Base-promoted hydroalkylation reactions of 1,3,5-Me3C6H3, p-MeC6H4CHMe2, C6Me6, p-MeC6H4Me, and MeC6H5 ligands coordinated

Article abstract of DOI:10.1021/om000375t

The [(η⁶-arene)RuCl₂]₂ (arene = 1,3,5-Me₃C₆H₃ (1), p-MeC₆H₄CHMe₂ (2), C₆Me₆ (3), p-MeC₆H₄Me (4), MeC₆

Full text of DOI:10.1021/om000375t

Organometallics 2000, 19, 3387-3392
3387
Ba se-P r om oted Hyd r oa lk yla tion Rea ction s of
1,3,5-Me3C6H3, p-MeC6H4CHMe2, C6Me6, p-MeC6H4Me, a n d
MeC6H5 Liga n d s Coor d in a ted to Ru th en iu m (II)
Kesete Y. Ghebreyessus and J ohn H. Nelson*
Department of Chemistry/ 216, University of NevadasReno, Reno, Nevada 89557-0020
Received May 2, 2000
The [(η6-arene)RuCl2]2 (arene ) 1,3,5-Me3C6H3 (1), p-MeC6H4CHMe2 (2), C6Me6 (3),
p-MeC6H4Me (4), MeC6H5 (5)) dimers react with diphenylvinylphosphine (DPVP) to produce
[(η6-1,3,5-Me3C6H3)Ru(DPVP)Cl2] (1a ), [(η6-p-MeC6H4CHMe2)Ru(DPVP) Cl2] (2a ), [(η6-C6Me6)-
Ru(DPVP)Cl2] (3a ), [(η6-p-MeC6H4Me)Ru(DPVP)Cl2] (4a ), and [(η6-MeC6H5)Ru(DPVP)-
Cl2] (5a ). In acetonitrile, compounds 1-5 undergo base-promoted hydroalkylation reactions
with potassium tert-butoxide and diphenylvinylphosphine to produce [{η6-3,5-Me2C6H3-1-
CH2CH2CH2P(C6H5)2}RuCl2] (1b), [{η6-p-Me2CHC6H4CH2CH2CH2P(C6H5)2}RuCl2] (2b), [{η6-
C6Me5CH2CH2CH2P(C6H5)2}RuCl2] (3b), [{η6-p-MeC6H4CH2CH2CH2P(C6H5)2}RuCl2] (4b), and
[{η6-C6H5CH2CH2CH2P(C6H5)2}RuCl2] (5b). The reaction with the p-MeC6H4CHMe2 complex
proceeds regioselectively at the methyl group to produce the most stable product. All the
complexes have been characterized spectroscopically and the crystal structures of several of
them have been obtained.
In tr od u ction
More recently reactions of other transition-metal arene
complexes have been studied. Among these, the [Fe(η6-
arene)2]2+ 22-29 [Fe(arene)Cp]+,4 and [Ru(arene)Cp]+ 30
complexes offer the possibility of synthesizing function-
alized cyclohexadienes and polyalkylated and polyfunc-
tionalized aromatics.22,23,26 The most studied reactions
consist of deprotonation of a methyl substituent with
an excess of a base and subsequent alkylation of the
methylene group by alkyl or aryl halides.
Despite the aforementioned work for functionalizing
coordinated arene ligands, to our knowledge, few reports
of intramolecular C-H hydroalkylations have appeared.
We have recently found that, in refluxing acetonitrile,
the rhodium complex [(η5-C5Me5)RhCl2]231,32 undergoes
a base-promoted hydroalkylation with potassium tert-
butoxide and diphenylvinylphosphine. We now have
extended these studies to the reactions of [(η6-arene)-
RuCl2]2 complexes under similar conditions. In this
π-Complexation of aromatics by transition-metal moi-
eties has a powerful effect on the reactivity of the
arene.1-9 Exploitation of this effect has led to significant
advances in transition-metal-mediated aromatic chem-
istry.10 One major feature is the enhancement of the
acidity of benzylic protons, which could lead to the
alkylation and functionalization of methylated aromatic
compounds.11-13 Extensive work has been done on
substitution and addition reactions with arenes com-
plexed to the Cr(CO)31,3,14-19 or Mn(CO)3+ 20,21 moieties.
,
(1) Semmelhack, M. F. Ann. N. Y. Acad. Sci. 1977, 36, 295.
(2) Abd-El-Aziz, A. S.; Lee, C. C.; Piorkv, A.; Sutherland, R. G. J .
Organomet. Chem. 1988, 348, 95.
(3) Kunding, P.; Simmons, D. P. J . Chem. Soc., Chem. Commun.
1983, 1320.
(4) Astruc, D. Acc. Chem. Res. 1986, 19, 377.
(5) Grundy, S. L.; Sam, A.-R. H.; Stobart, S. R. J . Chem. Soc., Perkin
Trans. 1 1989, 1663.
(6) Tam, W.; Vollhardt, K. P. C. J . Organomet. Chem. 1981, 216,
97.
(7) Silverthorn, W. E. Adv. Organomet. Chem. 1975, 13, 47.
(8) Ashby, M. T.; Asirvatham, V. S.; Kowalski, A. S.; Khan, M. A.
Organometallics 1999, 18, 5004.
(9) Hegedus, L. S. Transition Metals in the Synthesis of Complex
Organic Molecules; University Science Books: Mill Valley, CA, 1994.
(10) Hamon, J .-R.; Hamon, P.; Sinbandhit, S.; Guenot, P.; Astruc,
D. J . Organomet. Chem. 1991, 413, 243.
(11) Trujillo, H. A.; Casado, C. M.; Ruiz, J .; Astruc, D. J . Am. Chem.
