Organometallic complexes for nonlinear optics: Part 23. Quadratic and cubic hyperpolarizabilities of acetylide and vinylidene complexes derived from protected and free formylphenylacetylenes

Article abstract of DOI:10.1016/S0022-328X(01)01077-4

The acetylenes 4-HCCC₆H₄R [R=CH{OC(O)Me}₂ (1), CHO(CH₂)₃O (2)], ruthenium complexes [Ru(4-CCC₆H₄R)(PPh₃)₂(η-C ₅H₅)] [R=CH{OC(O)Me}₂ (3), CHO (4)], [Ru(n-C=CHC₆H₄R)Cl(dppm)₂]PF₆ [n=4, R=CHO(CH₂)₃O (7); R=CHO, n=3 (11), 2 (15)], and [Ru(n-CCC₆H₄R)Cl(dppm)₂] [n=4, R=CHO(CH₂)₃O (8); n=3, R=CHO (12)], and gold complexes [Au(n-CCC₆H₄R)(L)] [n=4, R=CHO, L=PPh₃ (5), PMe₃ (6); n=4, R=CHO(CH₂)₃O, L=PPh₃ (9), PMe₃ (10); n=3, R=CHO, L=PPh₃ (13), PMe₃ (14)] have been prepared, and 9 characterized by a single crystal X-ray diffraction study. Electrochemical data for the ruthenium complexes reveal reversible or quasi-reversible (alkynyl complexes) or irreversible (vinylidene complexes) processes assigned to the Ru^II/III couple; the effect on E_1/2 values of the various structural modifications across 3, 4, 7, 8, 11, 12 and 15 are discussed. The molecular quadratic and cubic optical nonlinearities of 1-15 have been determined by the hyper-Rayleigh scattering technique at 1064 nm and the Z-scan technique at 800 nm, respectively; β values increase on increasing the acceptor strength, proceeding from 3-acceptor-substituted to 4-acceptor-substituted arylalkynyl ligand, and an increasing phosphine donor strength, whereas γ values increase on increasing the number of phosphine aryl groups (i.e. increasing delocalization) proceeding from PMe₃ to PPh₃-containing complex.

Full text of DOI:10.1016/S0022-328X(01)01077-4

Journal of Organometallic Chemistry 633 (2001) 114–124
www.elsevier.com/locate/jorganchem
Organometallic complexes for nonlinear opticsꢀ
Part 23. Quadratic and cubic hyperpolarizabilities of acetylide and
vinylidene complexes derived from protected and free
formylphenylacetylenes
Stephanie K. Hurst a, Nigel T. Lucas a, Marie P. Cifuentes a, Mark G. Humphrey a,*,
Marek Samoc b, Barry Luther-Davies b, Inge Asselberghs c, Roel Van Boxel c,
Andre´ Persoons c
a Department of Chemistry, Australian National Uni6ersity, Canberra, Australian Capital Territory 0200, Australia
b Laser Physics Centre, Research School of Physical Sciences and Engineering, Australian National Uni6ersity, Canberra,
Australian Capital Territory 0200, Australia
c Laboratory of Chemical and Biological Dynamics, Centre for Research on Molecular Electronics and Photonics, Uni6ersity of Leu6en,
Celestijnenlaan 200D, B-3001 Leu6en, Belgium
Received 18 April 2001; accepted 20 June 2001
Abstract
¸¹¹¹¹¹¹º
The acetylenes 4-HCꢀCC6H4R [R=CH{OC(O)Me}2 (1), CHO(CH2)3O (2)], ruthenium complexes [Ru(4-CꢀCC6H4R)(PPh3)2-
¸¹¹¹¹¹¹º
(h-C5H5)] [R=CH{OC(O)Me}2 (3), CHO (4)], [Ru(n-CꢁCHC6H4R)Cl(dppm)2]PF6 [n=4, R=CHO(CH2)3O (7); R=CHO,
¸¹¹¹¹¹¹º
n=3 (11), 2 (15)], and [Ru(n-CꢀCC6H4R)Cl(dppm)2] [n=4, R=CHO(CH2)3O (8); n=3, R=CHO (12)], and gold complexes
¸¹¹¹¹¹¹º
[Au(n-CꢀCC6H4R)(L)] [n=4, R=CHO, L=PPh3 (5), PMe3 (6); n=4, R=CHO(CH2)3O, L=PPh3 (9), PMe3 (10); n=3,
R=CHO, L=PPh3 (13), PMe3 (14)] have been prepared, and 9 characterized by a single crystal X-ray diffraction study.
Electrochemical data for the ruthenium complexes reveal reversible or quasi-reversible (alkynyl complexes) or irreversible
(vinylidene complexes) processes assigned to the RuII/III couple; the effect on E1/2 values of the various structural modifications
across 3, 4, 7, 8, 11, 12 and 15 are discussed. The molecular quadratic and cubic optical nonlinearities of 1–15 have been
determined by the hyper-Rayleigh scattering technique at 1064 nm and the Z-scan technique at 800 nm, respectively; i values
increase on increasing the acceptor strength, proceeding from 3-acceptor-substituted to 4-acceptor-substituted arylalkynyl ligand,
and an increasing phosphine donor strength, whereas k values increase on increasing the number of phosphine aryl groups (i.e.
increasing delocalization) proceeding from PMe3 to PPh3-containing complex. © 2001 Published by Elsevier Science B.V.
Keywords: Ruthenium; Gold; Hyperpolarizability; Acetylide; Vinylidene; Electrochemistry; X-ray structure
1. Introduction
focused on nitroarylalkynyl complexes, for which sig-
nificant quadratic and cubic NLO coefficients have
been observed. Replacing the strong nitro acceptor by
an aldehyde functionality would be expected to reduce
nonlinearities, but would provide a functional group
which could be utilized to build more extended struc-
tures. Our attention has therefore recently turned to
formylphenylalkynyl ligands. We report herein synthe-
ses of a range of vinylidene and alkynyl complexes
containing such ligands, synthetic procedures to pre-
pare and introduce 1,3-dioxane and geminal diacetate-
protected formyl groups onto such ligands, and studies
The optical nonlinearities of organometallic com-
plexes have commanded significant recent interest [2–
4]. The particular target of our nonlinear optical (NLO)
studies has been ruthenium and gold acetylide com-
plexes [5–17], but our previous reports have largely
ꢀ Part 22: see Ref. [1].
* Corresponding author. Tel.: +61-2-6125-2927; fax: +61-2-6125-
0760.
E-mail address: mark.humphrey@anu.edu.au (M.G. Humphrey).
0022-328X/01/$ - see front matter © 2001 Published by Elsevier Science B.V.
PII: S0022-328X(01)01077-4

S.K. Hurst et al. / Journal of Organometallic Chemistry 633 (2001) 114–124
115
[19]. The identities of 1 and 2 were confirmed by IR,
UV–vis and 1H-NMR spectroscopy, mass spectrometry
(including accurate mass determinations of the molecu-
lar ion signal), and satisfactory microanalyses.
