Isocyanide ligation at ruthenium(II) complexes with chelating tertiary amine and porphyrin ligands. Structural and electrochemical studies

Article abstract of DOI:10.1016/S0022-328X(99)00596-3

Reaction of [Ru(Me₃tacn)(PMe₃)₂(O₂CCF ₃)]PF₆ with one equivalent of t-BuNC or 4-cyano-1-isocyano-2,6-diisopropylbenzene (L′) in refluxing 1,2-dichloroethane gave [Ru(Me₃tacn)(PMe₃)(t-BuNC)(O₂CCF ₃)]PF₆ (1)·PF₆ and [Ru(Me₃tacn)(PMe₃)(L′)(O₂CCF ₃)]PF₆ (3)·PF₆, respectively. In the presence of zinc amalgam, reactions of [Ru(Me₃tacn)(H₂O)₂(O₂CCF ₃)](OTf)₂, trans-[Ru(16-TMC)Cl₂]Cl and cis-[Ru(2,2,2-tet-Me₆)Cl₂]PF₆ with an excess of t-BuNC in 1,2-dichloroethane, followed by anion metathesis, afforded [Ru(Me₃tacn)(t-BuNC)₂(O₂CCF ₃)]PF₆ (2)·PF₆, trans-[Ru(16-TMC)(t-BuNC)₂](ClO₄)₂ (4)·(ClO₄)₂ and cis-[Ru(2,2,2-tet-Me₆)(t-BuNC)₂](PF₆) ₂ (5)·(PF₆)₂, respectively. Treatment of [Ru(Por)(CO)(MeOH)] (Por=TPP, 4-MeO-TPP or 4-F-TPP) with an excess of t-BuNC or L′ gave [Ru(TPP)(t-BuNC)₂] (6) or [Ru(4-MeO-TPP)(L′)₂] (7) and [Ru(4-F-TPP)(L′)₂] (8), respectively. 1·PF₆-5·(PF₆)₂ display a quasi-reversible Ru(III/II) couple at potentials ranging from +0.65 to +1.42 V vs. FeCp₂^+/0. The E_1/2(Ru^III/II) of 5·(PF₆)₂ (+1.42 V vs. FeCp₂^+/0) is notably high compared with that of 4·(ClO₄)₂ (+0.65 V), reflecting the strong π-back-bonding in the cis-bis(tert-butyl isocyanide)ruthenium(II) complex. Irrespective of the overall charge, the cationic complex 4 and the neutral complexes 6-8 all exhibit a virtually linear RNC-Ru-CNR moiety.

Full text of DOI:10.1016/S0022-328X(99)00596-3

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 595 (2000) 114–125
Isocyanide ligation at ruthenium(II) complexes with chelating
tertiary amine and porphyrin ligands. Structural and
electrochemical studies
Fu-Wa Lee, Mei-Yuk Choi, Kung-Kai Cheung, Chi-Ming Che *
Department of Chemistry, The Uni6ersity of Hong Kong, Pokfulam Road, Hong Kong, People’s Republic of China
Received 2 August 1999; received in revised form 28 August 1999
Abstract
Reaction of [Ru(Me3tacn)(PMe3)2(O2CCF3)]PF6 with one equivalent of t-BuNC or 4-cyano-1-isocyano-2,6-diisopropylbenzene
(L%) in refluxing 1,2-dichloroethane gave [Ru(Me3tacn)(PMe3)(t-BuNC)(O2CCF3)]PF6 (1)·PF6 and [Ru(Me3tacn)(PMe3)-
(L%)(O2CCF3)]PF6 (3)·PF6, respectively. In the presence of zinc amalgam, reactions of [Ru(Me3tacn)(H2O)2(O2CCF3)]-
(OTf)2, trans-[Ru(16-TMC)Cl2]Cl and cis-[Ru(2,2,2-tet-Me6)Cl2]PF6 with an excess of t-BuNC in 1,2-dichloroethane, followed by
anion metathesis, afforded [Ru(Me3tacn)(t-BuNC)2(O2CCF3)]PF6 (2)·PF6, trans-[Ru(16-TMC)(t-BuNC)2](ClO4)2 (4)·(ClO4)2 and
cis-[Ru(2,2,2-tet-Me6)(t-BuNC)2](PF6)2 (5)·(PF6)2, respectively. Treatment of [Ru(Por)(CO)(MeOH)] (Por=TPP, 4-MeO–TPP or
4-F–TPP) with an excess of t-BuNC or L% gave [Ru(TPP)(t-BuNC)2] (6) or [Ru(4-MeO–TPP)(L%)2] (7) and [Ru(4-F–TPP)(L%)2]
(8), respectively. 1·PF6–5·(PF6)2 display a quasi-reversible Ru(III/II) couple at potentials ranging from +0.65 to +1.42 V vs.
