(η6-arene)ruthenium(II) complexes with hemilabile η 3-dicyclohexylvinylphosphine (DCVP) and η 3-diphenylvinylphosphine (DPVP) phosphaallyl ligands: Formation of an unexpected trinuclear complex

Article abstract of DOI:10.1081/SIM-120024313

The complexes [(η⁶-arene)RuCl₂(Cy ₂PCH=CH₂)], [arene = MeC₆H₅, (1a); p-MeC₆H₄Me; (2a); p-MeC₆H₄CHMe ₂, (3a); 1,2,4,5-Me₄C₆H₂, (4a); and C₆Me₆, (5a)], have been synthesized by reacting [(η⁶-arene)RuCl₂]₂ with dicyclohexylvinylphosphine (DCVP). In the presence of AgPF₆, in a 1: 1 dichloromethane/acetone solvent mixture the compound [(η ⁶-C₆Me₆)RuCl₂(Cy ₂PCH=CH₂)] (5a) afforded [(η⁶-C ₆Me₆)RuCl(η³-DCVP) ]PF₆ (1b). A similar reaction was conducted with [(η⁶-C₆Me ₆)RuCl₂(Ph₂PCH=CH₂)] in an attempt to form [(η⁶-C₆Me₆)RuCl(η ³-DPVP)]PF₆ (2b). However, this reaction yielded, instead, the unexpected trinuclear heterobimetallic complex [{(η⁶-C ₆-Me₆)Ru(μ-Cl)₂(Ph₂PCH=CH ₂)}₂Ag](PF₆) (3b) the structure of which was determined by X-ray crystallography. Compound (1b) reacts with phenylisocyanide to form [(η⁶-C₆Me₆)RuCl(η ¹-DCVP)(CNPh)]PF₆. The complexes have been characterized by ¹H, ³¹P{¹H} and ¹³C{ ¹H} NMR spectroscopy, elemental analyses, cyclic voltammetry, and in some cases [compounds (4a), (1b) and (3b)] by X-ray crystallography.

Full text of DOI:10.1081/SIM-120024313

SYNTHESIS AND REACTIVITY IN INORGANIC AND METAL-ORGANIC CHEMISTRY
Vol. 33, No. 8, pp. 1329–1349, 2003
(Z6-Arene)ruthenium(II) Complexes with
Hemilabile Z3-Dicyclohexylvinylphosphine
(DCVP) and Z3-Diphenylvinylphosphine
(DPVP) Phosphaallyl Ligands: Formation
of an Unexpected Trinuclear Complex
*
John H. Nelson and Kesete Y. Ghebreyessus
Department of Chemistry, University of Nevada-Reno,
Reno, Nevada, USA
ABSTRACT
The complexes [(Z6-arene)RuCl2(Cy2PCH=CH2)], [arene = MeC6H5,
(1a); p-MeC6H4Me; (2a); p-MeC6H4CHMe2, (3a); 1,2,4,5-Me4C6H2,
(4a); and C6Me6, (5a)], have been synthesized by reacting [(Z6-
arene)RuCl2]2 with dicyclohexylvinylphosphine (DCVP). In the pres-
ence of AgPF6, in a 1:1 dichloromethane/acetone solvent mixture the
compound [(Z6-C6Me6)RuCl2(Cy2PCH=CH2)] (5a) afforded [(Z6-
C6Me6)RuCl(Z3-DCVP) ]PF6 (1b). A similar reaction was conducted
with [(Z6-C6Me6)RuCl2(Ph2PCH=CH2)] in an attempt to form [(Z6-
C6Me6)RuCl(Z3-DPVP)]PF6 (2b). However, this reaction yielded,
instead, the unexpected trinuclear heterobimetallic complex [{(Z6-C6-
*
Correspondence: John H. Nelson, Department of Chemistry, University of Nevada-
Reno, Reno, NV 89557-0020, USA; E-mail: jhnelson@unr.edu.
1329
DOI: 10.1081/SIM-120024313
0094-5714 (Print); 1532-2440 (Online)
www.dekker.com
Copyright D 2003 by Marcel Dekker, Inc.

1330
Nelson and Ghebreyessus
Me6)Ru(m-Cl)2(Ph2PCH=CH2)}2Ag](PF6) (3b) the structure of which
was determined by X-ray crystallography. Compound (1b) reacts with
phenylisocyanide to form [(Z6-C6Me6)RuCl(Z1-DCVP)(CNPh)]PF6.
The complexes have been characterized by 1H, 31P{1H} and 13C{1H}
NMR spectroscopy, elemental analyses, cyclic voltammetry, and in some
cases [compounds (4a), (1b) and (3b)] by X-ray crystallography.
Key Words: Phosphaallyl; Ruthenium; NMR spectroscopy; X-Ray
crystal structures; Cyclic voltammetry.
INTRODUCTION
Hemilabile ligands containing bifunctional phosphines have proven
important in providing novel applications in catalysis and organometallic
chemistry.[1–12] Typical examples are complexes containing phosphino-
ether, -amine and -ester hemilabile ligands.[13–17] The weakly coordinating
part of the ligand has been found to provide enhanced catalytic activity.
Notably, organonickel complexes containing hemilabile P, O ligands are ef-
ficient catalysts for the commercial oligomerization of ethylene into linear
a-olefins: ‘‘Shell Higher Olefin Process.’’[2,3,5] Thus, the coordination chem-
istry of heterodifunctional ligands bearing both hard and soft donor atoms is
an area of considerable current interest.
In the course of our investigation with olefinic phosphines we found that
diphenylvinylphosphine (DPVP) forms the novel hemilabile phosphaallyl
complexes [(Z5-C5H5)Ru(Z3-DPVP)(Z1-DPVP)]PF6 (A),[18] [(Z5-C5Me5)-
Ru(Z3-DPVP)(Z1-DPVP)]PF6 (B)[19] and [(Z5-C5H5Me)Ru(Z3-DPVP)(Z1-
DPVP)]PF6 (C)[20] (Figure 1).
We were interested in finding out whether similar phosphaallyl com-
pounds could be prepared by reacting the isoelectronic (Z6-arene)ruthe-
nium(II) complexes with the olefinic phosphines Ph2PCH=CH2 (DPVP) and
Cy2PCH=CH2 (DCVP). Despite the widespread application of arene-ruthe-
nium(II) complexes, there are only a few studies regarding hemilabile func-
tional phosphines coordinated to (Z6-arene)ruthenium(II) centers. Recently,
Figure 1. Z3-Phosphaallyl complexes reported to date.