2.2. Synthesis and characterization of |-acetylide and
6inylidene complexes
The synthetic methodologies used in the preparation
of the new complexes are adaptations of those utilized
successfully in the preparation of the corresponding
phenylacetylides. The bis{bis(diphenylphosphino)-
methane}ruthenium complexes were prepared by ex-
tending the method of Touchard et al. [20], a procedure
which also permits the isolation of the stable vinylidene
intermediates; we have previously utilized this proce-
dure to prepare the corresponding 4-formylphenyl-eth-
ynyl and -vinylidene complexes [1] (Scheme 2). The
behavior of the 2-formylphenylvinylidene complex 15
was markedly different, with attempted deprotonation
resulting in decomposition. Unlike the analogous trans-
[Ru(4-CꢀCC6H4CHO)Cl(dppm)2], it did not prove pos-
sible to prepare [Ru(4-CꢀCC6H4CHO)(PPh3)2(h-C5H5)]
by the most direct route, namely reaction of [RuCl-
(PPh3)2(h-C5H5)] with 4-HCꢀCC6H4CHO followed by
basic work-up; only decomposition products were ob-
served. Access to the 4-formylphenylethynyl complex
necessitated the preparation of a complex with a pro-
tected formyl group. The (cyclopentadienyl)bis(tri-
phenylphosphine)ruthenium acetylide complex 3,
containing a protected formyl group, was prepared in
good yield by the reaction of 1 with [RuCl(PPh3)2(h-
C5H5)] and deprotonation of the intermediate vinyli-
dene complex. Deprotection of 3 by extended treatment
with base afforded the formylphenylethynyl complex 4
in good yield (Scheme 3). Gold acetylide complexes
containing 3-formyl, 4-formyl or 4-(1,3-dioxane) sub-
stituents at the phenylethynyl ligand were prepared
Scheme 1. Syntheses of 1 and 2.
of the electrochemical, quadratic and cubic NLO prop-
erties of the resultant complexes.
2. Results and discussion
2.1. Synthesis and characterization of terminal
acetylenes
Arylacetylenes with a protected formyl group were
required for the subsequent preparation of alkynyl
complexes. 4-HCꢀCC6H4CH{OC(O)Me}2 (1) was pre-
pared by extending the method of Kochar et al. [18],
stirring 4-HCꢀCC6H4CHO in acetic anhydride with a
catalytic amount of FeCl3 (Scheme 1). The formyl
group can also be protected by conversion into a
1,3-dioxane moiety. This was accomplished by stirring
4-HCꢀCC6H4CHO in a mixture of dichloromethane
and 1,3-propanediol with a catalytic amount of 4-tolue-
nesulfonic acid monohydrate, to give 2 in good yield
(Scheme 1). While the current research was in progress,
synthesis of
2
was reported by acetalizing 4-
Me3SiCꢀCC6H4CHO with 1,3-propanediol, and desily-
lating the intermediate with K2CO3–methanol,
although the yield by this procedure was not specified
Scheme 2. Syntheses of trans-bis{bis(diphenylphosphino)methane}chlororuthenium acetylide and vinylidene complexes.

116
S.K. Hurst et al. / Journal of Organometallic Chemistry 633 (2001) 114–124
Scheme 3. Synthesis of complexes 3 and 4.
Intraphosphine bond lengths and bond angles in 9
are not unusual. The AuꢂP, AuꢂC(1) and C(1)ꢂC(2)
bond distances are within the range of the values
observed earlier for (phosphine)gold acetylide com-
plexes [11,21]. Angles about the PꢂAuꢂC(1)ꢂC(2) moi-
ety are close to linearity, with any deviations likely to
be the result of crystal packing forces. Distances within
the phenyl and 1,3-dioxane components of the alkynyl
ligand are not unexpected. Gold complexes have at-
tracted significant interest as many show aurophilic
Au···Au interactions in the solid state. In the present
in good yield by extending the method of Naulty et al.
[15] (Scheme 4).
The new complexes were characterized by SI mass
spectrometry, satisfactory microanalyses, UV–vis, IR,
1H- and 31P-NMR spectroscopy. Characteristic w(CꢀC)
bands are found in the ranges of 2053–2081 and 2112–
2120 cm−1 for the new ruthenium and gold alkynyl
complexes, respectively, and w(PF) bands are found at
about 840 cm−1 for the PF−6 salts of the vinylidene
complex cations. The cyclopentadienyl ligand resonates
1
as a sharp singlet in the H-NMR spectra of 3 (4.29
1
ppm) and 4 (4.33 ppm). The H-NMR spectra of the
,
case, though, there are no Au···Au contacts B5 A.
vinylidene complexes contain characteristic multiplets
for RuCꢁCH at 2.95 (7), 3.13 (11) and 6.40 (15) ppm,
the significant downfield shift observed in 15 pre-
sumably arises from chemical shift anisotropy effects of
the 2-formyl group. The 31P-NMR spectra of all com-
plexes contain one singlet resonance, consistent with the
molecular symmetry in the poly-phosphine complexes.
The UV–vis spectra for these alkynylmetal complexes
contain MLCT bands at low energy; for the gold
2.4. Electrochemical studies
The results of cyclic voltammetric investigations into
the new ruthenium acetylide complexes are summarized
in Table 3 together with data reported earlier for
related complexes. All new complexes show an anodic
wave assigned to the RuII/III oxidation process. The
tabulated data are consistent with several broad trends.
Alkynylruthenium complexes exhibit reversible or
quasi-reversible processes (in the range of 0.51–0.67 V
for the new complexes), whereas the vinylidene com-
plexes exhibit irreversible complexes at a considerably
more positive potential (the latter as expected for
cationic complexes). The 2-formylphenylvinylidene
complexes, replacing alkynyl substituent CHO by
¸¹¹¹¹¹¹º
CHO(CH2)3O results in a shift to higher energy, as does
replacing 4-CHO by 4-CH{OC(O)Me}2 for the ruthe-
nium complexes in proceeding from 4 to 3. The 2-
formylphenylvinylidene complex 15 is unusual in
possessing a much lower energy umax (555 nm); this
unique band may result from the interaction between
the vinylidene proton and the formyl oxygen, hydrogen
bonding between which forms a six-membered ring.
Support for this possibility can be seen in the 13C-NMR
chemical shifts of the formyl carbons [170.2 ppm (15),
cf. 191.9 ppm (12), 191.2 ppm (4)]
2.3. X-ray crystallographic study
The identity of 9 was confirmed by a single-crystal
X-ray diffraction study. Crystal data are given in Table
1 and selected bond lengths and bond angles are com-
piled in Table 2. Fig. 1 contains an ORTEP plot showing
the molecular geometry and atomic labeling scheme.
Scheme 4. Synthesis of (phosphine)alkynyl gold complexes.

S.K. Hurst et al. / Journal of Organometallic Chemistry 633 (2001) 114–124
117
Table 1
and lack of facile deprotonation to the corresponding
alkynyl complex can also be regarded as nonconform-
ing). Oxidation potentials vary on phenyl substituent
variation as 4-HB4-CH{OC(O)Me}2B4-CHOB4-
NO2, the increasingly stronger electron-withdrawing
groups resulting in increasing difficulty in oxidation.
Oxidation potentials vary on phenyl substituents loca-
tion as 3-CHOB4-CHO, the former out of conjuga-
tion, the latter in conjugation with the metal. These
results are consistent with the arylalkynyl bridge
providing an efficient conduit for electronic
communication.