Soc. 1999, 121, 5674.
(19) Lillya, C. P.; Sahatjian, R. A. Inorg. Chem. 1972, 11, 889.
(20) Chung, Y. K.; Sweigart, D. A.; Connelly, W. G.; Sheridan, J . B.
J . Am. Chem. Soc. 1985, 107, 2388.
(21) Brook, M.; Lukacs, A. J . Am. Chem. Soc. 1984, 106, 4161.
(22) Fillant, J .-L.; Astruc, D. J . Chem. Soc., Chem. Commun. 1993,
1320.
(23) Astruc, D. Tetrahedron 1983, 24, 4027.
(24) Fan, L.; Turner, M. L.; Adams, H.; Bailey, N. A.; Maitlis, P. M.
Organometallics 1995, 14, 676.
(25) Mandon, D.; Astruc, D. Organometallics 1990, 9, 341.
(26) Astruc, D.; Hamon, J .-R.; Roman, E.; Michaud, P. J . Am. Chem.
Soc. 1981, 103, 7502.
(12) Kahn, S. D.; Hehre, W. J .; Bartmess, J . E.; Caldwell, G.
Organometallics 1984, 3, 1740.
(13) Trujillo, H. A.; Cassado, C. M.; Astruc, D. J . Chem. Soc., Chem.
Commun. 1995, 7.
(14) Rose-Munch, F.; Rose, E.; Semra, A. J . Chem. Soc., Chem.
Commun. 1986, 1108.
(27) Astruc, D.; Hamon, J .-R.; Mandon, D.; Moulines, F. Pure Appl.
Chem. 1990, 62, 1165.
(28) Moulines, F.; Astruc, D. J . Chem. Soc., Chem. Commun. 1984,
614.
(15) Muntin, R.; Lucas, C.; Thivolk-Cazat, J .; Dufand, V.; Dany, F.;
Basset, J .-M. J . Chem. Soc., Chem. Commun. 1988, 896.
(16) Olah, G. A.; Yu, S. H. J . Org. Chem. 1976, 41, 717.
(17) Kursanov, D. N.; Setkina, V. N.; Petrovskii, P. V.; Zdanavich,
V. I.; Baranetskaya, N. K.; Rubin, I. D. J . Organomet. Chem. 1972,
37, 339.
(29) Buchholz, D.; Gloaguen, B.; Fillaut, J .-L.; Cotrait, M.; Astruc,
D. Chem. Eur. J . 1995, 1, 374.
(30) Casando, C. M.; Wagner, T.; Astuc, D. J . Organomet. Chem.
1995, 502, 143.
(31) Barthel-Rosa, L. P.; Catalano, V. J .; Maitra, K.; Nelson, J . H.
Organometallics 1996, 15, 3924.
(32) Barthel-Rosa, L. P.; Catalano, V. J .; Nelson, J . H. J . Chem. Soc.,
Chem. Commun. 1995, 1629.
(18) Losilkina, V. I.; Estekhina, M. N.; Baranetskaya, N. K.; Setkina,
V. N. J . Organomet. Chem. 1986, 299, 187.
10.1021/om000375t CCC: $19.00 © 2000 American Chemical Society
Publication on Web 07/25/2000

3388 Organometallics, Vol. 19, No. 17, 2000
Ghebreyessus and Nelson
Sch em e 1
plexes 1b-5b were obtained in good yields, in one-pot
reactions, after 48 h of reflux in acetonitrile. Following
1
workup and isolation of the products, the H, 31P{1H},
and 13C{1H} NMR spectra revealed the formation of
complexes 1b-5b. These results establish that the reac-
tion is facilitated by a base to initiate the hydroalkyla-
tion reaction. The use of excess base has been avoided,
since it seems to promote excessive decomposition of the
complexes 1a -5a . The reaction mixtures turned from
a clear red to a dark red upon addition of the base.
The novelty of this reaction is the unusual reaction
between the vinyl moiety on the coordinated phosphorus
and the methyl groups of the η6-arene ligands coordi-
nated to ruthenium(II). The terminal vinylic carbon
atom forms a new C-C bond to the methyl group with
a concomitant C-H bond cleavage and formation of a
new C-H bond on the carbon R to the phosphorus atom.
Thus, a common feature of these reactions is the prior
generation of a metal-stabilized benzyl carbanion that
adds to the â-carbon of the vinyl group to form a new
C-C bond and a carbanion R to the phosphorus that is
subsequently protonated. This reaction is formally a
base-catalyzed hydroalkylation of a C-C double bond.
A notable feature of the products of these reactions
is the simultaneous coordination of both the phosphine
and the η6-arene ligands to the ruthenium center. Thus,
even though there may be an alternative route for syn-
thesizing the phosphinopropyl substituted arene rings,
it would be very difficult if not impossible to coordinate
both the arene and the phosphine moieties to the
ruthenium center. Moreover, the reaction with the
p-MeC6H4CHMe2 arene ligand proceeds regioselectively
at the methyl group to produce the most stable product.
As far we are aware, only one similar ruthenium
complex (6) has been previously reported.34 Rhodium-
Sch em e 2
paper, details of the synthesis and characterization of
novel ruthenium complexes containing chelating (phos-
phinopropyl)arene ligands, which are formed by base-
promoted intramolecular hydroalkylations, are de-
scribed. Our chief aim in this work is to put a func-
tionality onto the methyl substituent which will act as
a hand to grasp and rigidly hold the arene moiety to
the metal in such a way that ring loss during reactions
and catalytic cycles is less of a problem.