(Z6-Arene)ruthenium(II) Complexes
1331
the hemilabile properties of methyldiphenylphosphino-acetate (Ph2PCH2C-
(=O)OMe), 2-diphenylphosphinoethylmethyl ether (Ph2PCH2 CH2O–Me) and
the iminophosphorane-phosphine (Ph2PCH2P(=NR)Ph2) ligands coordinated
to (Z6-arene)ruthenium(II) centers were investigated by Dixneuf and cow-
orkers,[13] Lindner et al.[14] and Gimeno and coworkers,[17] respectively. The
present paper reports 1) the synthesis of [(Z6-arene)RuCl2(DCVP)] [arene =
MeC6H5 (1a), p-MeC6H4Me (2a); p-MeC6H4CH-Me2 (3a); 1,2,4,5-Me4C6H2
(4a); C6Me6 (5a)], 2) the synthesis and reactivity of [(Z6-C6Me6)RuCl(Z3-
DCVP)]PF6 (1b) and 3) the isolation and structural characterization of the
novel trinuclear [{(Z6-C6Me6)Ru(m-Cl)2(DPVP)}2Ag]PF6 (3b). To the best
of our knowledge, (1b) and (3b) are the first Z3-coordinated phosphaallyl (Z6-
arene)-ruthenium(II) complexes.
RESULTS AND DISCUSSION
Synthesis of Dicyclohexylvinylphosphine
Treatment of chlorodicyclohexylphosphine[21] with vinylmagnesium
chloride resulted in the formation of dicyclohexylvinylphosphine as a
colorless-pale yellow liquid, b.p 145–148 °C (2.5–3.0 mmHg), which was
characterized by 1H, 13C{1H} and 31P{1H} NMR spectroscopy. After
distillation it was sufficiently pure for synthetic applications and was used
without further attempts to obtain an analytical state of purity.
Synthesis and Characterization of Complexes (1a)–(5a)
The [(Z6-arene)-RuCl2(Cy2PCH=CH2)] complexes, [arene = MeC6H5
(1a), p-MeC6H4Me (2a); p-Me C6H4-CHMe2 (3a); 1,2,4,5-Me4C6H2 (4a);
C6Me6 (5a)] were prepared by reacting the [(Z6-arene)RuCl2]2 com-
plexes[22] with 2.1 equivalents of dicyclohexylvinylphosphine (DCVP) in
dichloromethane at ambient temperature (Eq. 1).

1332
Nelson and Ghebreyessus
After work-up of the reaction mixture, the products were isolated as
microcrystalline red-orange solids from dichloromethane/diethyl ether
solvent mixtures. The products were obtained in good to moderate yields.
They are air- and moisture-stable solids that are soluble in halocarbons,
methanol, acetone, and acetonitrile.
The compounds were characterized by elemental analyses, melting point
determination, 1H, 13C{1H} and 31P{1H} NMR spectroscopy and cyclic
1
voltammetry. The H NMR spectra contain, in each case, three multiplets in
the olefinic region. The integrated ratios of these resonances to those of the
Z6-arene protons indicated one DCVP ligand per ruthenium. Compared to
the DPVP[23,24] complexes, the 31P{1H} resonances for the DCVP com-
plexes, are shifted significantly upfield, the difference in chemical shift being
from 6–15 ppm. This may be attributed to the higher electron-donating
ability of the dicyclohexylvinylphosphine and hence higher electron density
around the phosphorus center. The carbon and proton chemical shifts and
various coupling constants for the two series of complexes are very similar.
The structure of (4a) was determined by X-ray crystallography
(Figure 2). Crystallographic data are given in Table 1, and selected bond
distances and angles in Table 2. The geometry around the ruthenium center
is pseudo-octahedral with the arene ring, one phosphine and the two
Figure 2. Structural drawing of (4a) showing atom numbering scheme (20%
probability ellipsoids). Hydrogen atoms are omitted for clarity.

(Z6-Arene)ruthenium(II) Complexes
1333
Table 1. Crystallographic data and structure refinement for (4a), (1b), and (3b).
Compound
(4a)
(1b)
(3b)
Formula
Mw
Cryst.syst.
C24H39Cl2PRu
530.49
Monoclinic
P21/c
C26H42ClF6P2Ru
667.06
Monoclinic
P21/c
C27H33Ag0.5Cl4F3P1.5Ru
757.79
Triclinic
ꢀ
P1
Space group
˚
a (A)
˚
7.6650(15))
17.705(6)
18.343(3)
4
15.897(7)
14.892(4)
13.311(6)
4
9.250(3)
13.128(2)
13.244(3)
2
b (A)
˚
c (A)
Z
a (°)
b (°)
g (°)
90
101.181(11)
90
90
108.49(30
90
92.747(14)
99.20(2)
107.594(14)
1505.3(6)
1.672
3
˚
Volume (A )
2442.2(10)
1.443
4347
2989(2)
1.483
4904
rcalcd (Mg/m3)
Reflcns collcd.
Indepdt reflcns
6363
5288
3192
3904
a
R1
wR2
0.0653
0.0837
0.996
0.0833
0.1197
1.001
0.0606
0.1171
1.038
b
GOF
aThe data were refined by the method of full-matrix least squares on F2, with the final
b
R indices having I >2.00s(I), R1 = SkFo|ꢀ|Fck/SFo.
bwR2(F2) = S[w(Fo2ꢀFc2)]/S[w(Fo2)2]}1/2
.
chloride atoms completing the coordination sphere. The Ru–P and Ru–Cl
bond distances are similar to those of the DPVP[23,24] complexes.
The electrochemistry of the complexes was studied by cyclic voltam-
metry. The cylic votammograms in CH2Cl2 solution show a reversible one-
electron oxidation for the Ru(II)/Ru(III) redox couple. The trends in the
Ru(II)/Ru(III) potentials as a function of the arene follow the expected
decrease in the electron donating ability of the arene ligands. The potentials
for the DCVP complexes are only slightly lower than those for the
analogous DPVP[23,24] complexes. This may be attributed to the slightly
higher electron-donating ability of the dicyclohexylvinylphosphine ligand.
Electrochemical and 31P{1H} data for complexes (1a)–(5a) and their DPVP
analogs are summarized in Table 3.
Reactions of (1a)–(5a), with AgPF6
When (1a)–(4a) were stirred in a 1:1 acetone/dichloromethane solution
with AgPF6 either starting materials or decomposition products were re-