Crystallographic data and structure refinement parameters for com-
plex 9
Empirical formula
Formula weight
Temperature (K)
Wavelength (A)
Crystal system
Space group
C30H26AuO2P
646.47
200
0.71069
Monoclinic
P21/a (No. 14)
,
Unit cell dimensions
,
a (A)
13.8579(2)
12.2231(1)
14.9604(2)
96.492(7)
2517.84(6)
4
5.952
0.30×0.25×0.20
2.96–30.07
,
b (A)
,
c (A)
i (°)
3
,
V (A )
Z
2.5. Quadratic hyperpolarizabilities
Absorption coefficient (mm−1
)
We have determined the molecular quadratic nonlin-
earities of 1–12 and 15, together with acetylenes uti-
lized in the present study, using hyper-Rayleigh
Crystal size (mm)
Theta range for data collection
(°)
Index ranges
−195h519, −175k517,
−215l521
scattering at 1064 nm; the results of these studies, iexp
,
are given in Table 4, together with the two-level-cor-
rected values i0, and corresponding data for relevant
complexes. We have discussed earlier the potential in-
adequacies of the two-state model [13]. The low-energy
band for these complexes is MLCT in character;
higher-energy bands involve transitions with other lig-
ands, which result in little change in dipole moment
between ground and excited states, and hence little
contribution to nonlinearity, so it is probable that the
two-level-corrected values have some significance as an
indicator of zero-frequency nonlinearity.
Reflections collected
66 569
7701 (Rint=0.077)
0.222, 0.384
5733/0/307
R=0.0273, Rw=0.0334
R=0.0420, Rw=0.1448
Independent reflections
Max/min transmission
Data/restraints/parameters
Final R indices (I\2|(I)) a
R indices (all data) a
Largest difference peak and hole 1.30 and −1.96
−3
,
(e A
)
a R=ꢀꢁ ꢁFoꢁ−ꢁFcꢁ ꢁ/SꢁFoꢁ.
Rw=[ꢀw(ꢁFoꢁ−ꢁFcꢁ)2/SwFo2]1/2
,
w=
2 −1
[|2(Fo)+0.0004ꢁFoꢁ ]
.
The tabulated data reveal that phenyl substituent
Table 2
variation results in i values increasing as 4-HB4-
,
Selected bond lengths (A) and bond angles (°) for complex 9
¸¹¹¹¹¹¹º
CH{OC(O)Me}2, 4-CHO(CH2)3OB4-CHOB4-NO2,
the expected trend for increasing acceptor strength in
these dipolar molecules. In most instances, nonlineari-
ties increase significantly on proceeding from precursor
acetylene to product vinylidene or acetylide complex.
Nonlinearities for gold complexes are significantly less
than those for their ruthenium analogues, a result we
have noted previously for related pairs of complexes
[22]. Replacing PPh3 by PMe3 in proceeding from 9 to
10 results in a threefold increase in iexp and i0, the
opposite result to that seen in an earlier study of
5-nitro-2-pyridylalkynyl complexes [15]; PMe3 is a more
basic phosphine, resulting in a more electron-rich gold
donor, but PPh3 provides for more extensive p-delocal-
ization, and it is not immediately apparent which is the
more important factor influencing the magnitude of i
in these complexes. Phenyl substituent location affects
i, in replacing 3-CHO by 4-CHO (proceeding from 12
to trans-[Ru(4-CꢀCC6H4CHO)Cl(dppm)2]), with the
magnitude increasing upon formal conjugation of the
metal center with the acceptor formyl unit; however,
this result does not translate to increased corrected
nonlinearities, experimentally indistinguishable i0 val-
ues being observed. Vinylidene and acetylide complex
pairs (7, 8 and 11, 12) have very similar nonlinearities.
Bond lengths
AuꢂP
PꢂC(121)
AuꢂC(1)
C(2)ꢂC(3)
C(4)ꢂC(5)
C(6)ꢂC(7)
C(3)ꢂC(8)
C(9)ꢂO(1)
C(10)ꢂC(11)
C(12)ꢂO(2)
2.2726(7)
1.812(3)
2.006(3)
1.440(4)
1.381(4)
1.386(4)
1.391(4)
1.408(4)
1.500(6)
1.450(4)
PꢂC(111)
PꢂC(131)
C(1)ꢂC(2)
C(3)ꢂC(4)
C(5)ꢂC(6)
C(7)ꢂC(8)
C(6)ꢂC(9)
O(1)ꢂC(10)
C(11)ꢂC(12)
C(9)ꢂO(2)
1.821(3)
1.816(3)
1.194(4)
1.398(4)
1.389(4)
1.382(4)
1.505(4)
1.439(4)
1.513(6)
1.408(4)
Bond angles
PꢂAuꢂC(1)
177.5(1)
112.6(1)
170.9(3)
121.7(3)
120.6(3)
120.8(3)
121.2(3)
118.9(3)
108.0(3)
111.2(3)
AuꢂPꢂC(111)
AuꢂPꢂC(131)
113.1(1)
114.0(1)
174.5(3)
121.2(3)
118.6(3)
120.7(3)
122.5(3)
109.8(2)
110.1(3)
109.7(3)
110.0(3)
AuꢂPꢂC(121)
AuꢂC(l)ꢂC(2)
C(2)ꢂC(3)ꢂC(4)
C(4)ꢂC(5)ꢂC(6)
C(6)ꢂC(7)ꢂC(8)
C(3)ꢂC(8)ꢂC(7)
C(7)ꢂC(6)ꢂC(9)
C(6)ꢂC(9)ꢂO(2)
O(1)ꢂC(9)ꢂO(2)
C(1)ꢂC(2)ꢂC(3)
C(3)ꢂC(4)ꢂC(5)
C(5)ꢂC(6)ꢂC(7)
C(2)ꢂC(3)ꢂC(8)
C(5)ꢂC(6)ꢂC(9)
C(6)ꢂC(9)ꢂO(1)
C(9)ꢂO(1)ꢂC(10)
O(1)ꢂC(10)ꢂC(11)
C(12)ꢂO(2)ꢂC(9)
C(10)ꢂC(11)ꢂC(12) 110.0(3)
complex 15 has an anomalously low oxidation potential
(in this regard, its very low energy UV–vis transition

118
S.K. Hurst et al. / Journal of Organometallic Chemistry 633 (2001) 114–124
2.6. Cubic hyperpolarizabilities
3. Conclusions
Third-order nonlinearities for 1–9, 11, 12 and 15
were determined by Z-scan at 800 nm, data being
tabulated in Table 5. An electronic origin for cubic
nonlinearities in related metal acetylide complexes has
been demonstrated earlier by degenerate four-wave
mixing measurements, and nonlinearities for the present
series of compounds are therefore likely to be electronic
in origin [5].
Nonlinearities for the new compounds are low, with
large error margins in many instances, rendering the
extraction of structure–property relationships difficult.
Nevertheless, several points may be noted. Introduction
of ligated gold in proceeding from 2 to 9 and replacing
PMe3 by PPh3 in proceeding from 6 to 5 both result in
increased kreal and ꢁkꢁ, and the kreal and ꢁkꢁ values for 15
are larger than those of the 3- and 4-formylphenyl-
vinylidene complex analogues.
The present studies have afforded complexes contain-
ing protected and exposed formylphenylalkynyl or -vi-
nylidene ligands. As the aldehyde functional group can
be derivatized in a variety of useful ways, complexes
bearing these ligands should have utility in the assem-
bly of extended structures. The electronic properties of
these ligands are as predicted, their electron-withdraw-
ing character being less than the strong nitro acceptor,
and diminishing as the CHO substituent moves from
para to meta position with respect to the alkynyl/vinyl-
idene group. The magnitude of quadratic nonlinearities
in these complexes largely parallels the effectiveness of
this electron-withdrawing group. Cubic nonlinearities
are in most cases too low to comment confidently, but
the enhancement in kreal on replacing PMe3 by PPh3
(proceeding from 6 to 5) and replacing 4- and 3-
formylvinylidene ligand by 2-formylvinylidene ligand
¸¹¹¹¹¹¹º
Fig. 1. Molecular geometry and atomic labeling scheme for [Au{CꢀCC6H4CHO(CH2)3O}(PPh3)] (9).