Resu lts a n d Discu ssion
Syn t h esis a n d Ch a r a ct er iza t ion of 1a -5a . The
[(η6-arene)RuCl2]2 dimers33 (arene ) 1,3,5-Me3C6H3 (1),
p-MeC6H4CHMe2 (2), C6Me6 (3), p-MeC6H4Me (4),
MeC6H5 (5)) were treated with 2.1 equiv of diphenylvi-
nylphosphine (DPVP) under a nitrogen atmosphere, in
dichloromethane at ambient temperature. After 4 h of
stirring the ruthenium phosphine complexes 1a -5a
were isolated as microcrystalline red solids (Scheme 1).
In chloroform-d, the 31P{1H} NMR spectra of the
complexes show a singlet at δ 34.02 (1a ), 21.77 (2a ),
29.28 (3a ), 29.33 (4a ) and 25.17 ppm (5a ), respectively,
(I) complexes of ArX(CH2)2PPh2 (X ) O, CH2; 7) in which
both the arene and phosphine are coordinated to the
metal have also been described.35 These complexes are
1
corresponding to the coordinated DPVP. The H NMR
spectra (see Experimental Section) show three multip-
lets in the olefinic region. The relative ratios of these
resonances to those of the η6-arene protons confirmed
that there is only one DPVP coordinated to ruthenium
and the vinyl group has not undergone a hydroalkyla-
tion reaction with the η6-arene ligands.
(33) Redwine, K. D.; Hansen, H. D.; Bowley, S.; Isbell, J .; Sanchez,
M.; Vodak, D.; Nelson, J . H. Synth. React. Inorg. Met.-Org. Chem. 2000,
30(3), 379.
(34) (a) Thierrien, B.; Ward, T. R.; Angew. Chem., Int. Ed. 1999,
38, 405. (b) Thierrien, B.; Ko¨nig, A.; Ward, T. R. Organometallics 1999,
18, 1565.
(35) (a) Singewald, E. T.; Shi, X.; Mirkin, C. A.; Schofer, S. J .; Stern,
C. L. Organometallics 1996, 15, 3062. (b) Singewald, E. T.; Stone, C.
S.; Stern, C. L.; Mirkin, C. A.; Yap, G. P. A.; Liable-Sands, L. M.;
Rheingold, A. L. J . Am. Chem. Soc. 1997, 119, 3048.
Rea ction s of 1a -5a w ith Bu tOK. The reactions of
the complexes 1a -5a with 1.0 equiv of ButOK in aceto-
nitrile led to the formation of hydroalkylated products
1b-5b (Scheme 2). Moreover, if isolation of the com-
plexes 1a -5a was avoided, and the base was added 15
min after the dimers were treated with DPVP, com-

Base-Promoted Hydroalkylation Reactions
Organometallics, Vol. 19, No. 17, 2000 3389
F igu r e 1. Structural drawing of 4a with 40% probability
ellipsoids. Hydrogen atoms are omitted for clarity.
F igu r e 3. Structural drawing of 2b with 40% probability
ellipsoids. Hydrogen atoms are omitted for clarity.
overall structures. They differ mainly in the orientations
of the phenyl groups attached to phosphorus. None of
the Ru-P and Ru-Cl bond distances of the hydroalky-
lated products differ significantly from those of their
precursors.33 This indicates that there is no steric
encumbrance upon formation of the hydroalkylated
1
products. The H, 31P{1H}, and 13C{1H} NMR spectro-
scopic data for the precursors 1a and 4a as well as the
hydroalkylated products 1b-5b are in accord with the
assigned structures. Crystallographic data are sum-
marized in Table 1, and selected bond distances and
angles are given in Table 2.
The electron density at the ruthenium atom for the
precursors [(η6-arene)RuCl2(DPVP)] and the hydroalky-
lated products were estimated from the 31P{1H} chemi-
cal shifts and the oxidation potentials for the RuII/RuIII
couples, assuming that these data reflect the electron
density at the metal center. For both types of complexes
a reversible RuII/RuIII oxidation was observed. The cyclic
voltammograms in CH2Cl2 solution show that the
oxidation of the precursors and the hydroalkylated
products occur at the same potentials within experi-
mental error. The trends in RuII/RuIII potentials as a
function of the arene for both the precursors and the
hydroalkylated products follow the expected decrease
in the electron-donating ability of the arene ligands. The
31P{1H} chemical shifts generally move upfield by 6-8
ppm upon formation of the hydroalkylated products.
This indicates that there is a slight increase in electron
density around the metal center upon formation of the
hydroalkylated products. This may be attributed to the
relatively higher electron-donating ability of the pro-
pylene than the vinyl functionality.37 Electrochemical
and 31P{1H} data for the complexes 1a -5a and 1b-5b
are summarized in Table 3.
F igu r e 2. Structural drawing of 1b with 40% probability
ellipsoids. Hydrogen atoms are omitted for clarity.
hemilabile36 and undergo facile novel intramolecular
arene exchange reactions.