1334
Nelson and Ghebreyessus
˚
Table 2. Selected bond distances (A) and bond angles (°) for (4a), (1b), and (3b).
(4a)
(1b)
(3b)
Ru–P
Ru–Cl(1)
2.383(3)
2.425(3)
2.402(3)
2.219(10)
2.304(4)
2.398(4)
2.366(2)
2.429(2)
2.419(2)
2.233(7)
Ru–Cl(2)
[Ru–(C1)–(C6)]a
Ru–C(13)
Ru–C(14)
2.274(14)
2.219(12)
2.200(11)
1.389(15)
C(13)–C(14)
Ag–Cl(1)
Ag–Cl(2)
1.315(12)b
86.65(10)
1.302(11)
2.697(2)
2.682(2)
85.54(7)
P–Ru–Cl(1)
C(14)–Ru–Cl(1)
C(13)–Ru–Cl(1)
P–Ru–Cl(2)
Cl(1)–Ru–Cl(2)
Cl(1)–Ag–Cl(2)
88.07(14)
84.7(4)
106.5(4)
84.43(10)
87.69(11)
84.79(7)
84.46(7)
103.24(6)
a[(C1)–(C6)]-denotes the average Ru–C distances.
bC(11)–C(12).
Table 3. Phosphorus chemical shifts and Ru(II/III) potentials for (1a)–(5a) and
(1a’)–(5a’).
Compound
d
31P{1H}, ppm
E1/2 Ru(II/III) (V)a
DEp (mV)
(1a)
(2a)
18.76
15.34
12.80
12.70
12.63
25.17
29.33
21.77
24.29
29.28
0.71
0.67
0.55
0.52
0.39
0.74
0.67
0.68
0.57
0.47
248
102
97
(3a)
(4a)
138
174
107
138
91
(5a)
(1a’)b
(2a’)b
(3a’)b
(4a’)b
(5a’)b
97
75
aMeasured at 298 K in CH2Cl2 solutions at a glassy carbon working electrode, 0.1 M
tetrabutylammonium hexafluorophosphate as supporting electrolyte. All potentials are
vs. Fc/Fc+. Scan rate 100 mV/s.
bAnalogous compounds with L = DPVP Refs. [23,24].

(Z6-Arene)ruthenium(II) Complexes
1335
covered. But, when compound (5a) reacted with one equivalent of AgPF6 in
a 1:1 acetone/dichloromethane solvent mixture the Z3-coordinated phos-
1
phaallyl compound (1b) (Eq. 2) was produced. The H NMR spectrum of
the Z3-coordinated phosphaallyl compound (1b) displays three multiplets at
d 4.40, 4.06 and 3.32 ppm for Hb, Ha and Hc, respectively that are
significantly shifted upfield compared to the vinyl proton resonances for
(5a). The 13C{1H} NMR resonances of the Ca and Cb carbons occur at d
66.95 and 59.28 ppm. Furthermore, the 31P{1H} resonance (d 34.48) is
shifted significantly downfield compared to the corresponding signals for
(5a). This may be attributed to the ring contribution, DR, due to chelate
formation and the formation of a cationic complex.[25] All aspects of the
NMR data clearly indicate the formation of the phosphaallyl complex (1b).
Moreover, the exo orientation of the Z3-DCVP ligand in (1b) was
Figure 3. Expansion of the 500 MHz 1H-NOE (top), 1H{31P} (middle), and 1H NMR
spectra in the Z3-DCVP region of (1b) in acetone-d6.

1336
Nelson and Ghebreyessus
1
unequivocally established by H NOE experiments and X-ray crystallog-
raphy. When the methyl protons of the hexamethylbenzene ring were
irradiated, a strong NOE enhancement was observed for two of the vinyl
protons (Figure 3).
Crystals of (1b) were grown by slow diffusion of diethyl ether into a
nitromethane solution. A view of the geometry of the cation is shown in
Figure 4. Crystallographic data and details of structure determination are
given in Table 1. The geometry around the ruthenium center is pseudo-
octahedral with the hexamethylbenzene ring occupying three facial co-
ordination sites and the Z3-DCVP and the chloride occupying the other
three coordination sites. For (1b) the Z3-DCVP phosphaallyl ligand has a
˚
P–C(13) bond distance of 1.779(13) A which is slightly shorter than the P–
1
˚
C(11) distance of 1.810(10) A for (4a) of the Z -DCVP vinylphosphine
ligand. Moreover, the coordinated C(13)–C(14) bond of the Z3-DCVP
˚
ligand has a distance of 1.389(15) A which is significantly longer than the
1
˚
C(11)–C(12) bond distance 1.315(12) A for the Z -DCVP ligand in (4a).
The same trend was observed for the analogous compounds (A), (B) and
(C) in Figure 1.[18–20]
Similarly, the reaction of [(Z6-C6Me6)RuCl2(PPh2PCH=CH2)] with
AgPF6 in acetone/dichloromethane was attempted. However, in contrast to
expectations, the isolated product is not the monomeric Z3-DPVP phos-
phaallyl complex (2b) but the trinuclear species (3b) (Figure 5).
1
The H NMR spectrum of (3b) shows three signals between 5.89 and
3.97 ppm attributable to the vinyl protons of the DPVP ligand and some
multiplets in the aromatic region due to the phenyl protons. The 31P{1H}
NMR spectrum displays a singlet at 42.52 ppm in addition to the septet
resonance for the PF6 anion. The 13C{1H} NMR shows signals for the Ca
ꢀ
and Cb carbons at 93.97 and 90.09 ppm, respectively. All aspects of these
spectral data indicate the formation of a phosphaallyl compound; but were
inconclusive until the X-ray structure for this compound was determined. In
1
particular, the H resonances for the vinyl protons are not shifted as far