Table 3
Cyclic voltammetric data for ruthenium complexes a
Complex
E1/2 RuII/III (V)
[ipc/ipa
]
Reference
[Ru(CꢀCPh)(PPh3)2(h-C5H5)]
0.55
0.59
0.67
0.73
1.38
0.55
0.7
1
0.9
[6]
[Ru(4-CꢀCC6H4CH{OC(O)Me}2)(PPh3)2(h-C5H5)] (3)
[Ru(4-CꢀCC6H4CHO)(PPh3)2(h-C5H5)] (4)
[Ru(4-CꢀCC6H4NO2)(PPh3)2(h-C5H5)]
trans-[Ru(CꢁCHPh)Cl(dppm)2]PF6
This work
This work
[6]
[1]
[1]
1
b
trans-[Ru(CꢀCPh)Cl(dppm)2]
1
¸¹¹¹¹¹¹º
b
trans-[Ru{4-CꢁCHC6H4CHO(CH2)3O}Cl(dppm)2]PF6 (7)
1.48
This work
¸¹¹¹¹¹¹º
trans-[Ru{4-CꢀCC6H4CHO(CH2)3O}Cl(dppm)2] (8)
trans-[Ru(4-CꢁCHC6H4CHO)Cl(dppm)2]PF6
trans-[Ru(4-CꢀCC6H4CHO)Cl(dppm)2]
trans-[Ru(3-CꢁCHC6H4CHO)Cl(dppm)2]PF6 (11)
trans-[Ru(3-CꢀCC6H4CHO)Cl(dppm)2] (12)
trans-[Ru(2-CꢁCHC6H4CHO)Cl(dppm)2]PF6 (15)
0.51
1.50
0.66
1.34
0.60
1.23
1
This work
[1]
[1]
This work
This work
This work
b
1
b
0.9
b
a Ferrocene/ferrocenium couple (0.56 V) as an internal standard.
b Nonreversible process.

S.K. Hurst et al. / Journal of Organometallic Chemistry 633 (2001) 114–124
119
Table 4
Experimental linear optical spectroscopic and quadratic NLO response parameters a
Compound
umax (nm)
[m, 104 −1 cm−1
iexp
(10−30 esu) b
i0
(10−30 esu) c
Reference
M
]
4-HCꢀCC6H4CHO
271 [2.5]
252 [2.3]
7
11
4
7
This work
This work
4-HCꢀCC6H4CH{OC(O)Me}2 (1)
¸¹¹¹¹¹¹º
4-HCꢀCC6H4CHO{CH2}3O (2)
3-HCꢀCC6H4CHO
[Ru(CꢀCPh)(PPh3)2(h-C5H5)]
[Ru(4-CꢀCC6H4CH{OC(O)Me}2)(PPh3)2(h-C5H5)] (3)
[Ru(4-CꢀCC6H4CHO)(PPh3)2(h-C5H5)] (4)
[Ru(4-CꢀCC6H4NO2)(PPh3)2(h-C5H5)]
[Au(4-CꢀCC6H4CHO)(PPh3)] (5)
250 [1.9]
332 [0.1]
310 [2.0]
326 [2.3]
400 [2.3]
460 [8.5]
322 [5.0]
322 [5.0]
27
21
16
68
120
468
20
12
10
38
45
96
8
This work
This work
[13]
This work
This work
[7]
14
This work
This work
d
[Au(4-CꢀCC6H4CHO)(PMe3)] (6)
–
¸¹¹¹¹¹¹º
trans-[Ru{4-CꢁCHC6H4CHO(CH2)3O}Cl(dppm)2]PF6 (7)
¸¹¹¹¹¹¹º
317 [1.3]
64
38
This work
trans-[Ru{4-CꢀCC6H4CHO(CH2)3O}Cl(dppm)2] (8)
320 [1.2]
296 [1.7]
292 [0.8]
320 [1.1]
321 [0.9]
405 [6.0]
318 [0.5]
322 [0.1]
555 [0.2]
61
15
48
45
58
35
4
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[1]
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[Au(4-CꢀCC6H4CHO{CH2}3O)(PPh3)] (9)
[Au(4-CꢀCC6H4CHO{CH2}3O)(PMe3)] (10)
trans-[Ru(3-CꢁCHC6H4CHO)Cl(dppm)2]PF6 (11)
trans-[Ru(3-CꢀCC6H4CHO)Cl(dppm)2] (12)
trans-[Ru(4-CꢀCC6H4CHO)Cl(dppm)2]
[Au(3-CꢀCC6H4CHO)(PPh3)] (13)
13
26
34
38
–
106
d
d
[Au(3-CꢀCC6H4CHO)(PMe3)] (14)
trans-[Ru(2-CꢁCHC6H4CHO)Cl(dppm)2]PF6 (15)
–
2
27
a All measurements in thf solvent. All complexes are optically transparent at 1064 nm.
b HRS at 1064 nm; values 910%.
c HRS at 1064 nm corrected for resonance enhancement at 532 nm using the two-level model with io=i[l−(2umax/1064)2][1−(umax/1064)2];
damping factors not included.
d Too low to measure.
Table 5
Experimental linear optical spectroscopic and cubic NLO response parameters a
Compound
umax (nm)
[m, 104 −1 cm−1
kreal
kimag
ꢁkꢁ
Reference
M
]
(10−36 esu) b (10−36 esu) b (10−36 esu) b
4-HCꢀCC6H4CHO
271 [2.5]
252 [2.3]
326 [2.4]
400 [2.3]
322 [5.0]
322 [5.0]
1798
−180980
1009100
−75950
3009150
35920
0
1798
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4-HCꢀCC6H4CH{OC(O)Me}2 (1)
[Ru(4-CꢀCC6H4CH{OC(O)Me}2)(PPh3)2(h-C5H5)] (3)
[Ru(4-CꢀCC6H4CHO)(PPh3)2(h-C5H5)] (4)
[Au(4-CꢀCC6H4CHO)(PPh3)] (5)
595
0
210950
0
180980
1009100
220960
3009150
60935
[Au(4-CꢀCC6H4CHO)(PMe3)] (6)
45930
¸¹¹¹¹¹¹º
4-HCꢀCC6H4CHO(CH2)3O (2)
¸¹¹¹¹¹¹º
250 [1.9]
1597
393
1597
75975
50950
2109100
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trans-[Ru{4-CꢁCHC6H4CHO(CH2)3O}Cl(dppm)2]PF6 (7) 317 [1.3]
75975
50950
0
0
¸¹¹¹¹¹¹º
trans-[Ru{4-CꢀCC6H4CHO(CH2)3O}Cl(dppm)2] (8)
320 [1.2]
296 [1.7]
¸¹¹¹¹¹¹º
[Au(4-CꢀCC6H4CHO(CH2)3O}(PPh3)] (9)
¸¹¹¹¹¹¹º
[Au{4-CꢀCC6H4CHO(CH2)3O}(PMe3)] (10)
trans-[Ru(3-CꢁCHC6H4CHO)Cl(dppm)2]PF6 (11)
trans-[Ru(3-CꢀCC6H4CHO)Cl(dppm)2] (12)
[Au(3-CꢀCC6H4CHO)(PPh3)] (13)
[Au(3-CꢀCC6H4CHO)(PMe3)] (14)
trans-[Ru(2-CꢁCHC6H4CHO)Cl(dppm)2]PF6 (15)
trans-[Ru(4-CꢁCHC6H4CHO)Cl(dppm)2]PF6
2109100
0
c
c
292 [0.8]
320 [1.1]
321 [0.9]
318 [0.5]
322 [0.1]
555 [0.2]
403 [1.9]
This work
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[1]
2009200
0
2009200
1509150
1509150
0
d
d
d
d
4509150
0
150960
B20
4709160
B20
a All measurements as THF solutions (all complexes are optically transparent at 800 nm).
b All results are referenced to silica, nonlinear refractive index n2=3×10−16 cm2 W−1
c Too low to measure.
d Sample scattered light.