FeCp2+/0. The E1/2(RuIII/II) of 5·(PF6)2 (+1.42 V vs. FeCp2+/0) is notably high compared with that of 4·(ClO4)2 (+0.65 V),
reflecting the strong p-back-bonding in the cis-bis(tert-butyl isocyanide)ruthenium(II) complex. Irrespective of the overall charge,
the cationic complex 4 and the neutral complexes 6–8 all exhibit a virtually linear RNC–Ru–CNR moiety. © 2000 Elsevier
Science S.A. All rights reserved.
Keywords: Isocyanide complexes; Ruthenium; Crystal structures; Porphyrins; Electrochemistry; Tertiary amine
oligomeric materials or extended solids [6]. Recently,
1,4-diisocyanobenzene [7], 1,4-dicyanobenzene [6c] and
1. Introduction
CN–C6H2–R2-2,6-CN-4 (R=H or CH3) [8] have been
employed as bridging ligands in the synthesis of
When compared with phosphines [1], alkyl- and aryl-
isocyanides [2] are less commonly encountered as auxil-
organometallic polymers [2,9]. Indeed, Mayr and co-
iary ligands in organometallic chemistry. Our interest in
workers have synthesized [FeI2(CN–C6H2–Me2-2,6,-
transition metal isocyanide complexes stemmed from
CN-4)4] and demonstrated the usefulness of this
the recent report that functionalized isocyanides [3] are
complex as a building block for molecular materials [8].
versatile bridging ligands for the formation of
Because ruthenium(II) is a good p-donor, there would
organometallic supermolecules [4]. Because of the linear
–NꢀC moiety, isocyanide ligands are relatively not
be considerable p-back-bonding effect in ruthenium-
(II)–isocyanide complexes. Therefore, we envisage that
sterically demanding upon coordination to metal ions
substantial electronic delocalization would be observed
[5]. With proper design of peripheral functional groups,
in polymeric ruthenium(II)–isocyanide solids. In this
their complexes can act as building blocks for
work, we report the synthesis, crystal structures and
characterization of the ruthenium(II) complexes ob-
tained from ligation of tert-butyl isocyanide and 4-
* Corresponding author. Tel.: +852-2859-2154; fax: +852-2857-
cyano-1-isocyano-2,6-diisopropylbenzene (L%) to ru-
1586.
thenium(II) ion containing the chelating tertiary amines
and porphyrin ligands.
E-mail addresses: leefw@hkusua.hku.hk (F.-W. Lee), cm-
che@hku.hk (C.-M. Che)
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(99)00596-3

F.-W. Lee et al. / Journal of Organometallic Chemistry 595 (2000) 114–125
115
air stable in the solid state and in solution at ambient
temperature.
2. Results and discussion
2.1. Synthesis and characterization
2.2. NMR spectroscopy
Reaction of [Ru(Me3tacn)(PMe3)2(O2CCF3)]PF6
(Me3tacn=1,4,7 - trimethyl - 1,4,7 - triazacyclononane)
with one equivalent of t-BuNC or 4-cyano-1-isocyano-
2,6-diisopropylbenzene (L%) in refluxing 1,2-dichloro-
ethane gave [Ru(Me3tacn)(PMe3)(t-BuNC)(O2CCF3)]-
PF6 (1)·PF6 or [Ru(Me3tacn)(PMe3)(L%)(O2CCF3)]PF6
(3)·PF6, respectively in good yields. In an attempt to
prepare the bis(isocyanide) complexes, a mixture of
1·PF6 or 3·PF6 and a fivefold excess of isocyanide
ligand in 1,2-dichloroethane was stirred at elevated
temperature. 1·PF6 or 3·PF6, however, was recovered.
Presumably the PMe3 ligand in [Ru(Me3tacn)(PMe3)-
(t-BuNC)(O2CCF3)]+ or [Ru(Me3tacn)(PMe3)(L%)(O2-
CCF3)]+ is inert toward further substitution reaction.