(Z6-Arene)ruthenium(II) Complexes
1337
Figure 4. Structural drawing of (1b) showing atom numbering scheme (20%
probability ellipsoids). Hydrogen atoms Ha, Hb, and Hc have an arbitrary radius of 0.1
˚
A. The others are omitted for clarity.
upfield as they are for (1b). Moreover, no NOE enhancement was observed
between the methyl and vinyl hydrogens. However, when the X-ray data were
obtained the orange compound turned out to be the unexpected trinuclear
heterotrimetallic complex of formula [{(Z6-C6Me6)Ru(m-Cl)2(Ph2PCH=
CH2)}2Ag]PF6 (3b) rather than the expected monomeric phosphaallyl
˚
derivative (2b) (Figure 5). The Ag(1)–C(13) 3.098 (A), Ag(1)–C(14) 3.025
˚
˚
˚
(A), Ag(1)–C(13A) 3.098 (A) and Ag(1)–C(14A) 3.025 (A) separations for
(3b) are clearly too long for a normal s-bond, but approach the upper end of
what is known for weak Ag-olefin[26] interactions indicating the phosphaallyl
functionality. Based on the crystal structure, all aspects of the NMR data can
now be rationalized. Thus, the slight upfield shift of the vinyl protons is
indicative of a weak interaction between silver and the vinyl moiety of the
phosphine ligand which is in agreement with the solid state structure. The
significant downfield shift in the 31P{1H} NMR spectrum is also indicative of
ring formation[25] and hence, formation of the phosphaallyl compound (3b)
Recently, similar types of tetranuclear [{(Cy)RuAg(m-P1Ru,P2Ag-Ph2P1CH2-
CH2P2-tBu2)}2]PF6[27] and [{Ru(dippe)}2(m-Cl)3(s, Z2-C=CPh)2{Ag2(m-dip-
pe)}]BPh4[28] complexes have been reported.

1338
Nelson and Ghebreyessus
Figure 5. Expected (top) and unexpected (bottom) reactions of compound (5a) with
AgPF6.
Crystals of (3b) were grown by slow diffusion of diethyl ether into a
nitromethane solution. A view of the crystal structure is given in Figure 6.
The coordination sphere around the two ruthenium centers is pseudo-octa-
hedral with the Z6-hexamethylbenzene ring, the phosphorus of the PPh2 unit
and the two chloride atoms occupying the six coordination sites. There are
half-molecules of the cation with silver lying on a crystallographic inversion
center in the asymmetric unit. The geometry around the silver center is
rigorously planar but not square with one [Cl–Ag–Cl] angle being 103.76(6)
˚
A and the other is 76.26(6) A. The Ag–Cl(1) (2.697(2)) A and Ag–Cl(2)
˚
˚
˚
(2.682(2)) A bond lengths are only slightly shorter than Ag–Cl bond lengths
found in other chloride bridged silver–metal complexes.[25,26] The Ru–Cl(1)
˚
(2.429(2)) A and Ru–Cl(2) (2.419(2)) A bond lengths are also slightly longer
˚
˚
˚
than the average Ru–Cl(l) (2.4129(14) A and Ru–Cl(2) (2.4065(15) A bond
lengths for mononuclear [(arene)RuCl2(L)] compounds.[23,24]

(Z6-Arene)ruthenium(II) Complexes
1339
Figure 6. Structural drawing of (3b) showing atom numbering scheme (20%
probability ellipsoids). Hydrogen atoms are omitted for clarity.
Reactions of (1b)
The hemilabile property of the Z3-coordinated phosphaallyl ligand was
illustrated by reacting (1b) with excess phenylisocyanide in a dichloro-
methane solution to give (1c) as a yellow powder (Eq. 3).
The complex has been characterized by IR, and 1H, 13C{1H}, and
31P{1H} NMR spectroscopy. The complex exhibits a characteristic strong IR
absorption at 2138 cm–1 attributable to n (NꢁC) for the bound isocyanide

1340
Nelson and Ghebreyessus
ligand. The absorption occurred at a slightly higher energy than for the
uncoordinated phenylisocyanide (2126 cm–1) ligand. The 1H NMR spectrum
of the complex shows the three characteristic multiplets in the range 6.47 to
5.97 ppm for the Z1-DCVP ligand. This indicates that the Z3-coordinated
phosphaallyl ligand is displaced by the incoming phenyisocyanide.
CONCLUSIONS
A series of Ru(II) complexes of the type [(Z6-arene)RuCl2(Cy2PCH=
CH2)], were prepared and characterized. They are air- and moisture-stable
orange to red solids. The complexes show reversible Ru(II/III) redox
couples. The Ru–P and Ru–Cl distances are comparable to those of the
analogous DPVP complexes. Herein we also describe the synthesis, char-
acterization and reactivity of the first phosphaallyl arene [(Z6-C6Me6)-
RuCl(Z3-DCVP)]PF6 complex (1b). The phosphaallyl complex could only
be prepared with the most electron donating arene. The hemilabile properties
of (1b) were illustrated by the reaction of (1b) with phenylisocyanide.
Moreover, in an attempt to synthesize a similar phosphaallyl compound with
the DPVP ligand an unexpected trinuclear heterotrimetallic compound (3b)
was prepared.
EXPERIMENTAL SECTION
Reagents and Physical Measurements
All chemicals were reagent grade and were used as received or
synthesized as described below. Diethyl ether and tetrahydrofuran were
distilled from sodium/benzophenone ketyl under nitrogen. Vinylmagnesium
chloride was purchased from Aldrich and was used as received. Chlo-
rodicyclohexyl phosphine,[21] [(Z6-arene)RuCl2]2,[22] [(Z6-C6Me6)RuCl2-
(DPVP)][23,24] and 3,6-dimethylcyclohexa-1,4-diene[29] were synthesized by
literature procedures. All reactions involving phosphines were conducted
under a dry nitrogen atmosphere. Elemental analyses were performed by
Galbraith Laboratories, Knoxville, TN. Melting points were obtained using
a Mel-Temp apparatus and are uncorrected. NMR spectra were recorded on
CDCl3 or acetone-d6 solutions with a Varian Unity Plus 500-FT NMR
1
spectrometer operating at 500 MHz for H, 125 MHz for 13C{1H} and 202
MHz for 13P{1H}. Proton and carbon chemical shifts are quoted relative to
internal Me4Si, phosphorus chemical shifts are relative to external 85%
H3PO4(aq) with positive values being downfield of the respective reference.