.

120
S.K. Hurst et al. / Journal of Organometallic Chemistry 633 (2001) 114–124
(proceeding to 15) contrast with the effect of these
structural modifications on i values.
(SIMS) were recorded using a VG ZAB 2SEQ instru-
ment (30 kV Cs+ ions, current 1 mA, accelerating
potential 8 kV, 3-nitrobenzyl alcohol matrix) at the
Research School of Chemistry, Australian National
University; peaks are reported as m/z (assignment, rela-
tive intensity). Microanalyses were carried out at the
Research School of Chemistry, Australian National
University. IR spectra were recorded either as 1% KBr
discs or CH2Cl2 solutions using a Perkin–Elmer System
2000 FTIR. 1H-, 31P-, and 13C-NMR spectra were
recorded using a Varian Gemini-300 FT NMR spec-
trometer and are referenced to residual CHCl3 (7.24
ppm), CHCl3-d (77.0 ppm) or external 85% H3PO4 (0.0
ppm), respectively. The assignments follow the number-
ing scheme shown in Fig. 2. UV–vis spectra of solu-
tions were recorded in THF in 1 cm quartz cells using
a Cary 4 spectrophotometer. Electrochemical measure-
ments were recorded using a MacLab 400 interface and
MacLab potentiostat from ADInstruments. The sup-
porting electrolyte was 0.1 M [NnBu4][PF6] in distilled,
deoxygenated CH2Cl2. Solutions containing ca. 1×
10−3 M complex were maintained under nitrogen.
Measurements were carried out at 25 °C using plat-
inum disc working-, Pt wire auxillary- and Ag/AgCl
reference-electrodes, such that the ferrocene/ferroce-
nium redox couple was located at 0.56 V with a peak
separation of around 0.09 V. Scan rates were typically
4. Experimental
4.1. General conditions, reagents and instruments
All reactions were performed under a nitrogen atmo-
sphere with the use of standard Schlenk techniques
unless otherwise stated. Dichloromethane and Et3N
were dried by distilling over CaH2, Et2O and THF were
dried by distilling over sodium–benzophenone, and
other solvents were used as received. ‘Petroleum spirit’
refers to a fraction of petroleum ether of boiling range
60–80 °C. Chromatography was carried out on silica
gel (230–400 mesh ASTM) or basic ungraded alumina.
The following reagents were prepared by the litera-
ture procedures: cis-[RuCl2(dppm)2] [23], [AuCl(PPh3)]
[24], [AuCl(PMe3) [25], 4-HCꢀCC6H4CHO [26], 3-
HCꢀCC6H4CHO [26], 2-HCꢀCC6H4CHO [26]. Ammo-
nium hexafluorophosphate (Aldrich), 4-MeC6H4-
SO3H·H2O (Aldrich), 1,3-propanediol (Aldrich), FeCl3
(Ajax) and acetic anhydride (Aldrich) were used as
received.
EI (electron impact) mass spectra (both unit resolu-
tion and high resolution (HR)) were recorded using a
VG Autospec instrument (70 eV electron energy, 8 kV
accelerating potential) and secondary ion mass spectra
100 mV s−1
.
Fig. 2. Numbering scheme for NMR spectral assignments for 1–15.

S.K. Hurst et al. / Journal of Organometallic Chemistry 633 (2001) 114–124
121
orange product (235 mg, 62%). Anal. Found: C, 70.19;
H, 5.40%. Calc. for C54H46O4P2Ru: C, 70.35; H, 5.03%.
IR (CH2Cl2, cm−1): w(CꢀC) 2066. UV–vis: u (nm) (m,
4.2. Synthesis of terminal acetylenes
4.2.1. 4-HCꢀCC6H4CH{OC(O)Me}2 (1)
4-HCꢀCC6H4CHO (1.00 g, 7.69 mmol) was stirred in
Ac2O (6 ml) for 15 min, and then 0.1 g of anhydrous
ferric chloride was added. After stirring for a further 20
min, the reaction mixture was poured into 50 ml of
hexane and 10 ml of water. The aqueous phase was
washed with 3×30 ml portions hexane, and the com-
bined organic extracts were washed with 3×30 ml
water. The organic phase was dried and concentrated to
give the white product (690 mg, 39%). Anal. Found: C,
66.45; H, 5.31. Calc. for C13H12O4: C, 67.23; H, 5.21%.
IR (CH2Cl2, cm−1): w(HCꢀ) 3297, w(CꢀC) 2111. UV–
M
−1 cm−1) (THF): 327 (22 600). 1H-NMR (CDCl3,
300 MHz): l=2.10 (m, 6H, Me), 4.29 (s, 5H, C5H5),
7.10–7.50 (m, 30H, Ph), 7.64 (s, 1H, H9). 31P-NMR
(CDCl3, 121 MHz): l=51.3. SIMS: 922 ([M]+, 40),
863 ([M−OC(O)Me]+, 5), 660 ([M−PPh3]+, 10), 429
([M−PPh3−CꢀCC6H4CH{OC(O)Me}2]+, 100).
4.3.2. [Ru(4-CꢀCC6H4CHO)(PPh3)2(p-C5H5)] (4)
[Ru(4-CꢀCC6H4CH{OC(O)Me}2)(PPh3)2(h-C5H5)]
(3) (300 mg, 0.33 mmol) was dissolved in MeOH (15
ml) and a solution of CH3ONa in MeOH (1 M, 5 ml)
was added. The mixture was stirred at room tempera-
ture (r.t.) for 2 h and then the solvent reduced, yielding
the orange–red product (221 mg, 73%). Anal. Found:
C, 72.32; H, 5.32. Calc. for C50H40OP2Ru: C, 73.25; H,
4.92%. IR (CH2Cl2, cm−1): w(CꢀC) 2053. UV–vis: u
(nm) (m, M−1 cm−1) (THF): 400 (23 000). 1H-NMR
(CDCl3, 300 MHz,): l=4.33 (s, 5H, C5H5), 6.90–7.60
(m, 34H, Ph), 9.85 (s, 1H, H9). 31P-NMR (CDCl3, 121
MHz): l=51.0. SIMS: 820 ([M]+, 100), 691 ([M−
CꢀCC6H4CHO]+, 25), 558 ([M−PPh3−H]+, 20), 429
([Ru(PPh3)(h-C5H5)]+, 45).
vis: u (nm) (m, M−1 cm−1) (THF): 252 (17 000). H-
NMR: (CDCl3, 300 MHz): l=2.11 (s, 6H, H11), 3.10
(s, 1H, H1), 7.45 (d, JHH=9 Hz, 2H, H4), 7.51 (d,
1
J
HH=9 Hz, 2H, H5), 7.64 (s, 1H, H9). SIMS: 232
([M]+, 20), 189 ([M−C(O)Me]+, 25), 173 ([M−
OC(O)Me]+, 20), 129 ([M−MeC(O)OC(O)Me−H]+,
100), 101 ([M−CH{OC(O)Me}2]+, 40). HRMS; m/z:
Found: 232.0735. Calc. for C13H12O4: 232.0737.
