Synthesis and second-order NLO properties of donor - Acceptor σ-alkenyl ruthenium complexes

Article abstract of DOI:10.1021/om0605736

The compounds p-R-C₆H₄-CH=CH-C≡C-TMS (R = NO₂, N(CH₃)₂, OCH₃) were obtained from Wittig olefination of TMS-C≡C-CH₂PPh₃Br with p-R-C₆H₄-CHO in THF

Full text of DOI:10.1021/om0605736

196
Organometallics 2007, 26, 196-200
Synthesis and Second-Order NLO Properties of Donor-Acceptor
σ-Alkenyl Ruthenium Complexes
Ping Yuan,† Jun Yin,† Guang-ao Yu,† Quanyuan Hu,*,‡ and Sheng Hua Liu*,†,§
Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, College of Chemistry,
Central China Normal UniVersity, Wuhan 430079, People’s Republic of China, Ministry-of-Education,
Key Laboratory for the Synthesis and Application of Organic Functional Molecules, Hubei UniVersity,
Wuhan 430062, People’s Republic of China, and State Key Laboratory of Structural Chemistry, Fujian
Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002,
People’s Republic of China
ReceiVed June 29, 2006
The compounds p-R-C6H4-CHdCH-CtC-TMS (R ) NO2, N(CH3)2, OCH3) were obtained from
Wittig olefination of TMS-CtC-CH2PPh3Br with p-R-C6H4-CHO in THF, which can be desilylated
to give p-R-C6H4-CHdCH-CtC-H. Treatment of RuHCl(CO)(PPh3)3 with p-R-C6H4-CHdCH-
CtC-H produced RuCl(CO)(PPh3)2(CHdCH-CHdCH-C6H4-R-p). The later complexes reacted with
4-phenylpyridine (PhPy), 2,6-(Ph2PCH2)2C5H3N (PMP), and KTp (Tp ) hydridotris(pyrazolyl)borate)
to give RuCl(CO)(PhPy)(PPh3)2 (CHdCH-CHdCH-C6H4-R-p), RuCl(CO)(PMP)(CHdCH-CHdCH-
C6H4-R-p), and RuTp(CO)(PPh3) (CHdCH-CHdCH-C6H4-R-p), respectively. The structure of RuTp-
(CO)(PPh3)(CHdCH-CHdCH-C6H4-R-p) (R ) N(CH3)2, 7b) has been confirmed by X-ray diffraction.
The NLO properties (hyper-Rayleigh scattering measurements) of the complexes 5, 6, and 7 reveal that
changes induced in the ligands of ruthenium (5a-7a or 5b,6b) have a large impact on the
hyperpolarizability.
ties, previously reported examples of “push-pull” σ-alkenyl
complexes are limited,7 maybe because of synthesis difficulties.
In this paper, we report some novel σ-alkenyl complexes with
NLO properties, in which the ruthenium end-group and donor-
or acceptor-substituted phenyl are connected by a CHdCH-
CHdCH bridge. The ruthenium end-group behaves more like
an electron-rich group due to the coordinated P’s or N’s lone
electron pairs, though this effect is weakened by the strong
π-acceptor CO. As a result, when R ) NO2 on the other end of
the conjugated bridge, â0 is much larger than when R ) N(CH3)2
or OCH3. The present study focuses on the synthesis, structural
characterization, and NLO properties of these complexes.
Introduction
Synthesis of new organic and organometallic “push-pull”
molecules with NLO properties has been intensively pursued
in resent years due to their potential applications in optoelec-
tronics, telecommunications, and optical storage devices.1 Metal
(organometallic and coordination) complexes are attracting
considerable interest.2,3 Compared to organic molecules, they
offer a larger variety of molecular structures, the possibility of
high environmental stability, and a diversity of electronic
properties by virtue of the coordinated metal center.4 Among
them, metallocenyl and σ-alkynyl complexes command the most
attention. Compared with metallocenyl complexes, σ-multiple-
bond complexes incorporate the metal in the same plane as the
π-conjugated system, which has been suggested to enhance the
NLO response.5,6 Although alkenes tend to be more hyperpo-
larizable than alkynes, as already stated for the solvochromici-
Results and Discussion
Synthesis of Metal Complexes. The general synthetic route
for the preparation of “push-pull” σ-alkenyl complexes is
outlined in Scheme 1. The compounds p-R-C6H4-CHdCH-
CtC-TMS (R ) NO2, N(CH3)2, OCH3) (2) were obtained
from Wittig olefination of TMS-CtC-CH2PPh3Br with p-R-
C6H4-CHO in THF. Like most Wittig reactions, the product
was obtained as a mixture of E and Z isomers, which could not
be completely separated by chromatography. Treatment of 2
with n-Bu4NF in THF produced compounds p-R-C6H4-CHd
CH-CtC-H (R ) NO2, N(CH3)2, OCH3) (3), which were
purified by recrystallization. Compounds 3 were characterized
by NMR spectroscopy.
* Corresponding authors. E-mail: chshliu@mail.ccnu.edu.cn.
† Central China Normal University.
‡ Hubei University.
§ Fujian Institute of Research on the Structure of Matter.