(Z6-Arene)ruthenium(II) Complexes
1341
Figure 7. Proton and carbon numbering schemes for NMR chemical shift
assignments.
Cyclic voltammograms were recorded at 25 °C in freshly distilled CH2Cl2
solutions containing 0.1 M tetrabutylammonium hexafluorophosphate using
a BAS CV50-W voltammetric analyzer. A three-electrode system was used.
The working electrode was a glassy carbon disk; the auxiliary electrode was
a platinum electrode and the reference electrode was an aqueous Ag+/AgCl
electrode separated from the cell by a Luggin capillary. The Fc/Fc+couple
occurred at 508 mV under the same conditions.[30] Carbon atoms and the
attached hydrogen atoms are numbered as shown in Figure 7.
Synthesis
Preparation of Cy2PCH=CH2
To a solution containing 40.0 g (0.172 mole) Cy2PCl[21] in 300 mL of
dry THF were added dropwise 250 mL of 1.6 M (0.4 mol) vinylmagnesium
chloride in THF with stirring and cooling in an ice bath. The cooling bath
was removed after addition of the Grignard reagent was complete. After
removal of the cooling bath the mixture was heated at reflux for half an
hour, cooled to room temperature and stirred overnight. The resulting
suspension was placed in an ice bath and hydrolyzed with 300 mL 10%
aqueous ammonium chloride. The organic layer was separated and the
water layer was extracted three times with 100 mL of diethyl ether. The
combined organic washings were dried over Na2SO4, filtered, and con-
centrated under vacuum. The residue was distilled to obtain the product as a
colorless to pale yellow liquid; b.p. 145–148 °C (2.5–3.0 mm Hg), (19.3 g,
50% yield).
3
1H NMR (500.0 MHz, acetone-d6, 25 °C) d = 6.02 (ddd, J(HaHc) = 18.5
3
Hz, J(HaHb) = 11.8 Hz, J(PH) = 2.5 Hz, 1H, Ha), 5.59 (ddd, J(PH) = 35.0
2
3
Hz, 3J(HaHb) = 11.8 Hz, 2J(HbHc) = 3.0 Hz, 1H, Hb), 5.43 (ddd,
3
2
3J(HaHc) = 18.5 Hz, J(PH) = 14.5 Hz, J(HbHc) = 3.0 Hz, 1H, Hc), 1.75 (m,
10H, Cy), 1.27 (m, 12H, Cy).