X-ray crystallographic analysis confirmed the struc-
tures of both the precursors (1a and 4a ) and the
hydroalkylated products (1b, 2b, 4b, and 5b). The
quality of the crystals of 1a was poor but was sufficient
to establish the atom connectivity. The molecular struc-
ture for 4a and those of the hydroalkylated products
are illustrated in Figures1-5. Figures 4 and 5 appear
in the Supporting Information. The structures of the
precursors possess a pseudo-octahedral geometry around
the ruthenium center. For the hydroalkylated products,
the analysis revealed a pseudo-octahedral geometry at
ruthenium with η6-coordinated arene rings, one pro-
pyldiphenylphosphine moiety and two chlorides com-
pleting the metal coordination sphere. Each ruthenium
bound diphenylphosphine group is connected to the
arene rings via three methylene carbons. A similar
linkage was observed for the analogous rhodium com-
plex [{η5-C5Me3-1,3-CH2CH2CH2P(C6H5)2}2RhCl]PF6.31
For 1b there are two inequivalent molecules in the
asymmetric unit with very small differences in their
Con clu sion
Intramolecular base-promoted hydroalkylation of η6-
coordinated methyl arenes to diphenylvinylphosphine
occurs readily. The novel products of these reactions
contain a tethered phosphinopropyl-η6-arene ligand.
(36) Stone, C. S.; Weinberger, D. A.; Mirkin, C. A. Prog. Inorg. Chem.
1999, 48, 233.
(37) Grim, S. O.; Mcfarane, W. Nature 1965, 208, 995.

3390 Organometallics, Vol. 19, No. 17, 2000
Ta ble 1. Cr ysta llogr a p h ic Da ta for 4a , 1b, 2b, 4b a n d 5b
Ghebreyessus and Nelson
4a
1b
2b
4b
5b
empirical formula
Mw
cryst syst
space group
a (Å)
b (Å)
c (Å)
Z
C
22H23Cl2PRu
C23H25Cl2PRu
504.37
triclinic
C24H27Cl2PRu
518.40
triclinic
P1h
7.8102(5)
9.9985(5)
14.3465(11)
2
C22H23Cl2PRu
490.34
triclinic
P1h
7.8483(10)
10.4983(8)
12.5892(13)
2
C21H21Cl2PRu
476.32
triclinic
P1h
8.2080(6)
8.4318(4)
14.8847(11)
2
490.34
monoclinic
P21/n
16.7533(11)
7.2475(5)
17.4702(14)
4
P1h
12.0231(7)
14.9360(13)
18.37229(12)
a
4
R (deg)
â (deg)
γ (deg)
V (Å3)
90
100.337(6)
92.587(5)
106.386(6)
3097.8(4)
1.593
12574
10878
0.0643
0.1482
96.407(7)
91.310(6)
93.041(5)
1111.29(12)
1.549
4851
3918
0.0387
0.0665
79.294(8)
79.635(9)
88.685(9)
1002.53(18)
1.624
4368
3520
0.0305
0.0653
81.858(8)
79.742(8)
73.636(5)
968.04(11)
1.634
4174
3400
0.0371
0.0757
99.639(4)
90
2091.3(3)
1.557
4788
3687
0.0456
0.0848
1.003
F
calcd (Mg/m3)
no. of rflns collcd
no. of indep rflns
R1(F)a,b
wR2(F2)a,b
GOF
1.043
1.009
1.005
1.065
a
b
The data were refined by the method of full-matrix least squares on F2, with the final R indices having I > 2σ(I). R1(F) ) ∑(|Fo| -
2
2
2
|Fc|)2/∑(|Fo|); wR2(F2) ) [∑w(|Fo | - |Fc |)2/∑w|Fc |]1/2
.
Ta ble 2. Selected Bon d Dista n ces (Å) a n d Bon d An gles (d eg) for th e Com p lexes
4a
1b
2b
4b
5b
Ru-P
2.3529(14)
2.4129(14)
2.4065(15)
2.2103(6)
81.18(5)
2.326(2)
2.420(2)
2.397(2)
2.208(7)
93.13(7)
84.43(7)
88.39(7)
2.3226(11)
2.4040(10)
2.4073(11)
2.2041(6)
88.60(4)
2.3127(9)
2.4108(9)
2.4179(10)
2.2103(3)
84.38(3)
2.3243(11)
2.4183(12)
2.4002(11)
2.2105(9)
90.63(4)
Ru-Cl(1)
Ru-Cl(2)
Ru-(C1-C6)a
P-Ru-Cl(1)
P-Ru-Cl(2)
Cl(1)-Ru-l(2)
87.23(5)
88.24(6)
84.87(4)
89.75(2)
89.75(9)
89.36(2)
84.26(4)
88.79(5)
a
C1-C6 denotes the average Ru-C distances.
Ta ble 3. 31P {1H} NMR Da ta a n d Ru II/Ru III
P oten tia ls for 1a -5a a n d 1b-5b
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 a Varian
Unity Plus-500 FT-NMR spectrometer operating at 500 MHz
for 1H, 125.7 MHz for 13C, and 202.3 MHz for 31P. Proton and
carbon chemical shifts are relative to internal Me4Si, while
phosphorus chemical shifts are relative to external 85%
H3PO4 (aqueous) with positive values being downfield of the
respective reference. Cyclic voltammograms were recorded at
25 °C in freshly distilled CH2Cl2 containing 0.1 M tetrabutyl-
ammonium hexafluorophosphate using a BAS CV 50 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 509 mV
40under the same conditions.
compd
δ(31P{1H}) (ppm)
E1/2(RuII/RuIII) (V)a
∆Ep (mV)
1a
2a
3a
4a
5a
1b
2b
3b
4b
5b
34.02
21.77
29.28
29.33
25.17
27.74
21.13
25.17
20.46
20.10
0.61
0.68
0.47
0.67
0.74
0.61
0.66
0.47
0.67
0.74
105
91b
75b
138
107b
137
128
96
130
102
a
Measured in CH2Cl2 solution at a glassy-carbon working
electrode, with 0.1 M tetrabutylammonium hexafluorophosphate
as supporting electrolyte. All potentials are vs Fc/Fc+. The scan
b
rate was 250 mV/s. Data from ref 33.