Therefore, [Ru(Me3tacn)(PMe3)2(O2CCF3)]PF6 is not a
good precursor for the preparation of the ruthenium-
(II)-bis(isocyanide) complex. We turned to another
precursor [RuIII(Me3tacn)(H2O)2(O2CCF3)](OTf)2 [10]
(OTf−=trifluoromethanesulphonate). In the presence
of zinc amalgam, this complex reacted with an excess of
t-BuNC in 1,2-dichloroethane to give [Ru(Me3tacn)-
(t-BuNC)2(O2CCF3)]+ (2), which was isolated as a
PF−6 salt. However, the complex [Ru(Me3tacn)-
(L%)2(O2CCF3)]+ could not be obtained by a similar
method, presumably the sterically demanding isopropyl
substituents on L% prevent formation of the target com-
plex (Scheme 1).
Our success in the preparation of trans-[Ru(16-
TMC)(CꢀCAr)2] [11] (16-TMC=1,5,9,13-tetramethyl-
1,5,9,13-tetraazacyclohexadecane) prompted us to study
the analogous isoelectronic ruthenium complexes with
CꢀN–R ligands. trans-[Ru(16-TMC)(t-BuNC)2]2+ (4)
was prepared by reacting [Ru(16-TMC)Cl2]Cl with an
excess of t-BuNC in the presence of Zn amalgam in
refluxing methanol. This procedure, however, did not
give any Ru(16-TMC) complex of L%. cis-[Ru(2,2,2-tet-
Me6)(t-BuNC)2]2+(2,2,2-tet-Me6=N,N,N%,N%-3,6-hexa-
methyl-3,6-diazaoctane-1,8-diamine) (5) was also ob-
tained from reaction of cis-[Ru(2,2,2-tet-Me6)Cl2]PF6,
t-BuNC and zinc amalgam. As we have not been
successful in preparing Ru(II) complexes of L% contain-
ing the 16-TMC ligand, we changed to the preparation
of the Ru(Por) (Por=porphyrinato dianion) complex
of L%. Treatment of [Ru(Por)(CO)(MeOH)] (Por=
meso-tetraphenylporphyrinato (TPP), meso-tetrakis(4-
methoxyphenyl)porphyrinato (4-MeO–TPP) or meso-
tetrakis(4-fluorophenyl)porphyrinato (4-F–TPP)) with
a large excess of t-BuNC or L% gave the bisaxially
coordinated complexes [Ru(TPP)(t-BuNC)2] (6), [Ru(4-
MeO–TPP)(L%)2] (7) and [Ru(4-F–TPP)(L%)2] (8), re-
spectively. All the isocyanide complexes prepared are
The 1H-NMR spectrum of 1·PF6 displays a sharp
singlet for NC(CH3)3, a doublet for P(CH3)3 and multi-
plets for Me3tacn protons in an integral ratio of 9:9:21
whereas 2·PF6 shows only one sharp singlet for the
t-BuNC protons and multiplets for Me3tacn protons in
a ratio of 18:21. These results reveal that in 1, there is
only one t-BuNC per Me3tacn ligand but in 2, there is
a plane of symmetry bisecting the two t-BuNC and the
Me3tacn ligands. Complex 3·PF6 exhibits a septet for
CH(CH3)2, a doublet for C(CH3)2, a doublet for
P(CH3)3 and multiplets for Me3tacn protons in an
integral ratio of 2:12:9:21, suggesting that there is only
1
one L% per Me3tacn. The H-NMR spectra of 4·(ClO4)2
and 5·(PF6)2 show a singlet for t-BuNC in accordance
with pseudo-D4h and C2 symmetry, respectively. Inte-
gration reveals that in 4 and 5 there are two t-BuNC
per chelating tertiary amine ligand. As observed in
other metalloporphyrins [12,13], the proton signals of
the axial ligands in 6–8 are significantly upfield shifted
(6 by 1.88 ppm for t-BuNC; and 7 and 8 by \1.00
ppm for i-propyl and aryl protons) when compared to
those of free ligands due to the porphyrin ring current
effect. Integration shows that there are two isocyanide
ligands in 6–8 which also display a single resonance for
the pyrrolic protons.
Notably, the 13C signals for the bound t-BuNꢀC in 5
and Ar–NꢀC in 8 were found at 152.2 and 164.0 ppm,
respectively. The 31P{1H}-NMR spectra of cationic
complexes 1 and 3 show a single resonance at 2.8 and
0.4 ppm, respectively, which fall in the range observed
for coordinated PMe3 [10].
2.3. IR and UV–6is spectroscopy
Selected IR spectral data of 1·PF6–8 are summarized
in Table 1. Complexes 1·PF6–3·PF6 exhibit bands at ca.