1342
Nelson and Ghebreyessus
13C{1H} NMR(125.697 MHz, acetone-d6, 25 °C) d = 137.08 (d,
1J(PC) = 21.0 Hz, Ca), 131.84 (d, 2J(PC) = 32.8 Hz, Cb) 33.60 (d,
3
1J(PC) = 10.9 Hz, Ca’), 30.93 (Cb’), 30.79 (Cb’), 29.63 (d, J(PC) = 4.0 Hz,
3
Cg), 29.60 (d, J(PC) = 3.6 Hz, Cg), 27.60 (Cd). 31P{1H} NMR (202.3 MHz,
acetone-d6, 25 °C), d = ꢀ2.5 ppm.
Preparations of Complexes (1a)–(5a)
The complexes were synthesized from the appropriate [(Z6-arene)Ru-
Cl2]2 as follows. A suspension of 1.0 mmol of the dimer in 40 mL of
dichloromethane was treated with 2.1 equivalents of dicyclohexylvinylpho-
sphine via syringe. The mixture was stirred at ambient temperature for 4 h.
The volume of the solution was reduced to about 10 mL on a rotary
evaporator and then the solution was layered with diethyl ether to induce
crystallization. The products were isolated by filtration, washed with diethyl
ether and dried under vacuum to give the pure products as microcrystalline
orange-red solids. Their yields, melting points and analytical data are given
in Table 4. The NMR data are given below.
(1a). 1H NMR (500.0 MHz, CDCl3, 25 °C), d 6.37 (apparent td,
3
3
3J(HaHc) = 3J(PH) 19.5 Hz, J(HaHb) = 12.5 Hz, 1H, Ha), 5.88 (ddd, J(PH) =
33.0 Hz, 3J(HaHb) = 12.5 Hz, 2J(HbHc) = 0.5 Hz, 1H, Hb), 5.62 (dd, 3J(HaHc) =
19.5 Hz, 3J(PH) = 16.0 Hz, 1H, Hc), 5.60 (m, 2H, Hm), 5.34 (d, 3J(HH) = 6.0 Hz,
1H, Ho), 4.98 (t, 3J(HH) = 5.0 Hz, 1H, Hp), 2.23 (m, 2H, Haa), 2.22 (s, 3H, CH3),
2.08 (d, 2J(HH) = 12.5 Hz, 2H, Hbe), 1.96 (d, 2J(HH) = 13.0 Hz, 2H Hbe), 1.84
(d, 2J(HH) = 13.0 Hz, 2H, Hge), 1.78 (d, 2J(HH) = 10.5 Hz, 2H, Hde), 1.70 (d,
3J(HH) = 13.0 Hz, 2H, Hga), 1.52 (m, 2H, Hba), 1.35 (m, 2H, Hba), 1.24 (m, 6H,
Hgd). 13C{1H} NMR (125.7 MHz, CDCl3, 25 °C), d = 129.00 (d, 1J(PC) = 40.1
Hz, Ca), 127.11 (d, 2J(PC) = 5.8 Hz, Cb), 109.00 (d, J(PC) = 5.3 Hz, Cq, arene),
86.85 (Co, arene), 86.65 (d, J(PC) = 5.9 Hz, Cm, arene), 86.37 (Cp, arene), 36.69
(d, 1J(PC) = 23.8 Hz, Ca’), 31.72 (Cb’), 28.69 (d, 3J(PC) = 13.7 Hz, Cb’), 26.98
(d, 3J(PC) = 10.9 Hz, Cg’), 26.19 (Cg’), 25.55 (Cd’), 18.82 (CH3).
(2a). 1H NMR (500.0 MHz, CDCl3, 25 °C), d = 6.33 (apparent td,
3J(HaHc) = 2J(PH) = 19.0 Hz, 3J(HaHb) = 13.0 Hz, 1H, Ha), 5.82 (dd, 3J(PH) =
32.3 Hz, 3J(HaHb) = 13.0 Hz, 1H, Hb), 5.54 (dd, 3J(PH) = 20.0 Hz, 3J(HaHc) =
2
19.0 Hz, 1H, Hc), 5.41 (s, 4H, arene), 2.19 (apparent td, J(PH) = 20.0 Hz,
3J(HH) = 3J(HH) = 12.0 Hz, 2H Haa) 2.00 (s, 6H, CH3), 1.93 (d, 2J(HH) = 13.0
2
2
Hz, 2H, Hbe), 1.79 (d, J(HH) = 13.0 Hz, 2H, Hbe), 1.73 (d, J(HH) = 8.5 Hz,
2H, Hbe), 1.66 (d, 2J(HH) = 12.0 Hz, 2H, Hge), 1.46 (m, 4H, Hga), 1.23 (m, 8H,
H
bad). 13C{1H} NMR (125.7 MHz, CDCl3, 25 °C), d = 129.06 (d, 1J(PC) = 39.3
Hz, Ca), 126.29 (d, 2J(PC) = 6.3 Hz, Cb), 94.68 (Cq, arene), 88.18 (d,
J(PC) = 4.5 Hz, CH, arene), 36.37 (d, 1J(PC) = 23.0 Hz, Ca’), 31.73 (d,