Syn t h esis. P r ep a r a t ion s of 1a -5a . Complexes 1a -5a
were synthesized from the appropriate [(η6-arene)RuCl2]2
dimers as follows.33 A suspension of 1.0 mmol of the dimer in
40 mL of dichloromethane was purged with dry nitrogen for
15 min; then 2.1 mmol of diphenylvinylphosphine was added
via syringe. The mixture was stirred under dry nitrogen at
ambient temperature for 4 h. The solution volume was reduced
to about 10 mL on a rotary evaporator, and then ether was
added. The products were isolated by filtration, washed with
ether, and dried under vacuum to give the pure products as
microcrystalline solids (percent yield and melting point (°C)):
1a , 70 and 209-211; 2a , 95 and 195-196; 3a , 68 and 226-
228; 4a , 92 and 223-225; 5a , 85 and 207-209.
These complexes probably could not be prepared by any
other route. The new complexes are stable and are
electronically and structurally very similar to their
precursors. The chelate ring in these complexes is
strain-free. Their reactivity, which is expected to be
somewhat different from that of their precursors, is
presently under investigation.
Exp er im en ta l Section
R ea gen t s a n d P h ysica l Mea su r em en t s. All chemicals
were reagent grade and were used as received or synthesized
as described below. Acetonitrile was dried over CaH2 and
distilled immediately before use. 1,3,5-Trimethylcyclohexa-1,4-
diene, 3,6-dimethylcyclohexa-1,4-diene,38,39 and [(η6-arene)-
RuCl2]239 were synthesized by literature procedures. Elemental
1a : 1H NMR (500 MHz, CDCl3, 25 °C) δ 7.81 (m, 4H, Hm),
2
3
7.45 (m, 6H, Ho, Hp), 6.75 (ddd, J (PH) ) 24.5 Hz, J (HaHb) )
(38) Birch, A. J . Adv. Org. Chem. 1972, 8, 1.
(39) Bennett, M. A.; Smith, A. K. J . Chem. Soc., Dalton Trans. 1974,
233.
(40) Gagne, R. R.; Koval, C. A.; Lisensky, G. C. Inorg. Chem. 1980,
19, 2854.

Base-Promoted Hydroalkylation Reactions
Organometallics, Vol. 19, No. 17, 2000 3391
18.5 Hz, 3J (HaHc) ) 12.0 Hz, 1H, Ha), 5.91 (ddd, 3J (PH) ) 38.5
Hz, 3J (HaHc) ) 12.0 Hz, 2J (HbHc) ) 1.0 Hz, 1H, Hc), 5.31 (ddd,
3J (PH) ) 19.0 Hz, 3J (HaHb) ) 18.5 Hz, 2J (HbHc) ) 1.0 Hz, 1H,
Hb), 4.71 (s, 3H, CHring), 1.98 (s, 9H, 3CH3); 13C{1H} NMR
at room temperature for 15 min. To this solution was added
ButOK (0.03-0.04 g) and 5 mL of CH3CN. The clear red
solution turned dark red upon addition of the base. The
solution was refluxed for 48 h. Then the solvent was removed
2
(125.7 MHz, CDCl3, 25 °C) δ 134.33 (d, J (PC) ) 9.6 Hz, Co),
on a rotary evaporator. The residue was dissolved in a
2
1
132.57 (d, J (PC) ) 49.0 Hz, Ci), 131.35 (d, J (PC) ) 46.2 Hz,
CR), 130.61 (d, 4J (PC) ) 2.5 Hz, Cp), 128.35 (d, 2J (PC) ) 4.4
Hz, Câ), 128.11 (d, 3J (PC) ) 9.7 Hz, Cm), 103.42 (d, J (PC) )
2.5 Hz, Cring), 85.08 (d, J (PC) ) 4.1 Hz, Cring), 1.98 (s, CH3).
Anal. Calcd for C23H25Cl2PRu (1a ): C, 54.77; H, 4.99; Cl, 14.06.
Found: C, 54.69; H, 4.87; Cl, 13.92.
minimum amount of dichloromethane, and ether was added.
The mixture was then filtered and recrystallized from dichlo-
romethane/ether or dichloromethane/hexane solvent mixtures.
Drying the resulting solid in vacuo gave the pure products as
red crystals (% yield and melting point (°C)): 1b, 70 and 226-
228; 2b, 67 and 190-192; 3b, 48 and 220-222; 4b, 60 and
216-218; 5b, 52 and 198-200.