¸¹¹¹¹¹¹º
4.2.2. 4-HCꢀCC6H4CHO(CH2)3O (2)
4-HCꢀCC6H4CHO (200 mg, 1.54 mmol), 4-
MeC6H4SO3H·H2O (40 mg, 0.21 mmol) and
HO(CH2)3OH (140 mg, 1.85 mmol) were stirred in
CH2Cl2 (25 ml) for 8 h. The solution was neutralized
with saturated NaHCO3 solution, washed with water
and dried with MgSO4. The solvent was removed under
reduced pressure to obtain the pale-brown product (204
mg, 69%). Anal. Found: C, 75.89; H, 5.93. Calc. for
C12H12O2: C, 76.57; H, 6.43%. IR (CH2Cl2, cm−1):
w(CꢀC) 2112. UV–vis: u (nm) (m, M−1 cm−1) (THF):
250 (18 900). 1H-NMR: (CDCl3, 300 MHz): l=1.44
(m, 1H, H11), 2.10–2.30 (m, 1H, H11), 3.05 (s, 1H, H1),
3.90–4.05 (m, 2H, H10), 4.20–4.30 (m, 2H, H10), 5.47
(s, 1H, H9), 7.42 (d, JHH=9 Hz, 2H, H4), 7.48 (d,
4.3.3. [Au(4-CꢀCC6H4CHO)(PPh3)] (5)
[AuCl(PPh3)] (200 mg, 0.40 mmol) and 4-
HCꢀCC6H4CHO (57 mg, 0.44 mmol) were stirred in a
solution of CH3ONa in MeOH (0.1 M, 15 ml) for 16 h.
A solid precipitate was filtered to yield the yellow
product (135 mg, 57%). Anal. Found: C, 54.62; H, 3.39.
Calc. for C27H20AuOP: C, 55.12; H, 3.43%. IR
(CH2Cl2, cm−1): w(CꢀC) 2115. UV–vis: u (nm) (m,
M
−1 cm−1) (THF): 322 (50 000). 1H-NMR (CDCl3,
300 MHz): l=7.30–7.80 (m, 19H, Ph), 9.94 (s, 1H,
H9). 31P-NMR (CDCl3, 121 MHz): l=42.8. SIMS:
1047 ([M+Au(PPh3)]+, 75), 721 ([Au(PPh3)2]+, 20),
589 ([M]+, 30), 459 ([Au(PPh3)]+, 100).
J
HH=9 Hz, 2H, H5). EIMS: 188 ([M]+, 100), 129
([M−H−(CH2)3O]+, 95). HRMS; m/z: Found:
4.3.4. [Au(4-CꢀCC6H4CHO)(PMe3)] (6)
188.0836. Calc. for C12H12O2: 188.0837.
[AuCl(PMe3)] (154 mg, 0.50 mmol) and 4-
HCꢀCC6H4CHO (72 mg, 0.55 mmol) were stirred in a
solution of CH3ONa in MeOH (0.1 M, 15 ml) for 16 h.
The solid precipitate was collected by filtration to yield
the pale-yellow product (156 mg, 78%). Anal. Found:
C, 36.87; H, 3.71. Calc. for C12H14AuOP: C, 35.84; H,
3.51%. IR (CH2Cl2, cm−1): w(CꢀC) 2112. UV–vis: u
(nm) (m, M−1 cm−1) (THF): 322 (49 800). 1H-NMR
(CDCl3, 300 MHz): l=1.51 (d, JHP=10 Hz, 9H, Me),
7.54 (d, JHH=8 Hz, 2H, C6H4), 7.72 (d, JHH=8 Hz,
2H, C6H4), 9.92 (s, H9). 31P-NMR (CDCl3, 121 MHz):
l=1.6. SIMS: 675 ([M+Au(PMe3)−2H]+, 40), 403
([M]+, 60), 349 ([Au(PMe3)2]+, 45), 273 ([Au(PMe3)]+,
80).
4.3. Synthesis of metal complexes
4.3.1. [Ru(4-CꢀCC6H4CH{OC(O)Me}2)-
(PPh3)2(p-C5H5)] (3)
[RuCl(PPh3)2(h-C5H5)] (300 mg, 0.41 mmol),
NH4PF6 (101 mg, 0.62 mmol) and 4-HCꢀCC6H4CH-
{OC(O)Me}2 (1) (115 mg, 0.50 mmol) were added to
MeOH (25 ml), and the resultant mixture was refluxed
with stirring for 1 h, and then allowed to cool. A
solution of CH3ONa in MeOH (1 M, 5 ml) was added,
the mixture was stirred for 5 min, and then the solvent
removed under reduced pressure. Column chromatog-
raphy with 1:1 petroleum spirit–CH2Cl2 yielded the

122
S.K. Hurst et al. / Journal of Organometallic Chemistry 633 (2001) 114–124
¸¹¹¹¹¹¹º
¸¹¹¹¹¹¹º
4.3.5. trans-[Ru(4-CꢁCHC6H4CHO(CH2)3O)-
Cl(dppm)2][PF6] (7)
4.3.8. [Au{4-CꢀCC6H4CHO(CH2)3O}(PMe3)]·
1CH3CH2OH (10)
cis-[RuCl2(dppm)2] (200 mg, 0.21 mmol), NH4PF6
(70 mg, 0.43 mmol) and 2 (48 mg, 0.26 mmol) were
added to CH2Cl2 (25 ml), and the resultant mixture
stirred for 4 h. Petroleum spirit (50 ml) was added, and
the solvent removed under vacuum. The solid material
was triturated with ether and then filtered to yield the
pale-red product (220 mg, 84%). Anal. Found: C, 59.99;
H, 4.78. Calc. for C62H56ClF6O2P5Ru: C, 60.13; H,
[AuCl(PMe3)] (100 mg, 0.324 mmol) and 2 (80 mg,
0.40 mmol) were stirred in a solution of CH3ONa in
MeOH (0.1 M, 15 ml) for 16 h. A solid precipitate was
collected by filtration to yield the pale-yellow product
(108 mg, 72%). Anal. Found: C, 40.43; H, 4.28. Calc.
for C17H26AuO3P: C, 40.33; H, 5.18%. IR (CH2Cl2,
cm−1): w(CꢀC) 2118. UV–vis: u (nm) (m, M−1 cm−1
)
1
(THF): 292 (7600), 285 (23 200). H-NMR (CDCl3, 300
MHz): l=1.20 (t, JHH=4 Hz, 3H, CH3), 1.42 (br s,
lH, H11), 1.52 (br s, 9H, Me), 2.10–2.30 (m, lH, H11),
3.67 (q, JHH=6 Hz, 2H, CH2), 3.80–4.00 (m, 2H, H10),
4.15–4.30 (m, 2H, H10), 5.44 (s, 1H, H9), 7.33 (d,
4.56%. IR (KBr, cm−1): w(PF) 839. UV–vis: u (nm) (m,
1
M
−1 cm−1) (THF): 317 (m 13 400). H-NMR (CDCl3,
300 MHz): l=1.40 (m, 1H, H11), 2.10–2.20 (m, 1H,
H11), 2.95 (m, 1H, H2), 3.85–4.25 (m, 4H, H10), 5.06
(m, 2H, PCH2P), 5.30 (m, 2H, PCH2P), 5.35 (s, 1H,
H9), 5.48 (d, JHH=8 Hz, 2H, H4), 6.85 (d, JHH=8 Hz,
2H, H5), 7.10–7.50 (m, 40H, Ph). 31P-NMR (CDCl3,
121 MHz): l= −15.5. SIMS: 1092 ([M−PF6]+, 15),
905 [RuCl(dppm)2]+, 90), 869 ([Ru(dppm)2−H]+,
100), 485 ([Ru(dppm)]+−H, 90).