2110 and 1690 cm−1 attributable to the stretches of
–NꢀC in bound isocyanide and CꢁO in the h1-O2CCF3
ligand, respectively. Similar bands are observed for
[Ru(Me3tacn)(CNC6H3Me2-2,6)2(O2CCF3)]PF6 (2125
and 2145 cm−1 for w(–NꢀC) and 1695 cm−1 for
w(CꢁO)) [14] and [Ru(h5-C5Me5)(t-BuNC)2Cl] (2110
and 2046 cm−1 for w(–NꢀC)) [12].
Complexes 4·(ClO4)2 and 6 show only one intense
–NꢀC stretch in accordance with a trans configuration
of the bis-(alkyl isocyanide) ligands while 2·PF6 and
5·(PF6)2 show two –NꢀC stretches at ca. 2115 and
2158 cm−1
,
which are comparable to those of
[Ru(Me3tacn)(CNC6H3Me2-2,6)2(O2CCF3)]PF6 [14] and

/
5
(
1
125
Scheme 1. (Coordination of L% via the isocyano group.)

F.-W. Lee et al. / Journal of Organometallic Chemistry 595 (2000) 114–125
117
Table 1
Selected IR spectral data (from Nujol mull)
Compound
w(–NꢀC) (cm−1
)
w(–CꢀN) (cm−1
)
w(CꢀO) (cm−1
)
t-BuNC
2138
4-Cyano-1-isocyano-2,6-diisopropylbenzene (L%)
[Ru(Me3tacn)(t-BuNC)(O2CCF3)(PMe3)]PF6 (1)·PF6
[Ru(Me3tacn)(t-BuNC)2(O2CCF3)]PF6 (2)·PF6
[Ru(Me3tacn)(L%)(O2CCF3)(PMe3)]PF6 (3)·PF6
[Ru(Me3tacn)(CNC6H3Me2-2,6)2(O2CCF3)]PF6 [14]
trans-[Ru(16-TMC)(t-BuNC)2](ClO4)2 (4)·(ClO4)2
cis-[Ru(2,2,2-tet-Me6)(t-BuNC)2](PF6)2 (5)·(PF6)2
[Ru(TPP)(t-BuNC)2] (6) a
2123
2112
2110, 2154
2048
2125, 2145
2120
2115, 2158
2119
2077
2230
1689
1694
1693
1695
2233
[Ru(4-MeO–TPP)(L%)2] (7) a
2231
2234
[Ru(4-F–TPP)(L%)2] (8) a
2079
a From KBr pellets.
[Ru(h5-C5Me5)(t-BuNC)2Cl] [12]. On the other hand,
the IR spectra of 3·PF6, 7 and 8 display bands at ca.
2077 and 2231 cm−1 attributed to the –NꢀC and
–CꢀN stretches in L%, respectively. The –NꢀC stretch-
ing frequencies of the ruthenium complexes prepared in
this work are only slightly lower than those of the free
isocyanide ligands indicating that p-back-bonding to
the coordinated isocyanide ligands is not as important
as expected. The larger decrease in w(–NꢀC) values
observed for the complexes of aryl isocyanide L% as
compared to those of t-BuNC implies that aryl iso-
cyanide is a better p-acceptor than alkyl isocyanide [15].
Complexes 7 and 8 show similar w(–NꢀC) values al-
though the MeO and F substituents are expected to
exert opposite electronic effect. The w(–CꢀN) values of
3·PF6, 7 and 8 are close to that of free ligand L%
suggesting that the peripheral cyanide group remains
unperturbed.
tively assigned to be Ru(III/II). Oxidation of 1·PF6
occurs at a slightly lower potential than that of 2·PF6,
presumably PMe3 is a better s-donor but a weaker
p-acceptor than t-BuNC. On the other hand, L% is a
better p-acceptor than t-BuNC, thereby making 3·PF6
more resistant toward oxidation than 1·PF6. Moreover,
as PhCꢀC− is a much better s-donor than t-BuNC,
trans-[Ru(16-TMC)(CꢀCC6H5)2] (−0.74 V) [11] is
much easier to oxidize than 4·(ClO4)2. It is noteworthy
that the E1/2(RuIII/II
)
of cis-[Ru(2,2,2-tet-Me6)(t-
BuNC)2](PF6)2 5·(PF6)2 is notably high compared to
that of 4·(ClO4)2 although the w(–NꢀC) values of both
complexes are similar.