2a :1H NMR (500 MHz, CDCl3, 25 °C) δ 7.78 (m, 4H, Hm),
2
3
1b:
7.44 (m, 6H, Ho, Hp), 6.96 (ddd, J (PH) ) 25.0 Hz, J (HaHb) )
18.0 Hz, 3J (HaHc) ) 12.0 Hz, 1H, Ha), 5.92 (ddd, 3J (PH) ) 38.0
Hz, 3J (HaHc) ) 12.0 Hz, 2J (HbHc) ) 1.0 Hz, 1H, Hc), 5.17 (ddd,
3J (PH) ) 18.0 Hz, 3J (HaHb) ) 18.0 Hz, 2J (HaHc) ) 1.0 Hz, 1H,
3
Hb), 5.25 (m, 4H, CHring), 2.58 (septet, J (HH) ) 7.0 Hz, 1H,
3
CH), 1.87 (s, 3H, CH3), 0.93 (d, J (HH) ) 7.0 Hz, 6H, 2CH3);
2
13C{1H} NMR (125.7 MHz, CDCl3, 25 °C) δ 133.73 (d, J (PC)
) 9.0 Hz, Co), 132.85 (d, 1J (PC) ) 46.8 Hz, Ci), 131.05 (d, 1J (PC)
) 49.1 Hz, CR), 130.56 (d, 4J (PC) ) 2.4 Hz, Cp), 129.96 (d,
3
2J (PC) ) 4.5 Hz, Câ), 128.19 (d, J (PC) ) 9.8 Hz, Cm), 108.73
1H NMR (500 MHz, CDCl3, 25 °C) δ 7.59 (m, 4H, Ho), 7.33 (m,
(d, J (PC) ) 1.3 Hz, Cring) 94.92 (s, Cring), 89.24 (d, J (PC) ) 4.1
Hz, Cring), 85.87 (d, J (PC) ) 5.8 Hz, Cring), 30.03 (s, CH), 21.49
(s, 2CH3), 17.39 (s, CH3). Anal. Calcd for C24H27Cl2PRu (2a ):
C, 55.60; H, 5.25; Cl, 13.68. Found: C, 55.35; H, 5.18; Cl, 13.54.
3a : 1H NMR (500 MHz, CDCl3, 25 °C) δ 7.77 (m, 4H, Hm),
4
2H, Hp), 7.28 (m, 4H, Hm), 5.79 (s, 1H, H4), 4.67 (t, J (HH) )
1.5 Hz, 2H, H2,6), 2.49 (m, 2H, Hc), 2.46 (m, 2H, Ha), 2.27 (s,
6H, H7,8), 2.04 (appdquin, 3J (PH) ) 23.0 Hz, 3J (HH) ) 5.0 Hz,
2H, Hb); 13C{1H} NMR (125.7 MHz, CDCl3, 25 °C) δ 133.66 (d,
1
2J (PC) ) 8.7 Hz, Co), 132.81 (d, J (PC) ) 48.1 Hz, Ci), 130.00
2
3
7.43 (m, 6H, Ho, Hp), 6.79 (ddd, J (PH) ) 25.0 Hz, J (HaHc) )
(d, 4J (PC) ) 1.8 Hz, Cp), 127.63 (d, 3J (PC) ) 10.1 Hz, Cm),
104.65 (d, J (PC) ) 3.8 Hz, C1), 98.33 (d, J (PC) ) 12.1 Hz, C4),
3
3
18.0 Hz, J (HaHb) ) 12.5 Hz, 1H, Ha), 5.77 (dd, J (PH) ) 37.2
3
3
Hz, J (HaHb) ) 12.5 Hz, 1H, Hc), 5.28 (dd, J (PH) ) 18.0 Hz,
3
90.5 (d, J (PC) ) 0.9 Hz, C3,5), 80.3 (s, C2,6), 30.44 (d, J (PC) )
3J (HaHb) ) 18.0 Hz, 1H, Hb), 1.78 (s, 18H, CH3); 13C{1H} NMR
1
2
2.0 Hz, Cc), 23.00 (d, J (PC) ) 30.3 Hz Ca), 20.22 (d, J (PC) )
1.8 Hz, Cb), 18.01 (s, C7,8). Anal. Calcd for C23H25Cl2PRu (1b):
C, 54.77; H, 4.99; Cl, 14.06. Found: C, 54.64; H, 4.91; Cl, 13.86.
2b:
2
(125.7 MHz, CDCl3, 25 °C) δ 134.82 (d, J (PC) ) 9.2 Hz, Co),
Ci unresolved, 130.40 (d, 1J (PC) ) 50.0 Hz, CR), 130.29 (d,
2
4J (PC) ) 2.3 Hz, Cp), 128.63 (d, J (PC) ) 12.1 Hz, Câ), 127.91
(d, 3J (PC) ) 9.7 Hz, Cm), 96.15 (d, J (PC) ) 3.3 Hz, Cring), 15.17
(s, CH3). Anal. Calcd for C26H31Cl2PRu (3a ): C, 57.14; H, 5.72;
Cl, 12.97. Found: C, 57.02; H, 5.57; Cl, 12.68.
4a : 1H NMR (500 MHz, CDCl3, 25 °C) δ 7.80 (m, 4H, Hm),
3
3
7.45 (m, 6H, Ho, Hp), 6.90 (ddd, J (PH) ) 25.0 Hz, J (HaHb) )
18.5 Hz, 3J (HaHc) ) 12.3 Hz, 1H, Ha), 5.95 (ddd, 3J (PH) ) 26.5
Hz, 3J (HaHc) ) 12.0 Hz, 2J (HbHc) ) 1.0 Hz, 1H, Hc), 5.30
(ddd,3J (PH) ) 19.0 Hz, 3J (HaHb) ) 18.5 Hz, 2J (HbHc) ) 1.0
Hz, 1H, Hb), 5.16 (d, J (PH) ) 1.0 Hz, 4H, CHring), 1.85 (s, 6H,
2CH3); 13C{1H} NMR (125.7 MHz, CDCl3, 25 °C) δ 133.76 (d,
1H NMR (500 MHz, CDCl3, 25 °C) δ 7.61 (m, 4H, Ho), 7.34 (m,
2H, Hp), 7.31 (m, 4H, Hm), 5.48 (d, 3J (HH) ) 6.0 Hz, 2H, H3,5),
5.05 (dd, 3J (HH) ) 6.0 Hz, J (PH) ) 1.5 Hz, 2H, H2,6), 3.21
(septet, 3J (HH) ) 7.0 Hz, 1H, H7), 2.59 (t, 3J (HH) ) 5.5 Hz,
2H, Hc), 2.57 (dt, 2J (PH) ) 12.0 Hz, 3J (HH) ) 4.5 Hz, 2H, Ha),
2.15 (dtt, 3J (PH) ) 23.0 Hz, 3J (HH) ) 5.5 Hz, 3J (HH) ) 4.5
Hz, 2H, Hb), 1.39 (d, 3J (HH) ) 7.0 Hz, 6H, H8,9); 13C{1H} NMR
1
2J (PC) ) 9.3 Hz, Co), 132.73 (d, J (PC) ) 47.3 Hz, Ci), 131.08
(d, 1J (PC) ) 49.3 Hz, CR), 130.67 (d, 4J (PC) ) 2.3 Hz, Cp),
129.76 (d, 2J (PC) ) 4.7 Hz, Câ), 128.28 (d, 3J (PC) ) 9.8 Hz,
Cm), 95.99 (s, Cring), 89.71 (d, J (PC) ) 5.0 Hz, CHring), 17.52 (s,
2C, 2CH3). Anal. Calcd for C22H23Cl2PRu (4a ): C, 53.88; H,
4.73; Cl, 14.46. Found: C, 53.69; H, 4.67; Cl, 14.38.
