as B(H) ) 1.3 Beqv (C) Å. A final
Fourier difference map revealed no significant maximums. All
calculations were performed on a VAX computer using the
Enraf-Nonius VAX/Molen package.25 The absolute structure
was determined by comparing R, Rw, and GOF for x, y, z and
-x, -y, -z refinements and confirmed by refinement of Flack’s
x ) 0.20(2).26 Neutral atom scattering factor coefficients and
anomalous dispersion coefficients were taken from a standard
source.27
Orange crystals of 4 were grown from boiling methanol;
yellow crystals of 5 and pink/orange crystals of 7 were grown
by slow diffusion of Et2O into saturated CH2Cl2 solutions. The
crystals were coated with epoxy, mounted on glass fibers, and
placed on a Siemens P4 diffractometer. Two check reflections,
monitored every 100 reflections, showed random (<2%) varia-
tion during the data collection. Unit cell parameters were
determined by least-squares refinement of 24 reflections for
4, 5, and 7. The data were corrected for Lorentz, polarization,
and absorption (using an empirical model derived from azi-
muthal data collections). Scattering factors and corrections
for anomalous dispersion were taken from a standard source.28
Calculations were performed with the Siemens SHELXTL Plus
version 5.1 software package on a personal computer. The
structures were solved by direct methods. Anisotropic thermal
parameters were assigned to all non-hydrogen atoms. Hydro-
gen atoms were refined at calculated positions with a riding
model in which the C-H vector was fixed at 0.96 Å. The PF6
ions of structures 5 and 7 are disordered.
Cl2): δ 39.3 (s), -144.4 (septet, J (PF) ) 712.8 Hz, PF6-).
1
P r ep a r a tion of [(η5-C5Me5)Ru (η1-DP VP )2{CdC(CH2)2-
P P h 2CH2}][P F 6]2 (7). A 50 mL Schlenk flask was charged
with 6 (0.20 g, 0.17 mmol) and 20 mL of CH3CN. The reaction
solution was stirred at room temperature under N2 until the
color of the solution changed from yellow/orange to violet (∼24
h). The reaction mixture was then charged with DPVP (0.04
mL, 0.20 mmol) and HPF6 (0.03 mL, 0.20 mmol) and refluxed
for 24 h. The solution volume was then reduced to 10 mL,
and 20 mL of Et2O was added. The rose/pink precipitate was
collected on a glass frit and washed with 3 × 10 mL portions
of Et2O. The product was recrystallized from CH2Cl2/Et2O to
give 0.09 g of 7 in 44% yield. Anal. Calcd for C55H57F12P5Ru:
C, 54.96; H, 4.78. Found: C, 54.79; H, 4.68. 1H NMR (CD3-
2
3
1
Ph
P4
5
Ph
NO2): δ 7.98-6.72 (m, 30H, Ph), 5.88 (br, 4H, Hb,c), 5.16 (br,
2H, Ha), 4.40 (d, 2J (PH) ) 11.0 Hz, 2H, C(5)H2), 3.83 (dt,
3J (PH) ) 15.0 Hz, 3J (HH) ) 7.5 Hz, 2H, C(2)H2), 3.27 (dt,
2J (PH) ) 10.5 Hz, 3J (HH) ) 7.5 Hz, 2H, C(3)H2), 1.57 (t, 4J (PH)
) 0.9 Hz, 15H, CH3). 13C{1H} NMR (CD3NO2): δ 341.1 (br,
RudCRd), 137.1 (s, Cp, Ph2P+), 136.3 (br, Co, DPVP), 134.5 (br,
Cm, DPVP), 134.22, (d, 2J (PC) ) 10.8 Hz, Co, Ph2P+), 133.63
(s, Cp, Ph2P+), 133.13 (s, Cp, DPVP), 132.4 (s, CR, DPVP), 131.88
2
(d, J (PC) ) 12.7 Hz, Co, Ph2P+), 131.1 (br, Ci, DPVP), 130.7
(br, Ci, DPVP), 130.16 (d, 3J (PC) ) 10.1 Hz, Cm, Ph2P+), 129.88
(d, 3J (PC) ) 10.2 Hz, Cm, Ph2P+), 118.98 (d, 1J (PC) ) 81.3 Hz,
Ack n ow led gm en t. We are grateful to the National
Science Foundation (Grant CHE-9214294) for funds to
purchase the Varian Unity Plus 500 MHz NMR spec-
trometer and to J ohnson Mathey Aesar/Alfa for a
generous loan of RuCl3‚3H2O. We thank Dr. Vincent
J . Catalano for his training and assistance in determin-
ing the X-ray crystal structures of 4, 5, and 7.
2
Ci, Ph2P+), 116.12 (d, J (PC) ) 9.8 Hz, RudCdCâ), 106.19 (t,
2J (PC) ) 1.3 Hz, C5Me5), 24.80 (d, 1J (PC) ) 4.1 Hz, C5), 24.37
(d, 2J (PC) ) 1.7 Hz, C2), 23.28 (d, 1J (PC) ) 2.1 Hz, C3), 10.41
(s, CH3). 31P{1H} NMR (CD3CN): δ 42.9 (s, 1P, Ph2P+), 35.7
(br s, 2P, DPVP), -145.2 (septet, J (PF) ) 712.8 Hz, PF6-).
1
C. X-r a y Deter m in a tion a n d P r ocessin g for 1, 4, 5, a n d
7. Crystal data and details of data collection for 1, 4, 5, and
7 are given in Table 6. Data for 1 were collected in the ω/2θ
mode while data for 4, 5, and 7 were collected in the ω mode.
All data were collected with Mo KR graphite-monochromated
radiation (λ ) 0.710 73 Å). Yellow crystals of 1 were grown
from boiling absolute ethanol. Data were collected using an
Enraf-Nonius CAD4-F automatic diffractometer at room tem-
perature. Three standard reflections measured every hour
during the entire data collection period showed no significant
trend. The raw data were converted to intensities and
corrected for Lorentz, polarization, and absorption factors. The
structure was solved by the heavy atom method. After
refinement of the non-hydrogen atoms, difference Fourier
maps revealed maximums of residual electron density close
to positions expected for hydrogen atoms. Hydrogen atoms
Su p p or tin g In for m a tion Ava ila ble: For 1, 4, 5, and 7,
listings of atomic coordinates and isotropic displacement
parameters, H atom coordinates and isotropic displacement
parameters, anisotropic displacement parameterssU values,
and bond distances and angles (65 pages). Ordering informa-
tion is given on any current masthead page.
OM961068J
(25) Molen, An Interactive Structure Solution Procedure, Enraf-
Nonius, Delft, The Netherlands, 1990.
(26) Flack, H. D. Acta. Crystallogr. 1983, A39, 876.
(27) Cromer, D. T.; Waber, J . T. International Tables for X-ray
Crystallography; The Kynoch Press: Birmingham, England, 1974; Vol.
IV.
(28) International Tables for X-Ray Crystallography; D. Reidel
Publishing Co.: Boston, 1992; Vol. C.