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10.1021/om0605736 CCC: $37.00 © 2007 American Chemical Society
Publication on Web 12/07/2006

Donor-Acceptor σ-Alkenyl Ruthenium Complexes
Organometallics, Vol. 26, No. 1, 2007 197
Scheme 1
Compounds 3 reacted with RuHCl(CO)(PPh3)3 to give the
insertion products RuCl(CO)(PPh3)2(CHdCH-CHdCH-C6H4-
R-p) (R ) NO2, N(CH3)2, OCH3) (4), which could be isolated
as a solid (4a, purple; 4b, brown; 4c, red). These compounds
have been characterized by NMR. The 31P NMR spectrum in
CD2Cl2 of complex 4a showed a singlet at 31.23 ppm, which
is slightly downfield from that for complexes 4b (30.94 ppm)
and 4c (30.98 ppm) due to the electron acceptance effect of
NO2. These are typical for RuCl((E)-CHdCHR)(CO)(PPh3)2.8
The 1H NMR spectrum in CD2Cl2 of complex 4a displayed the
Ru-CH signal at 8.60 ppm (4b, 7.90; 4c, 7.76), the chemical
shift of which is similar to those of complexes [RuCl(CO)-
(PPh3)2]2(µ-(CHdCH)n)9 and [RuCl(CO)(PPh3)2]2(µ-CHdCH-
Ar-CHdCH),10 and the five-coordinated complexes 4 are air-
sensitive especially in solution.
PMP complexes, for example RuCl2(PPh3)(PMP) and RuHX-
(PPh3)(PMP) (X ) Cl, OAc),12 have also been reported.
Homonuclear bimetallic complexes [RuCl(PhPy)(CO)(PPh3)2]2-
(µ-(CHdCH)n) (n ) 3, 4), [RuCl(CO)(PMP)]2(µ-(CHdCH)n)
(n ) 3, 4),9b,c and [RuTp(CO)(PPh3)]2(µ-(CHdCH)2-C6H4-
(CHdCH)2)13 and heteronuclear bimetallic complexes Fc(CHd
CH)3RuCl(CO)(PhPy)(PPh3)2, Fc(CHdCH)3RuCl(CO)(PMP),
and Fc(CHdCH)3RuTp(CO)(PPh3)14 were also reported. The
structure of 7b has been confirmed by X-ray diffraction study
(Figure 1).
Crystal Structure of Complex RuTp(CO)(PPh3)(CHd
CH-CHdCH-C6H4-N(CH3)2-p) (7b). The molecular struc-
ture of RuTp(CO)(PPh3)(CHdCH-CHdCH-C6H4-N(CH3)2-
p) (7b) is depicted in Figure 1. The crystallographic details and
selected bond distances and angles are given in Tables 1 and 2,
respectively. The ruthenium center is a distorted octahedron with
Tp occupying three coordinational points. It is worth noting that
the vinyl groups are essentially coplanar with Ru-CO. Thus
Ru(1), C(40), O(1), C(1), and C(2) form a plane with maximum
deviation from the least-squares plane of 0.0105 Å for C(1).
This coplanar phenomenon of the vinyl group and CO is
expected due to the strong π-interaction between CO and vinyl
with metal centers in such a conformation.15 The Ru-N(1) bond
(2.194(3) Å) of complex 7b is slightly longer than the Ru-
N(2) bond (2.125(3) Å) and Ru-N(3) bond (2.154 Å), due to
the strong trans influence of the vinyl ligand.16 The (CH)4 unit
Several related six-coordinated complexes were prepared from
complex 4. Reaction of 4 with 4-phenylpyridine (PhPy), 2,6-
(Ph2PCH2)2C5H3N (PMP), and KTp (Tp ) hydridotris(pyra-
zolyl) borate) gave the corresponding six-coordinated complexes
RuCl(CO)(PhPy)(PPh3)2(CHdCH-CHdCH-C6H4-R-p) (R )
NO2, N(CH3)2, OCH3) (5), RuCl(CO)(PMP)(CHdCH-CHd
CH-C6H4-R-p) (R ) NO2, N(CH3)2, OCH3) (6), and RuTp-
(CO)(PPh3)(CHdCH-CHdCH-C6H4-R-p)(R)NO2,N(CH3)2,
OCH3) (7), respectively. These complexes have been character-
ized by NMR spectroscopy. Closely related mononuclear
complexes RuCl(CHdCHR)(L)(CO)(PPh3)2 (L ) 2e nitrogen
donor ligands) have been previously prepared from the reaction
of HCtCR with RuHCl(L)(CO)(PPh3)2.11 A few ruthenium
(11) (a) Torres, M. R.; Vegas, A.; Santos, A.; Ros, J. J. Organomet.
Chem. 1986, 309, 169. (b) Santos, A.; Lo´pez, J.; Gala´n, A.; Gonza´lez, J.
J.; Tinono, P.; Echavarren, A. M. Organometallics 1997, 16, 3482. (c)
Romereo, A.; Santos, A.; Lo´pez, J.; Echavarren, A. M. J. Organomet. Chem.
1990, 391, 219.
(8) Torres, M. R.; Vegas, A.; Santos, A.; Ros, J. J. Organomet. Chem
1986, 309, 169.