5a : 1H NMR (500 MHz, CDCl3, 25 °C) δ 7.75 (m, 4H, Hm),
2
(125.7 MHz, CDCl3, 25 °C) δ 133.82 (d, J (PC) ) 8.5 Hz, Co),
2
3
1
4
7.46 (m, 6H, Ho, Hp), 6.83 (ddd, J (PH) ) 25.0 Hz, J (HaHb) )
132.17 (d, J (PC) ) 48.6 Hz, Ci), 130.14 (d, J (PC) ) 2.6 Hz,
Cp), 127.79 (d, 3J (PC) ) 9.9 Hz, Cm), 122.34 (d, J (PC) ) 9.3
Hz, C1), 87.32 (s, C4), 86.79 (s, C3,5), 84.16 (s, C2,6), 30.78 (s,
C7), 30.12 (d, 3J (PC) ) 0.6 Hz, Cc), 22.70 (d, 1J (PC) ) 31.0 Hz,
3
3
18.5 Hz, J (HaHc) ) 12.5 Hz, 1H, Ha), 5.99 (dd, J (PH) ) 39.0
3
3
Hz, J (HaHc) ) 12.5 Hz, 1H, Hc), 5.38 (dd, J (PH) ) 18.5 Hz,
3J (HaHb) ) 18.5 Hz, 1H, Hb), 5.33 (td, 3J (HH) ) 6.0 Hz, 2J (PH)
3
2
) 2.0 Hz, 2H, Hm), 5.19 (d, J (HH) ) 6.0 Hz, 2H, Ho), 4.68 (t,
Ca), 21.70 (s, C8,9), 20.33 (d, J (PC) ) 1.0 Hz, Cb). Anal. Calcd
3J (HH) ) 6.0 Hz, 1H, Hp), 2.16 (s, 3H, CH3); 13C{1H} NMR
for C24H27Cl2PRu (2b): C, 55.60; H, 5.25; Cl, 13.68. Found:
2
(125.7 MHz, CDCl3, 25 °C) δ 133.65 (d, J (PC) ) 9.3 Hz, Co),
C, 55.44; H, 5.22; Cl, 13.61.
3b:
1
1
132.73 (d, J (PC) ) 48.6 Hz, Ci), 130.91 (d, J (PC) ) 50.3 Hz,
CR), 130.72 (d, 4J (PC) ) 2.4 Hz, Cp), 129.96 (d, 2J (PC) ) 4.4
Hz, Câ), 128.38 (d, 3J (PC) ) 9.9 Hz, Cm), 108.05 (d, J (PC) )
5.0 Hz, Cring), 88.60 (d, J (PC) ) 1.6 Hz, CHring), 87.85 (d, J (PC)
) 6.2 Hz, CHring), 80.11 (s, CHring), 18.72 (s, CH3). Anal. Calcd
for C21H21Cl2PRu (5a ): C, 52.95; H, 4.44; Cl, 14.88. Found:
C, 52.76; H, 4.25; Cl, 14.67.
P r ep a r a tion s of 1b-5b. Gen er a l P r oced u r e. These
complexes were all prepared by the same general procedure
as follows. A suspension of the [(η6-arene)RuCl2]2 dimer (0.20
g) in 25 mL of CH3CN was purged with dry nitrogen for 15
min, after which diphenylvinylphosphine (0.13-0.17 mL) was
added via syringe, and then the clear red mixture was stirred
1H NMR (500 MHz, CDCl3, 25 °C) δ 7.64 (m, 4H, Ho), 7.30 (m,
3
6H, Hm, Hp), 2.59 (t, J (HH) ) 6.5 Hz, 2H, Hc), 2.43 (m, 2H,
3
Ha), 2.24 (d, J (PH) ) 2.5 Hz, 3H, H9), 2.19 (dquin, J (HH) )

3392 Organometallics, Vol. 19, No. 17, 2000
Ghebreyessus and Nelson
3
4.5 Hz, J (PH) ) 24.0 Hz, 2H, Hb), 2.09 (s, 6H, H8,10), 1.76 (s,
(t, 3J (HH) ) 11.5 Hz, 2H, H2,6), 5.15 (dd, 3J (PH) ) 5.0 Hz,
6H, H7,11); 13C{1H} NMR (125.7 MHz, CDCl3, 25 °C) δ 133.31
3J (HH) ) 3.5 Hz, 2H, H3,5), 2.61 (t, J (HH) ) 6.0 Hz, 2H, Hc),
3
(d, 2J (PC) ) 8.5 Hz, Co), 132.75 (d, J (PC) ) 46.4 Hz, Ci), 129.