(Z6-Arene)ruthenium(II) Complexes
1343

1344
Nelson and Ghebreyessus
2J(PC) = 2.0 Hz, Cb’), 30.05 (d, 3J(PC) = 3.5 Hz, Cb’), 28.37 (d, 3J(PC) = 13.2
Hz, Cg’), 26.82 (d, 3J(PC) = 10.4 Hz, Cg’), 26.03 (Cd’), 17.68 (2CH3).
(3a). 1H NMR (500.0 MHz, CDCl3, 25 °C), d = 6.36 (apparent td, 2J(PH) =
3J(HaHc) = 19.0 Hz, 3J(HaHb) = 12.5 Hz, 1H, Ha), 5.89 (dd, 3J(PH) = 31.5 Hz,
3J(HaHb) = 12.5 Hz, 1H, Hb), 5.59 (dd, 3J(HaHc) = 19.0 Hz, 3J(PH) = 15.0 Hz,
3
3
1H, Hc), 5.47 (m, AB, J(HH) = 5.5 Hz, 4H, arene), 2.79 (sept, J(HH) = 6.5,
Hz, 1H, CH), 2.28 (apparent td, 2J(PH) = 21.5 Hz, 3J(HH) = 10.5 Hz, 2H, Haa)
2.05 (s, 3H, CH3) 1.97 (d, 3J(HH) = 13.0 Hz, 2H, Hbe), 1.81 (d, 3J(HH) = 11.0
Hz, 2H, Hde), 1.77 (d, 3J(HH) = 11.0 Hz, 2H, Hda), 1.69 (d, 3J(HH) = 11.0 Hz,
3
3
2H, Hga), 1.38 (d, J(HH) = 12.5 Hz, 2H, Hbe), 1.43 (apparent J(HH) = 12.5
3
3
Hz, 2H, Hge), 1.32 (d, J(HH) = 13.0 Hz, 2H, Hba), 1.22 (d, J(HH) = 6.5 Hz,
6H, CH3), 1.20 (m, 8H, Hgd). 13C{1H} NMR (125.7 MHz, CDCl3, 25 °C),
d = 129.13 (d, 1J(PC) = 38.8 Hz, Ca), 126.51 (d, 2J(PC) = 6.3 Hz, Cb), 107.67
(Cq, arene), 94.81 (Cq, arene), 87.90 (d, J(PC) = 3.8 Hz, CH, arene), 84.09 (d,
J(PC) = 5.2 Hz, CH, arene), 36.31 (d, 1J(PC) = 24.0 Hz, Ca’), 30.36 (CH), 28.58
(Cb’), 28.18 (Cb’), 27.25 (d, 3J(PC) = 10.9 Hz, Cg’), 26.93 (d, 3J(PC) = 10.31 Hz,
Cg’), 26.16 (Cd’), 22.09 (2CH3), 17.92 (CH3).
(4a). 1H NMR (500.0 MHz, CDCl3, 25 °C), d = 6.41 (apparent td,
2J(PH) = 3J(HaHc) = 19.0 Hz, 3J(HaHb) = 13.0 Hz, 1H, Ha), 5.85 (dd,
3J(PH) = 32.5Hz, 3J(HaHb) = 12.5 Hz, 1H, Hb), 5.54 (dd, 3J(HaHc) = 19.0
3
2
Hz, J(PH) = 18.0 Hz, 1H, Hc), 5.30 (s, 2H, arene), 2.24 (dtt, J(PH) 20.5
Hz, 3J(HH) = 3J(HH) = 12.0 Hz, 3J(HH) = 3.0 Hz, 2H Haa) 1.98 (s, 12H
3
CH3), 1.97 (d, J(HH) = 12.5 Hz, 2H, Hbe), 1.91 (d, J(HH) = 12.5 Hz, 2H,
3
3
Hbe), 1.85 (d, J(HH) = 12.5 Hz, 2H, Hg), 1.76 (d, J(HH) = 11.0 Hz, 2H,
3
Hd), 1.69 (d, J(HH) = 12.0 Hz, 2H, Hbe), 1.36 (td, J(PH) = 2J(HH) = 13.0
3
3
Hz,3J(HH) = 3.0 Hz, 2H, Hba), 1.35 (td,3J(PH) = 37.5 Hz, 2J(HH) =
3J(HH) = 12.5 Hz, J(HH) = 3.0 Hz, 2H, Hba), 1.23 (m, 6H, Hgd). 13C{1H}
3
1
NMR (125.7 MHz, CDCl3, 25 °C), d = 129.07 (d, J(PC) = 38.2 Hz, Ca),
126.39 (d, J(PC) = 6.2 Hz, Cb), 96.21 (d, J(PC) = 2.4 Hz, Cq, arene), 89.36
2
1
(d, J(PC) = 4.7 Hz, CH, arene), 35.09 (d, J(PC) = 22.1 Hz, Ca’), 28.93 (Cb’),
3
28.27 (d, J(PC) = 2.1 Hz, Cb’), 27.43 (d, J(PC) = 10.8 Hz, Cg’), 27.07 (d,
3
3J(PC) = 9.9 Hz, Cg’), 26.63 (d, J(PC) = 1.3 Hz, Cd’), 16.59 (CH3).
4
(5a). 1H NMR (500.0 MHz, CDCl3, 25 °C), d = 6.41 (ddd,
2J(PH) = 23.0 Hz, 3J(HaHc) = 19.0 Hz, 3J(HaHb) = 13.0 Hz, 1H, Ha), 5.81
3
3
2
(ddd, J(PH) = 30.5Hz, J(HaHb) = 12.5 Hz, J(HbHc) = 1.5 Hz, 1H, Hb), 5.57
(ddd, 3J(HaHc) = 19.0 Hz, 3J(PH) = 17.5 Hz, 2J(HbHc) = 1.5 Hz, 1H, Hc),
2.35 (apparent td, 2J(PH) = 22.0 Hz, 3J(HH) = 3J(HH = 12.0 Hz, 2H Haa)
2.21 (d, 2J(HH) = 12.5 Hz, 2H, Hbe), 1.96 (s, 18H CH3), 1.70 (bs, 4H, Hbeg),
2
1.63 (bs, 2H, Hg), 1.41 (apparentq, J(HH) = 3J(HH) = 11.0 Hz, 2H, Hba),
1.17 (m, 8H, Hgd). 13C{1H} NMR (125.7 MHz, CDCl3, 25 °C), d = 131.24
(d, 1J(PC) = 34.3 Hz, Ca), 124.67 (d, 2J(PC) = 3.8 Hz, Cb), 94.78 (d,
1
J(PC) = 2.9 Hz, Cq, arene), 36.77 (d, J(PC) = 20.6 Hz, Ca’), 30.11 (Cb’),

(Z6-Arene)ruthenium(II) Complexes
1345
3
30.08 (Cb’), 27.69 (d, J(PC) = 8.7 Hz, Cg’), 27.48 (d, J(PC) = 12.1 Hz, Cg’),
3
4
26.27 (d, J(PC) = 1.1 Hz, Cd’), 15.47 (CH3).
Preparation of Complexes (1b) and (3b)
These two compounds were prepared in the same way. To a solution of
(5a) (0.30 g, 0.54 mmol) in a 1:1 acetone/dichloromethane mixture was
added (0.14 g, 0. 55 mmol) of AgPF6. After addition of AgPF6 a white
precipitate formed immediately and the red color of the solution changed to
green. The reaction mixture was stirred for 24 h in the dark. The now orange-
yellow solution was filtered through Celite to remove AgCl. The filtrate was
evaporated to dryness by rotary evaporation. The residue was dissolved in a
minimum amount of dichloromethane, filtered and the filtrate was layered
with ether to induce crystallization. The products were isolated by filtration
as orange powders, washed with diethyl ether and dried under vacuum.
(1b). 1H NMR (500.0 MHz, acetone-d6, 25 °C), d = 4.40 (ddd,
2J(PH) = 30.5 Hz, 3J(HaHb) = 9.0 Hz, 3J(HaHc) = 1.5 Hz, 1H, Hb), 4.06
3
3
(apparent td, J(PH) = 3J(HaHc) = 13.0 Hz, J(HaHb) = 9.0 Hz, 1H, Ha), 3.32
(ddd, 3J(HaHc) = 13.0 Hz, 3J(PH) = 9.5 Hz, 2J(HbHc) = 1.5 Hz, 1H, Hc), 2.30–
1.45 (m, 22H, C6H11), 2.29 (s, 18H, CH3). 13C{1H} NMR (125.7 MHz,
acetone-d6, 25 °C), d = 107.58 (d, J(PC) = 1.8 Hz, Cq, arene), 66.95, (d,
2J(PC) = 2.5 Hz, Cb), 59.28 (d, 1J(PC) = 19.6 Hz, Ca), 40.34 (d, 1J(PC) = 24.6
Hz, Ca’), 36.32 (d, 2J(PC) = 17.1 Hz, Cb’), 34.71 (Cb’), 33.38 (Cb’), 29.86 (Cb’),
29.18 (Cb’), 28.34 (Cd’), 28.25 (Cd’), 27.99 (Cg’), 27.86 (Cg’), 27.48 (Cg’), 27.40
(Cg’), 26.12 (CH3). 31P{1H} NMR (202.3 MHz, acetone-d6, 25 °C), d = 36.48
(1 P, DCVP), ꢀ145.0 (sept, 1J(PF) = 708.0 Hz, 1P, PF6).
1
(3b). H NMR (500.0 MHz, CD3NO2, 25 °C), d = 7.70 (m, 10H, Ph),
3
5.89 (ddd, J(HaHc) = 15.0 Hz, J(PH) = 11.5 Hz, J(HaHb) = 10.3 Hz, 1H,
2
3
Ha), 5.49 (dd, 3J(PH) = 25.0 Hz, 3J(HaHb) = 10.3 Hz, 1H, Hb), 3.97 (dd,
3
3J(HaHc) = 15.0 Hz, J(PH) = 13.0 Hz, 1H, Hc), 1.93 (s, 18H, CH3). 13C{1H}
2
NMR (125.7 MHz, CD3NO2, 25 °C), d = 136. 42 (d, J(PC) = 8.0 Hz, Co),
131.85 (Cp), 130.68 (d, J(PC) = 47.9 Hz, Ci), 129.44 (d, J(PC) = 10.8 Hz,
1
3
3
1
Cm), 129.35 (d, J(PC) = 12.4 Hz, Cm), 127.17 (d, J(PC) = 48.4 Hz, Ci),
1
97.73 (d, J(PC) = 2.6 Hz, Cq, arene), 93.97 (d, J(PC) = 41.6 Hz, Ca), 90.09,
(Cb), 14.63 (CH3). 31P{1H} NMR (202.3 MHz, acetone-d6, 25 °C), d =
1
45.52 (1 P, DPVP), ꢀ145.0 (sept, J(PF) = 707.0 Hz, 1P, PF6).
Preparation of (1c)
To a solution of (1b) (0.2 g 0.36 mmol) in 10 mL of dichloromethane
was added (0.2 g 1.94 mmole) of phenylisocyanide via syringe. The re-
action mixture was stirred for 24 h at room temperature under nitrogen.