(9) (a) Xia, H. P.; Yeung, R. C. Y.; Jia, G. Organometallics 1998, 17,
4762. (b) Liu, S. H.; Xia, H. P.; Wen, T. B.; Zhou, Z. Y.; Jia, G.
Organometallics 2003, 22, 737. (c) Liu, S. H.; Chen, Y. H.; Wan, K. L.;
Wen, T. B.; Zhou, Z. Y.; Lo, M. F.; Williams, I. D.; Jia, G. Organometallics
2002, 21, 4984. (d) Liu, S. H.; Hu, Q. Y.; Xue, P.; Wen, T. B.; Williams,
I. D.; Jia, G. Organometallics 2005, 24, 769.
(10) (a) Go´mez-Lor, B.; Santos, A.; Ruiz, M.; Echavarren, A. M. Eur.
J. Inorg. Chem. 2001, 2305. (b) Jia, G.; Wu, W. F.; Yeung, R. C. Y.; Xia,
H. P. J. Organomet. Chem. 1997, 539, 53. (c) Santos, A.; Lo´pez, J.;
Montoya, J.; Noheda, P.; Romero, A.; Echavarren, A. M. Organometallics
1994, 13, 3605.
(12) (a) Jia, G.; Lee, H. M.; Williams, I. D.; Lau, C. P.; Chem, Y.
Organometallics 1997, 16, 3941. (b) Rahmouni, N.; Osborn, J. A.; Decian,
A.; Fischer, J.; Ezzamarty, A. Organometallics 1998, 17, 2470, and
references therein.
(13) Liu, S. H.; Xia, H. P.; Wan, K. L.; Yeung, R. C. Y.; Hu, Q. Y.; Jia,
G. J. Organomet. Chem. 2003, 683, 331.
(14) Yuan, P.; Liu, S. H.; Xiong, W.; Yin, J.; Yu, G.; Sung, H. Y.;
Williams, I. D.; Jia, G. Organometallics 2005, 24, 1452.
(15) Choi, S. H.; Bytheway, I.; Lin, Z.; Jia, G. Organometallics 1998,
17, 3974.
(16) Coe, B. J.; Glenwright, S. J. Coord. Chem. ReV. 2000, 203, 5.

198 Organometallics, Vol. 26, No. 1, 2007
Yuan et al.
Table 2. Selected Bond Lengths and Bond Angles of
Complex 7b
Bond Lengths (Å)
Ru(1)-C(40)
Ru(1)-C(1)
Ru(1)-N(2)
Ru(1)-N(3)
Ru(1)-N(1)
Ru(1)-P(1)
B(1)-N(5)
B(1)-N(6)
1.817(5)
B(1)-N(4)
B(1)-H(1)
O(1)-C(40)
C(1)-C(2)
C(2)-C(3)
C(3)-C(4)
C(4)-C(5)
1.538(6)
1.04(4)
2.049(4)
2.125(3)
2.154(3)
2.194(3)
2.3455(9)
1.521(6)
1.528(6)
1.139(5)
1.209(7)
1.449(6)
1.361(7)
1.538(8)
Bond Angles (deg)
C(40)-Ru(1)-C(1)
C(1)-Ru(1)-N(2)
C(1)-Ru(1)-N(3)
C(40)-Ru(1)-N(1)
N(2)-Ru(1)-N(1)
C(40)-Ru(1)-P(1)
N(2)-Ru(1)-P(1)
N(1)-Ru(1)-P(1)
C(1)-C(2)-C(3)
C(3)-C(4)-C(5)
C(6)-C(5)-C(4)
92.7(2)
C(40)-Ru(1)-N(2)
90.33(16)
87.33(15) C(40)-Ru(1)-N(3) 175.18(15)
86.2(2)
Figure 1. Molecular structure of RuTp(CO)(PPh3)(CHdCH-CHd
CH-C6H4-N(CH3)2) (7b).
N(2)-Ru(1)-N(3)
84.93(12)
167.50(18)
84.64(11)
93.95(13)
92.50(9)
95.71(18) C(1)-Ru(1)-N(1)
83.44(11) N(3)-Ru(1)-N(1)
92.26(13) C(1)-Ru(1)-P(1)
177.05(9)
94.90(8)
131.2(7)
128.3(6)
114.7(5)
Table 1. Crystal Data and Structure Refinement for
Compound 7b
N(3)-Ru(1)-P(1)
O(1)-C(40)-Ru(1) 176.6(4)
formula
fw
C40H39BN7OPRu
776.63
C(4)-C(3)-C(2)
C(10)-C(5)-C(4)
130.1(6)
122.2(6)
temperature, K
wavelength, Å
cryst syst
space group
a, Å
293(2)
0.71073
monoclinic
P2(1)/c
Table 3. HRS Results at a Wavelength of 1500 nm for
Complexes 5-7a
13.4803(9)
ꢀ (×104
â(1500)
â0 (×10-30
b, Å
14.9598(9)
M-1 cm-1
)
(×10-30 esu)
esu)
c, Å
18.767(1)
complex
λ
max (nm)
R, deg
90
98.342(1)
90
3744.6(4)
5a
6a
7a
5b
6b
463
472
472
346
348
5.13
4.70
3.17
2.01
5.22
689
860
698
84
386
469
380
63
â, deg
γ, deg
V, Å3
Z
d
4
40
29
calc, g cm-3
1.378
a Using external reference method (ERM) to calculate the â1500 values.