It can be seen from Table 2 that both 7 and 8 exhibit
two reversible oxidation couples in the potential range
+0.20 to +0.90 V. In the absence of a strong p-acid
ligand such as terminal carbonyl [18], the first oxidation
couple is assignable to Ru(II/III) while the second one
is ascribed to the oxidation of the porphyrin ring and
As observed for [Ru(NH3)4(C7H7NC)]2+ [16], which
gives a metal-to-ligand charge transfer (MLCT) band at
244 nm, complexes 1, 2, 3 and 5 exhibit similar elec-
tronic transition(s) at ca. 250–320 nm. For example,
complex 3·PF6 exhibits an intense absorption band at
317 nm, attributed to RuII“p*(L%) transition. For the
porphyrin complexes 6–8, the dp(Ru)“p* (isocyanide)
transitions are probably mixed with the p“p* transi-
tion of the porphyrin ring and therefore could not be
located [17].
formation of
a
Ru(III)–cation radical complex,
[RuIII(Por)(L%)2]+ (Por=4-MeO–TPP, 4-F–TPP). The
Table 2
Selected electrochemical data a
Complex
E1/2 (RuIII/II
)
E1/2 (RuII/I
)
1·PF6
2·PF6
3·PF6
4·(ClO4)2
5·(PF6)2
7
+0.73
+0.89
+0.89
+0.65
2.4. Electrochemical studies
+1.42
+1.30 b,c
+0.71 b
+0.25
−2.01 c
−2.02 c
Electrochemistry of the title ruthenium(II)–iso-
cyanide complexes has been examined by cyclic voltam-
metry (CV) and the electrochemical data are listed in
Table 2. Complexes 1·PF6–5·(PF6)2 display a quasi-re-
versible oxidation couple at potentials ranging from
+0.65 to +1.42 V. The peak current is comparable to
that of the Cp2Fe+/ 0 couple measured at the same
concentration under identical conditions; hence a one-
electron process is implied. These couples are tenta-
8
+1.56 b,c
+0.86 b
+0.33
a E1/2 (V vs. Cp2Fe+/0, scan rate=100 mV s−1) in acetonitrile at
298 K with 0.1 M NBun4PF6 as supporting electrolyte.
b Formation of cationic radical (see text).
c Irreversible couple.

118
F.-W. Lee et al. / Journal of Organometallic Chemistry 595 (2000) 114–125
Fig. 1. Perspective view of complex 4 with the atomic numbering scheme. Hydrogen atoms have been omitted for clarity. Thermal ellipsoids are
shown at 40% probability.
Fig. 2. Perspective view of complex 6 with the atomic numbering scheme. Hydrogen atoms have been omitted for clarity. Thermal ellipsoids are
shown at 40% probability.
irreversible oxidation wave at +1.30 V for 7 or +1.56
V for 8 suggests that the Ru(III)-dication is unstable on
the CV time scale. In addition, 7 and 8 undergo an
irreversible reduction at −2.01 V which can be at-
tributed to the formation of highly unstable
[RuI(Por)(L%)2]− [18]. In general, the oxidation couples
of 8 were found at higher potentials than those of 7,
reflecting the stronger electron withdrawing effect of
–F substituent compared to the –OMe group.
2.5. Crystal structures
Figs. 1–4 show perspective views of complexes 4 and
6–8, respectively. Crystal data are collected in Table 3

F.-W. Lee et al. / Journal of Organometallic Chemistry 595 (2000) 114–125
119
while selected bond distances and angles are listed in
Table 4. As shown from the perspective view of 4, the
ruthenium atom resides in a distorted octahedral envi-
ronment and is coordinated by four equatorial nitrogen
atoms of 16-TMC and two t-BuNꢀC ligands in a
trans-configuration. The crystal structure of 4 consists
of one CH3CN molecule as the solvent of crystalliza-
tion. The six-membered chelate rings of the Ru(16-
TMC) fragment are all in chair forms with the
N-methyl groups adopting the ‘two up, two down’
configuration as in trans-[Ru(16-TMC)(CꢀCC6H5)2]
atoms in 6–8 reside in a pseudo octahedral environ-
ment; all are situated at the centre of the mean plane
defined by the four nitrogen atoms of the porphyrin
ligands and bonded to the two axial isocyanide ligands.