1346
Nelson and Ghebreyessus
The solution was filtered and the volume of the filtrate was reduced to ca. 2
mL by rotary evaporation. The solution was layered with diethyl ether to
induce cystallization. The product was isolated by filtration as a yellow
powder and dried under vacuum.
1
(1c). H NMR (500 MHz, acetone-d6, 25 °C) d = 7.80 (m, 2H, H2),
7.60 (m, 3H, H3,4), 6.47 (appaent td, 2J(PH) = 3J(HaHc) = 18.5 Hz,
3
3
3J(HaHb) = 12.5 Hz, 1H, Ha), 6.24 (ddd, J(PH) = 35.5Hz, J(HaHb) = 12.5
Hz, 2J(HbHc) = 1.0 Hz, 1H, Hb), 5.97 (ddd, 3J(HaHc) = 18.5 Hz,
3J(PH) = 16.5 Hz, J(HbHc) = 1.0 Hz, 1H, Hc), 2.63 (qt, J(PH) = 22.0 Hz,
2
2
3J(HH) = 12.5 Hz, J(HH) = 2.5 Hz, 2H Haa) 2.27 (s, 18H, CH3), 1.88 (m,
3
4H, Hbe), 1.67 (m, 4H, Hg), 1.47 (m, 6H, Hbg), 1.25 (m, 6H, Hgd). 13C{1H}
2
NMR (125.7 MHz, acetone-d6, 25 °C), d = 132.09 (d, J(PC) = 3.5 Hz, Cb),
131.80 (C4), 131.15 (C3), 130.93 (C1), 129 50 (d, J(PC) = 51.8 Hz, Ca),
1
128. 98 (C2), 109.21 (d, J(PC) = 2.0 Hz, Cq, arene), 37.89 (d, J(PC) = 51.5
1
Hz, Ca’), 28.21 (d, J(PC) = 10.9 Hz, Cb’), 28.08 (d, J(PC) = 4.0 Hz, Cb’),
27.99 (Cg’), 27.95 (d, 3J(PC) = 3.5 Hz, Cg’), 27.85 (Cd’), 15.47 (CH3).
31P{1H} NMR (202.3 MHz, acetone-d6, 25 °C), d = 35.43 (P, DCVP),
1
ꢀ145.0 (sept, J(PF) = 708.0 Hz, 1P, PF6).
X-Ray Data Collection and Processing
Crystals of the compounds were obtained by slow diffusion of diethyl
ether into CH2Cl2 (4a) or nitromethane solutions for (1b) and (3b). They
were mounted on glass fibers, coated with epoxy and placed on a Siemens
P4 diffractometer. Intensity data were taken in the o-mode at 298 K with
˚
Mo-Ka graphite monochromated radiation (l = 0.71073 A). Three check
reflections monitored every 100 reflections showed random (<2%) variation
during the data collections. The data were corrected for Lorentz, polari-
zation effects and absorption [except for (1b)] using an empirical model
derived from azimuthal data collections. Scattering factors and corrections
for anomalous dispersion were taken from a standard source.[31] Calcu-
lations were performed with the Siemens SHELXTL plus version 5.10
software package on a personal computer. The structures were solved by
patterson methods. Anisotropic thermal parameters were assigned to all
non-hydrogen atoms. Hydrogen atoms were refined at calculated positions
˚
with a riding model in which the C–H vector was fixed at 0.96 A. (3b)
crystallized as a CH2Cl2 solvate.
Supporting Information Available
Tables of crystal data and structure refinement, atomic coordinates, iso-
tropic and anisotropic displacement parameters, bond lengths and angles, and
hydrogen coordinates for (4a) (1b) and (3b) are available from the authors.

(Z6-Arene)ruthenium(II) Complexes
ACKNOWLEDGMENTS
1347
This research was supported by an award from the Research Corporation
and by the donors of the Petroleum Research Fund Administered by the
American Chemical Society. We are grateful for this support.
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Received December 2, 2002
Accepted April 24, 2003
Referee I: K. Moedritzer
Referee II: J. T. Mague

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