Disperse Red 1 as reference, â1500(DR1) ) 30.2 × 10-30 esu. HRS
experiments were operated according to the literature, except that the RG715
filter was replaced by a RG9 filter before collecting the HRS signals. The
value of â0 was extrapolated from the value of â1500 according to the two-
level model. References: see HRS experiment.
θ range, deg
abs coeff, mm-1
F(000)
1.75 to 25.50
0.503
1600
-10 e h e 16,
-18 e k e 17,
-22 e l e 22
3876
index ranges, deg
no. of reflns
no. of ind reflns
19 169/6928 [R(int) ) 3.23%]
MLCT transition.5,17 Within the series studied, changes induced
in the ligands of ruthenium (5a-7a or 5b,6b) have a large
impact on the hyperpolarizability, and introduction of an
acceptor group, such as NO2, results in an increase in â and â0.
For this series of complexes, increasing â is not correlated with
no. of data/restraints/params
final R indices [I > 2σ(I)]
goodness of fit
6928/0/464
R1 ) 0.0497, wR2 ) 0.1202
1.047
0.990
largest diff peak, e Å-3
largest diff hole, e Å-3
-0.436
a red-shift in λmax
.
shows a single/double alternation pattern of carbon-carbon
bonds. Both of the olefinic double bonds are in trans geometry.
The Ru-C(1) bond is 2.049(4) Å, and the bond length of C-C
in the C(1)-C(2)-C(3)-C(4)-C(5) chain is 1.209(7), 1.449-
(6), 1.361(7), and 1.538(8) Å in turn, which shows that in
complex 7b the length of single bonds and double bonds all
increase with the increasing of their distance from the ruthenium
center.
Summary
We have successfully prepared donor-acceptor σ-alkenyl
ruthenium complexes with conjugated side chains by insertion
reaction of RuHCl(CO)(PPh3)3 and p-R-C6H4-CHdCH-Ct
CH. The structure of RuTp(CO)(PPh3)(CHdCH-CHdCH-
C6H4-N(CH3)2-p) (7b) has been confirmed by X-ray diffraction.
The NLO properties (hyper-Rayleigh scattering measurements)
of complexes 5, 6, and 7 reveal that changes induced in the
ligands of ruthenium (5a-7a or 5b,6b) have a large impact on
the hyperpolarizability.
NLO Properties of Metal Complexes. The molecular
second-order nonlinearities for complexes 5-7 as determined
by the hyper-Rayleigh scattering (HRS) technique are given in
Table 3. The HRS experiments were carried out in chloroform
solutions of the complexes at 1500 nm fundamental wavelength.
Some of them, such as 7b, 5c, 6c, and 7c, are absent in this
table, since their signals are too weak to be examined. Changes
of the ligands of the ruthenium end-group leads to no obviously
change in λmax, but replacing the other end-group from NO2 to
N(CH3)2 in proceeding from 5a to 5b or 6a to 6b results in a
Experimental Section
All manipulations were carried out at room temperature under a
nitrogen atmosphere using standard Schlenk techniques, unless
otherwise stated. Solvents were distilled under nitrogen from sodium
benzophenone (hexane, diethyl ether, THF, benzene) or calcium
blue-shift in λmax
.
(17) (a) Whittall, I. R.; McDonagh, A. M.; Humphrey, M. G.; Samoc,
M. AdV. Organomet. Chem. 1998, 42, 291. (b) Whittall, I. R.; Humphrey,
M. G.; Houbrechts, S.; Persoons, A. Organometallics 1996, 15, 1935. (c)
Verbiest, T.; Houbrechts, S.; Kauranen, M.; Clays, K.; Persoons, A. J. Mater.
Chem. 1997, 7, 2175.
The second-order nonlinearities for complexes 5a, 6a, and
7a are larger than related metallocenyl complexes since the in-
plane MLCT transition is more efficient than the out-plane

Donor-Acceptor σ-Alkenyl Ruthenium Complexes
Organometallics, Vol. 26, No. 1, 2007 199
hydride (dichloromethane, CHCl3). The starting materials RuHCl-
(CO)(PPh3)3,18 2,6-(Ph2PCH2)2C5H3N (PMP),19 and KTp20 were
prepared according to literature methods. Elemental analyses (C,
H, N) were performed by the Microanalytical Services, College of
55.20 (s, OCH3), 78.40 (s, CtCH), 83.23 (s, CtCH), 104.44 (s,
dC-Ct), 114.08 (s, 2C, CH3OCC2H2C2H2C), 127.63 (s, 2C, CH3-
OCC2H2C2H2C), 128.60 (s, CH3OCC2H2C2H2C), 142.58 (s, C6H4-
CHd), 160.18 (s, CH3OCC2H2C2H2C).