The crystal structures of 7 and 8 consist of three and
five benzene molecules, respectively, as the solvent of
crystallization. The Ru–C distances of 6 (molecule 1:
,
,
,
2.015(5) A), 7 (1.980(4) A) and 8 (1.988(5) A) are within
the range observed for Ru–C bond [14,19] and com-
parable to that of 4. It is apparent that the Ru–C and
RuCꢀNR distances [14,20] found in this work are not
sensitive to the nature of the macrocyclic ligand, irre-
spective of 16-TMC and porphyrinato anion. It is
interesting to note that the RNC–Ru–CNR fragment
is essentially linear in these structures. For example, the
Ru–C(1)–N(3) and C(1)–N(3)–C(2) angles in 4 are
178.8(7) and 179.4(7)°, respectively. As L% can act as a
bridging ligand, 7 and 8 are potential building blocks
for extended solids or molecular materials.
,
[11]. The Ru–C distance observed for 4 (1.989(7) A)
falls in the normal range for Ru–C bonds [19] and is
comparable to those in cis-[Ru(Me3tacn)(CNC6H3Me2-
,
2,6)2(O2CCF3)]PF6 (1.921(4) and 1.912(4) A) [14] and
,
trans-[Ru(16-TMC)(CꢀCC6H5)2] (2.077(4) A) [11] as ex-
pected since 2,6-Me2C6H3NC, t-BuNC and PhCꢀC−
are isoelectronic.
It can be seen from Figs. 2–4 that the ruthenium
Fig. 3. Perspective view of complex 7 with the atomic numbering scheme. Hydrogen atoms have been omitted for clarity. Thermal ellipsoids are
shown at 40% probability.

120
F.-W. Lee et al. / Journal of Organometallic Chemistry 595 (2000) 114–125
Fig. 4. Perspective view of complex 8 with the atomic numbering scheme. Hydrogen atoms have been omitted for clarity. Thermal ellipsoids are
shown at 40% probability.
3. Conclusions
virtually linear RNꢀC–Ru–CꢀNR moieties, which are
essential for making 1-D polynuclear assemblies and
supramolecular structures via peripheral –CN groups.
A series of ruthenium(II) mono- and bis-isocyanide
complexes supported by chelating tertiary amine and
porphyrinato ligands have been synthesized. They are
air stable in the solid state and in solution at ambient
temperature and show a quasi-reversible Ru(II/III) cou-
ple. It is worth noting that the cis-[RuII(t-BuNC)2]2+
moiety in 5 is much more resistant to oxidation com-
pared to trans-[RuII(t-BuNC)2]2+ in 4. Results from
X-ray diffraction studies reveal that the Ru–C and
RuCꢀNR distances are evidently insensitive to the over-
all electronic charges of the metal complexes and within
the normal range. It is apparent that 6–8 consist of
4. Experimental
4.1. General procedures
All reactions were performed under a nitrogen atmo-
sphere using standard Schlenk techniques unless other-
wise stated. Solvents were dried by standard methods
and distilled before use. 4-Cyano-1-isocyano-2,6-diiso-
propylbenzene (L%) was a donation from Dr M.-X. Li

F.-W. Lee et al. / Journal of Organometallic Chemistry 595 (2000) 114–125
121
[8]. [Ru(Me3tacn)(H2O)2(O2CCF3)](OTf)2 [10], [Ru-
(Me3tacn)(PMe3)2(O2CCF3)]PF6, trans-[Ru(16-TMC)-
Cl2]Cl, cis-[Ru(2,2,2-tet-Me6)Cl2]PF6 [21], [Ru(TPP)-
(CO)(MeOH)] [22], [Ru(4-MeO–TPP)(CO)(MeOH)]
and [Ru(4-F–TPP)(CO)(MeOH)] [23] were prepared by
published procedures. Zinc powder (BDH), mercury(II)
chloride (Merck), ammonium hexafluorophosphate
(Aldrich) and tert-butyl isocyanide (Aldrich) were used
as received.
ical Systems (BAS) model 100 B/W electrochemical
analyser. A conventional two-compartment electro-
chemical cell was used. The glassy carbon electrode was
polished with 0.05 mm alumina on a microcloth, soni-
cated for 5 min in deionized water and rinsed with
acetonitrile before use. An Ag/AgNO3 (0.1 M in
CH3CN) electrode was used as reference electrode. All
solutions were degassed with argon before experiments.
E1/2 values were taken from the average of the cathodic
and anodic peak potentials for the oxidative and reduc-
tive waves. The E1/2 value of the ferrocenium/ferrocene
couple (Cp2Fe+/ 0) measured in the same solution was
used as an internal reference.