J
HH=8 Hz, 2H, H4), 7.44 (d, JHH=8 Hz, 2H, H5).
31P-NMR (CDCl3, 121 MHz): l=1.7. SIMS: 459
([M+Au(PMe3)]+, 10), 459 ([M−H]+, 100).
4.3.9. trans-[Ru(3-CꢁCHC6H4CHO)Cl(dppm)2][PF6]
(11)
¸¹¹¹¹¹¹º
cis-[RuCl2(dppm)2] (400 mg, 0.43 mmol), NH4PF6
(140 mg, 0.86 mmol) and 3-HCꢀCC6H4CHO (174 mg,
0.86 mmol) were added to CH2Cl2 (25 ml), and the
resultant mixture refluxed for 2 h. Petroleum spirit (50
ml) was added, and the resulting precipitate was col-
lected and washed with ether to afford the pale-red
solid (409 mg, 76%). Anal. Found: C, 59.67; H, 4.44.
Calc. for C59H50ClF6OP5Ru: C, 60.03; H, 4.27%. IR
4.3.6. trans-[Ru{4-CꢀCC6H4CHO(CH2)3O}-
Cl(dppm)2]·0.5CH2Cl2 (8)
¸¹¹¹¹¹¹º
trans-[Ru{4-CꢁCHC6H4CHO(CH2)3O}Cl(dppm)2]-
[PF6] (7) (200 mg, 0.16 mmol) was added to CH2Cl2 (25
ml) and Et3N (1 ml) and the resultant mixture stirred
for 10 min at r.t. The mixture was passed through an
alumina plug, petroleum spirit (50 ml) was added, and
the resulting precipitate was collected and washed with
petroleum spirit yielding the pale-red product (153 mg,
87%). Anal. Found: C, 66.85; H, 5.09. Calc. for
(KBr, cm−1): w(PF) 839. UV–vis:
−1 cm−1) (THF): 320 (10 900). 1H-NMR (CDCl3,
u
(nm) (m,
M
C
62.5H56Cl2O2P4Ru: C, 66.14; H, 4.97%. IR (CH2Cl2,
300 MHz): l=3.13 (m, 1H, H2), 5.12 (m, 2H, PCH2P),
5.32 (m, 2H, PCH2P), 5.75–6.90 (4H, H4, H5), 7.10–
7.60 (m, 40H, Ph), 9.54 (s, H9). 31P-NMR (CDCl3, 121
MHz): l= −15.9. SIMS: 1035 ([M−PF6]+, 40), 999
([M−Cl−PF6]+, 10), 904 ([RuCl(dppm)2]+, 70), 869
([Ru(dppm)−H]+, 100).
cm−1): w(CꢀC) 2081. UV–vis: u (nm) (m, M−1 cm−1
)
(THF): 320 (11 600). 1H-NMR (CDCl3, 300 MHz):
l=1.40 (m, 1H, H11), 2.20–2.40 (m, 1H, H11), 3.80–
4.00 (m, 2H, H10), 4.20–4.30 (m, 2H, H10), 4.88 (m, 4H,
PCH2P), 5.27 (s, 1H, CH2Cl2), 5.35 (s, H9), 5.97 (d,
J
HH=8 Hz, 2H, H4), 6.90–7.50 (m, 42H, Ph+H5).
31P-NMR (CDCl3, 121 MHz): l= −6.1. SIMS: 1092
([M]+, 100), 905 ([RuCl(dppm)2]+, 15), 869
([Ru(dppm)2−H]+, 50), 486 ([Ru(dppm)]+, 30).
4.3.10. trans-[Ru(3-CꢀCC6H4CHO)Cl(dppm)2] (12)
cis-[RuCl2(dppm)2] (300 mg, 0.32 mmol), NH4PF6
(104 mg, 0.64 mmol) and 3-HCꢀCC6H4CHO (90 mg,
0.69 mmol) were added to CH2Cl2 (25 ml), and the
resultant mixture stirred for 4 h. Triethylamine (1 ml)
and petroleum spirit (20 ml) were then added, and the
solution filtered through an alumina plug. The solvent
was removed under vacuum, the solid was then tritu-
rated with petroleum spirit and filtered to afford the
yellow product (156 mg, 83%). Anal. Found: C, 68.06;
H, 4.75%. Calc. for C59H49ClOP4Ru: C, 68.50; H,
4.77%. IR (CH2Cl2, cm−1): w(CꢀC) 2075. UV–vis: u
(nm) (m, M−1 cm−1) (THF): 321 (9500), 260 (32 300).
1H-NMR (CDCl3, 300 MHz): l=4.89 (m, 4H,
PCH2P), 6.28 (d, JHH=8 Hz, lH, H4 or H6), 6.39 (s,
1H, H8), 7.05–7.60 (m, 42H, Ph+H5+H4 or H6), 9.54
(s, 1H, H9). 31P-NMR (CDCl3, 121 MHz): l= −6.0.
SIMS: 1034 ([M−H]+, 100), 999 (M−Cl]+, 20), 905
¸¹¹¹¹¹¹º
4.3.7. [Au{4-CꢀCC6H4CHO(CH2)3O}(PPh3)] (9)
[AuCl(PPh3)] (100 mg, 0.20 mmol) and 2 (46 mg, 0.24
mmol) were stirred in a solution of CH3ONa in MeOH
(0.1 M, 15 ml) for 16 h. A solid precipitate was
collected by filtration to yield the pale-yellow product
(121 mg, 93%). Anal. Found: C, 54.66; H, 4.32. Calc.
for C30H26AuO2P: C, 54.88; H, 4.46%. IR (CH2Cl2,
cm−1): w(CꢀC) 2117. UV–vis: u (nm) (m, M−1 cm−1
)
1
(THF): 296 (16 600), 288 (30 600). H-NMR (CDCl3,
300 MHz): l=1.43 (m, 1H, H11), 2.10–2.30 (m, lH,
H11), 3.90–4.00 (m, 2H, H10), 4.20–4.30 (m, 2H, H10),
5.45 (s, 1H, H9), 7.35 (d, JHH=8 Hz, 2H, H4), 7.38–
7.60 (m, 17H, Ph+H5). 31P-NMR (CDCl3, 121 MHz):
42.8. SIMS: 721 ([Au(PPh3)2]+, 20), 647 ([M]+, 30), 459
([Au(PPh3)]+, 100).