1
Chemistry, CCNU. H, 13C, and 31P NMR spectra were collected
General Synthesis of Complexes RuCl(CO)(PPh3)2(CHd
CHCHdCH-C6H4-R-p) (4). To a suspension of RuHCl(CO)-
(PPh3)3 (0.57 g, 0.60 mmol) in CH2Cl2 (20 mL) was slowly added
a solution of 3 (0.63 mmol) in CH2Cl2 (15 mL). The reaction
mixture was stirred for 30 min to give a red solution. The reaction
mixture was filtered through a column of Celite. The volume of
the filtrate was reduced to ca. 5 mL under vacuum. Addition of
hexane (50 mL) to the residue produced a solid (4a, purple; 4b,
brown; 4c, red), which was collected by filtration, washed with
hexane, and dried under vacuum.
on an American Varian Mercury Plus 400 spectrometer (400 MHz).
1H and 13C NMR chemical shifts are relative to TMS, and 31P NMR
chemical shifts are relative to 85% H3PO4.
General Synthesis of Compounds p-R-C6H4-CHdCHCt
CTMS (2). To a slurry of (3-trimethylsilyl-2-propyl)triphenylphos-
phonium bromide (2.20 g, 5.0 mmol) in THF (50 mL) was added
a 2 M THF solution of NaN(SiMe3)2 (2.5 mL, 5.0 mmol). The
mixture was stirred for 30 min, and then a solution of the aldehyde
p-R-C6H4-CHO (1) (4.7 mmol) in THF (20 mL) was added
slowly. The resulting solution was stirred for another 30 min, and
then water (50 mL) was added. The layers were separated, and the
aqueous layer was extracted with diethyl ether (3 × 50 mL). The
combined organic layers were washed with a saturated aqueous
solution of sodium chloride (2 × 20 mL) and dried over MgSO4,
filtered, and then concentrated under rotary evaporation. The crude
product was purified by column chromatography (silica gel,
eluent: ether/petroleum ether ) 5/95) to give a yellow solid.
2a: Yield: 0.51 g, 45%. Anal. Calcd for C13H15NO2Si: C, 63.64;
4a: Yield: 0.25 g, 48.3%. 31P NMR (160 MHz, CD2Cl2): δ
1
31.23 (s). H NMR (400 MHz, CD2Cl2): δ 5.62 (m, 1H, C6H4-
CHdCH), 5.74 (d, J(HH) ) 15.6 Hz, 1H, Ph-CHd), 6.68 (q,
J(HH) ) 10.8, 15.2 Hz, 1H, C6H4-CHdCH-CHd), 7.03-7.99
(m, 34H, Ph, PPh3), 8.60 (d, J(HH) ) 12.8 Hz, 1H, Ru-CH).
4b: Yield: 0.32 g, 62.0%. 31P NMR(160 MHz, CD2Cl2): δ 30.94
1
(s). H NMR (400 MHz, CD2Cl2): δ 2.80 (s, 6H, N(CH3)2), 5.40
(m, 1H, C6H4-CHdCH), 5.63 (m, 1H, Ph-CHd), 6.20-7.80 (m,
35H, C6H4-CHdCH-CHd, Ph, PPh3), 7.76 (d, J(HH) ) 13.2
Hz, 1H, Ru-H).
4c: Yield: 0.20 g, 39.3%. 31P NMR(160 MHz, CD2Cl2): δ 30.98
(s). 1H NMR (400 MHz, CD2Cl2): δ 3.67 (s, 3H, OCH3), 5.43 (m,
1H, Ph-CHdCH), 5.64 (d, J(HH) ) 15.2 Hz, 1H, C6H4-CHd),
6.37 (q, J(HH) ) 15.2, 10.0 Hz, 1H, C6H4-CHdCH-CHd), 6.69
(m, 2H, CH3OCC2H2C2H2C), 7.10 (m, 2H, CH3OCC2H2C2H2C),
7.20-7.60 (m, 30H, PPh3), 7.90 (d, J(HH) ) 12.8 Hz, 1H, Ru-
H).
1
H, 6.16; N, 5.71. Found: C, 63.28; H, 6.21; N, 5.56. H NMR
(400 MHz, CDCl3): δ 0.23 (s, 9H, SiMe3), 6.33 (d, J(HH) ) 16.0
Hz, 1H, dCHCt), 7.02 (d, J(HH) ) 15.6 Hz, 1H, C6H4-CHd),
7.50 (d, J(HH) ) 8.0 Hz, 2H, O2NCC2H2C2H2C), 8.19 (d, J(HH)
) 8.8 Hz, 2H, O2NCC2H2C2H2C).
2b: Yield: 0.55 g, 48%. Anal. Calcd for C15H21NSi: C, 74.01;
1
H, 8.70; N, 5.75. Found: C, 73.89; H, 8.88; N, 5.60. H NMR
(400 MHz, CDCl3): δ 0.23 (s, 9H, SiMe3), 3.00 (s, 6H, N(CH3)2),
5.98 (d, J(HH) ) 16.0 Hz, 1H, dCHCt), 6.66 (d, J(HH) ) 8.0
Hz, 2H, (CH3)2NCC2H2C2H2C), 6.96 (d, J(HH) ) 16.0 Hz, 1H,
C6H4-CHd), 7.28 (m, 2H, (CH3)2NCC2H2C2H2C).
General Synthesis of Complexes RuCl(CO)(PhPy)(PPh3)2-
(CHdCHCHdCH-C6H4-R-p) (5). A mixture of complex 4
(0.12 mmol) and 4-phenylpyridine (0.03 g, 0.19 mmol) in CH2Cl2
(20 mL) was stirred for 30 min. The solution was filtered through
a column of Celite. The volume of the filtrate was reduced to ca.