1H-, 13C{1H}- and 31P{1H}-NMR spectra were
recorded on Jeol 270, Bruker DPX-300, and Bruker
DRX-500 FT-NMR spectrometers. Chemical shifts
1
were referenced to Me4Si (for H, 13C) and 85% H3PO4
(for 31P). In the 13C{1H}-NMR spectra, multiplets for
16-TMC were observed because of the flexible nature of
the propylene groups, and the chemical shifts listed
correspond to the most intense signals. Fast atom bom-
bardment (FAB) mass spectra were obtained on a
Finnigan MAT 95 mass spectrometer with a 3-ni-
trobenzyl alcohol matrix. Infrared spectra were
recorded from Nujol mulls or KBr pellets on a Bio-Rad
FTIR spectrometer. UV–vis spectra were recorded on
Perkin–Elmer Lambda 19 and Milton Roy (Spectronic
3000 Array) diode array spectrophotometers. Elemental
analyses were performed by the Butterworth Laborato-
ries Ltd., Teddington, UK.
4.2. [Ru(Me3tacn)(PMe3)(t-BuNC)(O2CCF3)]PF6
(1)·PF6
A
mixture of [Ru(Me3tacn)(PMe3)2(O2CCF3)]PF6
(0.10 g, 0.14 mmol) and t-BuNC (1.0 cm3) in 1,2-
dichloroethane (10 cm3) was refluxed under a nitrogen
atmosphere for 12 h. After cooling, the solvent was
removed in vacuo. The solid residue was washed with
diethyl ether (10 cm3×5) and dried to give a pale
yellow solid. Diffusion of diethyl ether into an acetone
solution gave a yellow crystalline solid. Yield=0.06 g
(56%). Anal. Calc. for C19H39N4F9O2P2Ru: C, 33.10; H,
Cyclic voltammetry was performed with a Bioanalyt-
Table 3
Crystal data for 4·(ClO4)2·CH3CN and 6–8·5C6H6
4·(ClO4)2·CH3CN
6
7·3C6H6
8·5C6H6
Formula
C26H54N6O8Cl2Ru·CH3CN C54H46N6Ru
C76H68N8O4Ru·3C6H6 C72H56F4N8Ru·5C6H6
Mr
791.78
880.07
1492.83
1600.92
Crystal size, mm
Crystal system
Space group
0.35×0.20×0.10
Monoclinic
C2/c (No. 14)
18.832(3)
10.772(3)
18.605(3)
0.30×0.20×0.10
Triclinic
0.30×0.20×0.10
Triclinic
0.20×0.15×0.15
Triclinic
(
(
(
P1 (No. 2)
P1(No. 2)
P1 (No. 2)
,
a (A)
11.651(2)
14.039(2)
15.292(2)
78.71(2)
67.82(2)
90.31(2)
2262.7(8)
2
12.352(4)
12.773(3)
14.780(3)
103.13(2)
93.67(2)
115.96(2)
2006(1)
1
11.525(4)
14.034(4)
14.872(4)
68.17(2)
72.14(2)
84.33(2)
2125(1)
1
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
96.43(2)
3
,
V (A )
Z
3750(1)
4
1.402
6.13
Dcalc (g cm−3
)
1.292
3.90
912
1.236
2.52
782
1.251
2.46
834
v(Mo–Kh) (cm−1
F(000)
)
1664
2qmax (°)
50.0
50.9
50.0
50.0
No. of data measured
No. of unique data
No. of observed data (I\3|(I))
No. of variables
3615
3497
2024
211
0.050, 0.068
2.35
+0.71, −0.38
24277
7544
5108
553
0.045, 0.061
1.37
+0.62, −0.71
6115
5767
4408
439
0.048, 0.065
1.88
+0.83, −0.45
7838
7503
4469
445
0.051, 0.067
1.74
+0.61, −0.39
R a, wR b
GoF
Residual z (e A
−3
,
)
a R=ꢀꢁꢁFoꢁ−ꢁFcꢁꢁ/ꢀꢁFoꢁ.
2
2 1/2
b wR=[ꢀ wꢁꢁFoꢁ−ꢁFcꢁꢁ /ꢀ wꢁFoꢁ ]
.