S.K. Hurst et al. / Journal of Organometallic Chemistry 633 (2001) 114–124
123
([RuCl(dppm)2]+, 25), 869 ([Ru(dppm)2−H]+, 60), 485
([Ru(dppm)−H]+, 35).
solution of 9 at r.t. A single pale-yellow prism was
mounted on a fine glass capillary using Paratone oil,
and data were collected at 200 K on a Nonius Kappa-
CCD diffractometer using graphite-monochromated
Mo–Ka radiation. The unit cell parameters were ob-
tained by least-squares refinement [27] of 38310 reflec-
tions with 2.95q530.0. The data were corrected for
absorption using numerical methods [28], implemented
from within maXus [29]; equivalent reflections were
merged. The structure was solved by direct methods
[30] and expanded using Fourier techniques [31]. Non-
hydrogen atoms were refined anisotropically; hydrogen
atoms were included in idealized positions which were
frequently recalculated. The final cycle of full-matrix
least-squares refinement on F was based on 5733 ob-
served reflections (I\2|(I)) and 307 variable parame-
ters, and converged to R=0.027. Selected crystal data
and structure refinement parameters are tabulated in
Table 1.
4.3.11. [Au(3-CꢀCC6H4CHO)(PPh3)] (13)
[AuCl(PPh3)] (200 mg, 0.404 mmol) and 3-
HCꢀCC6H4CHO (63 mg, 0.49 mmol) were stirred in a
solution of CH3ONa in MeOH (0.1 M, 15 ml) for 16 h.
The solid precipitate was washed with petroleum ether
and filtered to yield the pale-yellow product (136 mg,
57%). Anal. Found: C, 54.43; H, 3.53. Calc. for
C27H20AuOP: C, 55.11; H, 3.43%. IR (CH2Cl2, cm−1):
w(CꢀC) 2120. UV–vis: u (nm) (m, M−1 cm−1) (THF):
1
318 (4700), 286 (18 400). H-NMR (CDCl3, 300 MHz):
l=7.30–7.80 (m, 19H, Ph), 9.93 (s, 1H, H9). 31P-NMR
(CDCl3, 121 MHz): l=42.9. SIMS; 721 ([Au(PPh3)2]+,
50), 589 ([M]+, 5), 459 ([Au(PPh3)]+, 100).
4.3.12. [Au(3-CꢀCC6H4CHO)(PMe3)]·2C6H6 (14)
[AuCl(PMe3)] (200 mg, 0.65 mmol) and 3-
HCꢀCC6H4CHO (101 mg, 0.78 mmol) were stirred in a
solution of CH3ONa in MeOH (0.1 M, 15 ml) for 16 h.
The solid precipitate was collected by filtration and
washed with petroleum spirit to yield the off-white
product which was recrystallized from benzene (167
mg, 64%). Anal. Found: C, 50.75; H, 3.95. Calc. for
C24H38AuOP: C, 51.62; H, 4.69%. IR (CH2Cl2, cm−1):
w(CꢀC) 2116. UV–vis: u (nm) (m, M−1 cm−1) (THF):
4.5. Hyper–Rayleigh scattering measurements
An injection-seeded Nd:YAG laser (Q-switched
Nd:YAG Quanta Ray GCR5, 1064 nm, 8 ns pulses, 10
Hz) was focused into a cylindrical cell (7 ml) containing
the sample. The intensity of the incident beam was
varied by the rotation of a half-wave plate placed
between crossed polarizers. Part of the laser pulse was
sampled by a photodiode to measure the vertically
polarized incident light intensity. The frequency dou-
bled light was collected by an efficient condenser system
and detected by a photomultiplier. The harmonic and
linear scatterings were distinguished by appropriate
filters; gated integrators were used to obtain the intensi-
ties of the incident and harmonic scattered light. The
absence of a luminescence contribution to the harmonic
signal was confirmed by using interference filters at
different wavelengths near 532 nm. All measurements
were performed in THF using p-nitroaniline (i=
21.4×10−30 esu) [32] as a reference. The absorption of
the scattered light was negligible as the solutions were
sufficiently dilute. Further details on the experimental
procedure have been reported in Refs. [33,34].
1
322 (1000). H-NMR (CDCl3, 300 MHz): l=1.54 (br
s, 9H, Me), 7.30–8.00 (m, 4H, C6H4), 7.32 (s, 12H,
C6H6), 9.92 (s, 1H, H9). 31P-NMR (CDCl3, 121 MHz):
l=1.6. SIMS; 675 ([M+Au(PMe3)−2H]+, 15), 403
([M]+, 5), 349 ([Au(PMe3)2]+, 100), 273 ([Au(PMe3)]+,
60).
4.3.13. trans-[Ru(2-CꢁCHC6H4CHO)Cl(dppm)2][PF6]
(15)
cis-[RuCl2(dppm)2] (300 mg, 0.32 mmol), NH4PF6
(104 mg, 0.64 mmol) and 2-HCꢀCC6H4CHO (90 mg,
0.69 mmol) were added to CH2Cl2 (25 ml), and the
resultant mixture stirred for 4 h. The solution was
filtered, petroleum spirit (20 ml) was added, and the
solvent removed under vacuum. The solid was triturated
with ether and the purple solid was collected by filtration
(305 mg, 81%). Anal. Found: C, 59.95; H, 4.69. Calc. for
C59H50ClF6OP5Ru: C, 60.03; H, 4.27%. IR (KBr, cm−1):
w(PF) 841. UV–vis: u (nm) (m, M−1 cm−1) (THF): 555
4.6. Z-scan measurements
1
(2000), 355 (7400). H-NMR (CDCl3, 300 MHz): l=
Measurements were performed at 800 nm using a
system consisting of a Coherent Mira Ar-pumped Ti-
sapphire laser generating a mode-locked train of ca. 100
fs pulses and a home-built Ti-sapphire regenerative
amplifier pumped with a frequency-doubled Q-switched
pulsed YAG laser (Spectra Physics GCR) at 30 Hz and
employing chirped pulse amplification. The solutions
were examined in a glass cell with a 0.1 cm path length.
The Z-scans were recorded at two concentrations for
each compound and the real and imaginary parts of the
nonlinear phase change were determined by numerical
5.25 (m, 2H, PCH2P), 5.39 (m, 2H, PCH2P), 5.67 (d,
J
HH=9 Hz, 1H, H7), 6.40 (m, 1H, H2), 6.80–7.60 (m,
43H, Ph+C6H4), 8.53 (s, 1H, H9). 31P-NMR (CDCI3,
121 MHz): l= −7.6. LDTOFMS; 1059 ([M−PF6+
Na]+, 100), 869 ([Ru(dppm)2−H]+, 35).
4.4. X-ray crystallographic study of 9
Crystals suitable for the X-ray structural analysis
were grown by liquid diffusion of MeOH into a CH2Cl2

124
S.K. Hurst et al. / Journal of Organometallic Chemistry 633 (2001) 114–124
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5. Supplementary material
Crystallographic data for structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC no. 160385 for 9. Copies of this
information may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge, CB2
1EZ, UK (Fax: +44-1223-336033; e-mail: deposit@
ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
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Acknowledgements
We thank the Australian Research Council
(M.G.H.), the Belgian Government (Grant No. IUAP-
PIV/11) (A.P.), the Fund for Scientific Research-Flan-
ders (G.0338.98, G.0407.98) (A.P.), the K.U. Leuven
(GOA/2000/03) (A.P.) for supporting this work, and
Johnson–Matthey Technology Centre (M.G.H.) for the
generous loan of ruthenium salts. M.P.C. held an ARC
Australian Postdoctoral Research Fellowship, N.T.L.
was an Australian Postgraduate Awardee and M.G.H.
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