2 mL under vacuum. Addition of hexane (15 mL) to the residue
produced a yellow solid, which was collected by filtration, washed
with hexane, and dried under vacuum.
2c: Yield: 0.45 g, 42%. Anal. Calcd for C14H18OSi: C, 72.99;
1
H, 7.88. Found: C, 72.62; H, 8.03. H NMR (400 MHz, CDCl3):
δ 0.23 (s, 9H, SiMe3), 3.82 (s, 3H, OCH3), 6.05 (d, J(HH) ) 16.0
Hz, 1H, dCHCt), 6.88 (m, 2H, CH3OCC2H2C2H2C), 6.97 (d,
J(HH) ) 16.0 Hz, 1H, C6H4-CHd), 7.33 (m, 2H, CH3-
OCC2H2C2H2C).
General Synthesis of Compounds p-R-C6H4-CHdCHCt
CH (3). To a solution of complex 2 (2.0 mmol) in THF (10 mL)
was slowly added a 1 M THF solution of n-Bu4N+F- (2.0 mL, 1
M in THF with 5% water) with stirring. After 2 h, the solvent was
removed. The crude product was purified to give a yellow solid.
3a: Yield: 0.31 g, 90%. Anal. Calcd for C10H7NO2: C, 69.36;
5a: Yield: 0.10 g, 82.0%. Anal. Calcd for C58H47ClN2O3P2Ru:
C, 68.40; H, 4.65; N, 2.75. Found: C, 68.76; H, 4.82; N, 2.47. 31
P
NMR (160 MHz, CD2Cl2): δ 26.75 (s). 1H NMR (400 MHz, CD2-
Cl2): δ 5.65 (d, J(HH) ) 15.6 Hz, 1H, C6H4-CHd), 5.84 (q, J(HH)
) 10.2, 16.2 Hz, 1H, C6H4-CHdCH), 6.72 (br q, J(HH) ) 10.4,
15.2 Hz, 3H, C5H2H2N, C6H4-CHdCH-CHd), 7.04-7.52 (m,
37H, Ph, O2NCC2H2C2H2C), 7.97 (d, J(HH) ) 8.8 Hz, 2H, O2-
NCC2H2C2H2C), 8.39 (br, 2H, C5H2H2N), 9.00 (d, J(HH) ) 15.6
Hz, 1H, Ru-CH).
1
H, 4.07; N, 8.09. Found: C, 69.50; H, 4.21; N, 8.01. H NMR
(400 MHz, CDCl3): δ 3.21 (d, J(HH) ) 2.4 Hz, 1H, tCH), 6.30
(q, J(HH) ) 2.2, 16.6 Hz, 1H, dCHCt), 7.08 (d, J(HH) ) 16.0
Hz, 1H, C6H4-CHd), 7.53 (d, J(HH) ) 8.8 Hz, 2H, O2-
NCC2H2C2H2C), 8.20 (d, J(HH) ) 8.8 Hz, 2H, O2NCC2H2C2H2C).
3b: Yield: 0.30 g, 88%. Anal. Calcd for C12H13N: C, 84.17; H,
5b: Yield: 0.10 g, 82.0%. Anal. Calcd for C60H53ClN2OP2Ru:
C, 70.89; H, 5.26; N, 2.76. Found: C, 71.23; H, 5.01; N, 2.70. 31
P
NMR(160 MHz, CD2Cl2): δ 26.55 (s). 1H NMR (400 MHz, CD2-
Cl2): δ 2.82 (s, 6H, N(CH3)2), 5.54 (d, J(HH) ) 15.6 Hz, 1H,
C6H4-CHd), 5.61 (q, J(HH) ) 9.6, 16.0 Hz, 1H, C6H4-CHd
CH), 6.41 (q, J(HH) ) 9.8, 15.4 Hz, 1H, C6H4-CHdCH-CHd),
6.55 (d, J(HH) ) 8.4 Hz, 2H, (CH3)2NCC2H2C2H2C), 6.70 (br,
2H, C5H2H2N), 6.96-7.54 (m, 37H, Ph, (CH3)2NCC2H2C2H2C),
8.14 (d, J(HH) ) 16.4 Hz, 1H, Ru-CH), 8.40 (br, 2H, C5H2H2N).
1
7.65; N, 8.18. Found: C, 84.02; H, 7.81; N, 7.95. H NMR (400
MHz, CDCl3): δ 2.98 (bs, 7H, N(CH3)2, tCH), 5.90 (q, J(HH) )
2.0, 16.0 Hz, 1H, dCHCt), 6.65 (d, J(HH) ) 8.8 Hz, 2H, (CH3)2-
NCC2H2C2H2C), 6.96 (d, J(HH) ) 16.0 Hz, 1H, C6H4-CHd), 7.28
(d, J(HH) ) 8.8 Hz, 2H, (CH3)2NCC2H2C2H2C).