2.59 (t, 3J (HH) ) 6.0 Hz, 2H, Ha) 2.23 (dquin, 3J (HH) ) 5.0
Hz, 3J (PH) ) 23.0 Hz, 2H, Hb); 13C{1H} NMR (125.7 MHz,
CDCl3, 25 °C) δ 133.91 (d, 2J (PC) ) 8.4 Hz, Co), 131.87 (d,
1
4
3
58 (d, J (PC) ) 1.9 Hz, Cp), 127.54 (d, J (PC) ) 9.8 Hz, Cm),
106.19 (d, J (PC) ) 10.9 Hz, C1), 101.18 (d, J (PC) ) 4.5 Hz,
C4), 91.55 (s, C3,5), 85.48 (d, J (PC) ) 1.4 Hz, C2,6), 24.91 (d,
4
1J (PC) ) 49.4 Hz, Ci), 130.41 (d, J (PC) ) 2.6 Hz, Cp), 127.97
3J (PC) ) 1.9 Hz, Cc), 22.58 (d, J (PC) ) 3.0 Hz, Cb), 21.66 (d,
(d, 3J (PC) ) 10.2 Hz, Cm), 100.98 (d, J (PC) ) 10.3 Hz, C1),
2
1J (PC) ) 30.7 Hz, Ca), 16.01 (s, C7,11), 15.51 (s, C8,10), 14.88 (d,
J (PC) ) 1.3 Hz, C9). Anal. Calcd for C26H31Cl2PRu (3b): C,
57.14; H, 5.72; Cl, 12.97. Found: C, 57.15; H, 5.60; Cl, 12.73.
4b:
89.75 (s, C4), 88.31 (s, C3,5), 84.48 (s, C2,6), 30.52 (d, J (PC) )
3
1.5 Hz, Cc), 22.67 (d, 1J (PC) ) 31.3 Hz, Ca), 20.26 (d, 2J (PC) )
1.3 Hz, Cb). Anal. Calcd for C21H21Cl2PRu (5b): C, 52.95; H,
4.44; Cl, 14.88. Found: C, 52.69; H, 4.28; Cl, 14.71.
X-r a y Da ta Collection a n d P r ocessin g. Crystals of the
complexes, obtained from CH2Cl2/ether mixtures were mounted
on glass fibers coated with epoxy and placed on a Siemens P4
diffractometer. Intensity data were taken in the ω-mode at
298 K with Mo KR graphite-monochromated radiation (λ )
0.710 73 Å). Three check reflections monitored every 100
reflections showed random (<2%) variation during the data
collections. The data were corrected for Lorentz, polarization
effects, and absorption using an empirical model derived from
azimuthal data collections. Scattering factors and corrections
for anomalous dispersion were taken from a standard source.41
Calculations 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 Å.
1H NMR (500 MHz, CDCl3, 40 °C) δ 7.64 (m, 4H, Ho), 7.35 (m,
6H, Hm, Hp), 5.39 (d, 3J (PH) ) 5.5 Hz, 2H, H3,5), 5.06 (d, J (PH)
3
) 5.5 Hz, 2H, H2,6), 2.61 (t, J (HH) ) 6.0 Hz, 2H, Hc), 2.59 (t,
3J (HH) ) 6.0 Hz, 2H, Ha) 2.19 (appdquin, 3J (HH) ) 5.5 Hz,
3J (PH) ) 24.0 Hz, 2H, Hb), 2.44 (s, 3H, H7); 13C{1H} NMR
2
(125.7 MHz, CDCl3, 40 °C) δ 133.81 (d, J (PC) ) 8.5 Hz, Co),
1
4
132.46 (d, J (PC) ) 48.4 Hz, Ci), 130.26 (d, J (PC) ) 1.9 Hz,
Cp), 127.95 (d, 3J (PC) ) 10.1 Hz, Cm), 88.90 (d, J (PC) ) 6.3
Hz, C1), 88.88 (s, C4), 85.59 (s, C3,5), 85.32 (s, C2,6), 30.11 (d,
3J (PC) ) 1.4 Hz, Cc), 22.72 (d, 1J (PC) ) 31.7 Hz, Ca), 20.55 (d,
2J (PC) ) 0.88 Hz, Cb), 18.43 (s, C7). Anal. Calcd for C22H23
-
Ack n ow led gm en t. This research was supported by
an award from the Research Corp., for which we are
grateful.
Cl2PRu (4b): C, 53.88; H, 4.73; Cl, 14.46. Found: C, 53.72; H,
4.65; Cl, 14.22.
5b:
Su p p or tin g In for m a tion Ava ila ble: Structural drawings
of 4b and 5b and tables of crystal data and structure
refinement, atomic coordinates, isotropic and anisotropic
displacement parameters, bond lengths and angles, and
hydrogen coordinates for 4a , 1b, 2b, 4b, and 5b. This material
is available free of charge via the Internet at http://pubs.acs.org.
OM000375T
1H NMR (500 MHz, CDCl3, 25 °C) δ 7.63 (m, 4H, Ho), 7.38 (m,
2H, Hp), 7.32 (m, 4H, Hm) 6.40 (t, J (HH) ) 11.5 Hz, H4), 5.78
(41) International Tables for X-ray Crystallography; D. Reidel:
Boston, MA, 1992; Vol. C.
3