3c: Yield: 0.29 g, 92%. Anal. Calcd for C11H10O: C, 83.52; H,
1
6.37. Found: C, 83.63; H, 6.50. H NMR (400 MHz, CDCl3): δ
5c: Yield: 0.09 g, 73.8%. Anal. Calcd for C59H50ClNO2P2Ru:
3.02 (d, J(HH) ) 2.4 Hz, 1H, tCH), 3.82 (s, 3H, OCH3), 5.99 (q,
J(HH) ) 2.4, 16.4 Hz, 1H, dCHCt), 6.87 (m, 2H, CH3-
OCC2H2C2H2C), 7.00 (d, J(HH) ) 16.0 Hz, 1H, Ph-CHd), 7.33
(m, 2H, CH3OCC2H2C2H2C). 13C NMR (100 MHz, CDCl3): δ
C, 70.62; H, 5.02; N, 1.40. Found: C, 70.48; H, 5.25; N, 1.28. 31
P
NMR (160 MHz, CD2Cl2): δ 27.27 (s). 1H NMR (400 MHz, CD2-
Cl2): δ 3.72 (s, 3H, OCH3), 5.57 (d, J(HH) ) 16.0 Hz, 1H, Ph-
CHd), 5.65 (m, 1H, C6H4-CHdCH), 6.45 (q, J(HH) ) 10.2, 15.4
Hz, 1H, C6H4-CHdCH-CHd), 6.70 (br d, J(HH) ) 8.8 Hz, 4H,
C5H2H2N, CH3OCC2H2C2H2C), 6.91-7.46 (m, 37H, Ph, CH3-
OCC2H2C2H2C), 8.27 (d, J(HH) ) 16.4 Hz, 1H, Ru-CH), 8.40
(br, 2H, C5H2H2N).
(18) Ahmad, N.; Levison, J. J.; Robinson, S. D.; Uttley, M. F.; Wonchoba,
E. R.; Parshall, G. W. Inorg. Synth. 1974, 15, 45.
(19) Dahlhoff, W. V.; Nelson, S. M. J. Chem. Soc. (A) 1971, 2184.
(20) Trofimenko, S. Inorg. Synth. 1970, 12, 99.

200 Organometallics, Vol. 26, No. 1, 2007
Yuan et al.
General Synthesis of Complexes RuCl(CO)(PMP)(CHd
CHCHdCH-C6H4-R-p) (6). A mixture of complex 4 (0.12
mmol) and PMP (0.06 g, 0.12 mmol) in CH2Cl2 (20 mL) was stirred
for 15 h. The solution was filtered through a column of Celite.
The volumn of the filtrate was reduced to ca. 2 mL under vacuum.
Addition of hexane (20 mL) to the residue produced a yellow solid,
which was collected by filtration, washed with hexane, and dried
under vacuum.
diffraction were grown from a dichloromethane solution layered
with hexane. A crystal was mounted on a glass fiber, and the
diffraction intensity data were collected on a Bruker CCD 4K
diffractometer with graphite-monochromatized Mï KR radiation
(λ ) 0.71073 Å). Lattice determination and data collection were
carried out using SMART version 5.625 software. Data reduction
and absorption corrections were performed using SAINT version
6.45 and SADABS version 2.03. Structure solution and refinement
were performed using the SHELXTL version 6.14 software
package. All non-hydrogen atoms were refined anisotropically. All
hydrogens were included in their idealized positions and refined
using a riding model. Further crystallographic details are sum-
marized in Table 2, and selected bond distances and angles are
given in Table 3.
6a: Yield: 0.09 g, 92.0%. Anal. Calcd for C42H35ClN2O3P2Ru:
C, 62.00; H, 4.33; N, 3.44. Found: C, 62.31; H, 4.50; N, 3.26. 31
P
NMR (160 MHz, CD2Cl2): δ 49.16 (s). 1H NMR (400 MHz,CD2-
Cl2): δ 4.12 (m, 2H, CHH(C5H3N)CHH), 4.51 (m, 2H, CHH-
(C5H3N)CHH), 5.34 (d, J(HH) ) 15.2 Hz, 1H, C6H4-CHd), 5.60
(m, 1H, C6H4-CHdCH), 5.72 (m, 1H, C6H4-CHdCH-CHd),
6.73-8.00 (m, 28H, Ph, C5H3N, Ru-CH).
Hyper-Rayleigh Scattering (HRS) Measurement. Details for
the experiment are similar to the setup described in ref 21. A high-
energy picosecond Nd:YAG laser (Continuum Leopard) provides
35 ps wide pulses of 60 mJ vertically polarized 355 nm radiation
at 10 Hz. The beam was pumped into the optical parameter
amplification (OPA) apparatus and generated a 2-3 mJ idler wave
at 1500 nm. All measurements were carried out in chloroform with
sample concentrations of 10-4 M. Disperse Red 1 (DR1) was used
as reference with a value of â1500(DR1) ) 74 × 10-30 esu.21 DR1
was synthesized and recrystallized from methanol, and the purity
6b: Yield: 0.08 g, 81.8%. Anal. Calcd for C44H41ClN2OP2Ru:
C, 65.06; H, 5.09; N, 3.45. Found: C, 65.34; H, 4.91; N, 3.33. 31
P
NMR (160 MHz, CD2Cl2): δ 49.85 (s). 1H NMR (400 MHz,CD2-
Cl2): δ 2.81 (s, 6H, N(CH3)2), 4.15 (m, 2H, CHH(C5H3N)CHH),
4.53 (m, 2H, CHH(C5H3N)CHH), 5.18-5.33 (m, 2H, C6H4-CHd
, C6H4-CHdCH), 5.43 (q, J(HH) ) 9.4, 15.4 Hz, 1H, C6H4-
CHdCH-CHd), 6.00-7.78 (m, 28H, Ph, C5H3N, Ru-CH).
6c: Yield: 0.08 g, 83.4%. Anal. Calcd for C43H38ClNO2P2Ru:
C, 64.62; H, 4.79; N, 1.75. Found: C, 64.37; H, 4.95; N, 1.87. 31
P
NMR (160 MHz, CD2Cl2): δ 49.42 (s). 1H NMR (400 MHz,CD2-
Cl2): δ 3.63 (s, 3H, OCH3), 4.14 (m, 2H, CHH(C5H3N)CHH), 4.50
(m, 2H, CHH(C5H3N)CHH), 5.21 (d, J(HH) ) 15.4 Hz, 1H, C6H4-
CHd), 5.35 (q, J(HH) ) 9.8, 15.4 Hz, 1H, C6H4-CHdCH), 5.46
(q, J(HH) ) 9.8, 15.0 Hz, 1H, C6H4-CHdCH-CHd), 6.11-7.80
(m, 28H, Ph, C5H3N, Ru-CH).
is proved by H and 13C NMR. Solutions were filtered through a
1
0.2 µm Teflon filter to remove macroscopic particles that may
introduce spurious signals in HRS experiments.
Assuming that the scattering contribution from the solvent is
negligibly small, an external reference method (ERM)22 is used to
calculate the â values of chromophores according to eq 1:
General Synthesis of Complexes RuTp(CO)(PPh3) (CHd
CHCHdCH-C6H4-R-p) (7). A mixture of complex 4 (0.12
mmol) and KTp (0.03 g, 0.13 mmol) in CH2Cl2 (20 mL) was stirred
for 2 h. The solution was filtered through a column of Celite to
remove the KCl. The volume of the filtrate was reduced to ca. 2
mL under vacuum. Addition of hexane (20 mL) to the residue
produced a solid, which was collected by filtration, washed with
hexane, and dried over vacuum.
Sc
2
2
â )
â
x
)
â
x
ref
(1)
c
c
S
x
ref
where S is the slope of the appropriate I2ωversus concentration plot
and âref is the orientational average of the first hyperpolarizability
of the reference sample.
7a: Yield: 0.08 g, 87.0%. Anal. Calcd for C38H33BN7O3PRu:
C, 58.62; H, 4.27; N, 12.59. Found: C, 58.25; H, 4.12; N, 12.75.
Acknowledgment. The authors acknowledge financial sup-
port from National Natural Science Foundation of China (Nos.
20472023, 20572029), New Century Excellent Talents in
University (NCET-04-0743), the Cultivation Fund of the Key
Scientific and Technical Innovation Project, Ministry of Educa-
tion of China (No. 705039), the National Key Project for Basic
Research of China (No. 2004CCA00100), and Program for
Excellent Research Group of Hubei Province (No. 2004ABC002).
1
31P NMR (160 MHz, CD2Cl2): δ 48.92 (s). H NMR (400 MHz,
CD2Cl2): δ 5.84-8.00 (m, 32H, PPh3, CHd, Tp), 8.37 (d, J(HH)
) 16.0 Hz, 1H, Ru-CH).
7b: Yield: 0.08 g, 87.0%. Anal. Calcd for C40H39BN7OPRu:
C, 61.86; H, 5.06; N, 12.62. Found: C, 61.58; H, 5.18; N, 12.28.
1
31P NMR (160 MHz, CD2Cl2): δ 49.49 (s). H NMR (400 MHz,
CD2Cl2): δ 2.81 (s, 6H, N(CH3)2), 5.80-7.67 (m, 33H, PPh3, CHd
, Tp).
Supporting Information Available: This material is available
7c: Yield: 0.08 g, 88.0%. Anal. Calcd for C39H36BN6O2PRu:
C, 61.34; H, 4.75; N, 11.01. Found: C, 61.66; H, 4.58; N, 10.86.
free of charge via the Internet at http://pubs.acs.org.
OM0605736
1
31P NMR (160 MHz, CD2Cl2): δ 49.48 (s). H NMR (400 MHz,
CD2Cl2): δ 3.79 (s, 3H, OCH3), 5.80-7.82 (m, 32H, PPh3, CHd,
Tp), 7.80 (d, J(HH) ) 16.0 Hz, 1H, Ru-CH).
Crystallographic Analysis for RuTp(CO)(PPh3)(CHdCH-
CHdCH-C6H4-N(CH3)2-p) (7b). Crystals suitable for X-ray
(21) Stadler, S.; Dietrich, R.; Bourhill, G.; Bra¨uchle, C.; Pawlik, A.;
Grahn, W. Chem. Phys. Lett. 1995, 247, 271.
(22) Lequan, M.; Branger, C.; Simon, J.; Thami, T.; Chauchard, E.;
Persoons, A. Chem. Phys. Lett. 1994, 229, 101.