122
F.-W. Lee et al. / Journal of Organometallic Chemistry 595 (2000) 114–125
Table 4
,
Selected bond distances (A) and angles (°) for 4·(ClO4)2 and 6–8
Complex 4·(ClO4)2
Ru–N(1)
N(3)–C(1)
2.246(6)
1.143(8)
Ru–N(2)
N(3)–C(2)
2.255(5)
1.469(8)
Ru–C(1)
N(1)–C(6)
1.989(7)
1.470(1)
N(1)–Ru–N(1*)
N(1)–Ru–N(2)
N(1)–Ru–C(1)
C(1)–Ru–C(1*)
N(2)–Ru–C(1*)
180.0
Ru–C(1)–N(3)
N(1)–Ru–N(2*)
N(1)–Ru–C(1*)
N(2)–Ru–C(1)
C(1)–N(3)–C(2)
178.8(7)
88.9(2)
91.1(2)
88.6(2)
179.4(7)
91.1(2)
88.9(2)
180.0
91.4(2)
Complex 6
Ru–N(1)
Ru–N(2)
Ru–C(1)
Molecule 1
2.057(3)
2.073(3)
2.015(5)
1.153(6)
Molecule 2
2.065(4)
2.063(3)
2.011(5)
1.151(6)
N(3)–C(1)
N(1)–Ru–N(1*)
N(1)–Ru–N(2)
N(1)–Ru–C(1)
C(1)–Ru–C(1*)
C(1)–N(3)–C(2)
Ru–C(1)–N(3)
180.0
180.0
91.0(1)
90.1(2)
180.0
167.8(5)
170.6(4)
90.2(1)
93.2(2)
180.0
167.6(5)
169.3(4)
Complex 7
Ru–N(1)
N(3)–C(11)
2.057(3)
1.154(5)
Ru–N(2)
N(4)–C(18)
2.049(3)
1.120(7)
Ru–C(11)
Ru–C(11)
1.980(4)
1.988(5)
N(1)–Ru–N(1*)
N(1)–Ru–N(2)
N(1)–Ru–C(11)
180.0
90.2(1)
92.8(1)
C(11)–Ru–C(11*)
C(11)–N(3)–C(12)
Ru–C(11)–N(3)
180.0
178.3(4)
173.7(4)
Complex 8
Ru–N(1)
N(3)–C(11)
2.058(4)
1.156(6)
Ru–N(2)
N(4)–C(18)
2.060(4)
1.115(7)
N(1)–Ru–N(1*)
N(1)–Ru–C(11)
C(11)–N(3)–C(12)
180.0
86.4(2)
173.9(5)
N(1)–Ru–N(2)
C(11)–Ru–C(11*)
Ru–C(11)–N(3)
90.1(1)
180.0
174.2(4)
5.70; N, 8.12. Found: C, 33.37; H, 5.79; N, 7.92.
1H-NMR (300 MHz, (CD3)2CO): 1.52 (d, JPH=8.6 Hz,
9H, P(CH3)3), 1.63 (s, 9H, C(CH3)3), 2.90–3.39 (m,
21H, Me3tacn). 13C{1H}-NMR (500 MHz, (CD3)2CO):
17.4 (d, JPC=28.7 Hz, P(CH3)3), 31.0 (C(CH3)3, 52.1,
53.1, 58.3 (Me3tacn), 58.5 (C(CH3)3), 58.8, 59.2, 60.1,
61.0, 63.0, 63.2 (Me3tacn). 31P{1H}-NMR (202 MHz,
(CD3)2CO): 2.8. Infrared (Nujol, cm−1): w(–NꢀC)
2112s; w(CꢁO) 1689s. FAB MS (m/z): 545, [M+]. UV–
vis umax, nm (log mmax) in CH3CN: 236 (3.71), 258 (3.24),
540 (1.41).
(10 cm3×3). Recrystallization by diffusion of diethyl
ether into an acetone solution gave a yellow crystalline
solid. Yield=0.05
g
(72%). Anal. Calc. for
C21H39N5F9O2PRu: C, 36.21; H, 5.64; N, 10.05. Found:
C, 36.18; H, 5.40; N, 10.01. 1H-NMR (300 MHz,
CDCl3): 1.54 (s, 18H, C(CH3)3), 2.86–3.23 (m, 21H,
Me3tacn). 13C{1H}-NMR (500 MHz, CDCl3): 31.0
(C(CH3)3), 51.3, 57.6 (Me3tacn), 58.1 (C(CH3)3), 58.2,
59.0, 61.3 (Me3tacn). Infrared (Nujol, cm−1): w(–NꢀC)
2110s, 2154s; w(CꢁO) 1693s. FAB MS (m/z): 552, [M+].
UV–vis umax, nm (log mmax) in CH3CN: 237 (3.90), 316
(2.54).
4.3. [Ru(Me3tacn)(t-BuNC)2(O2CCF3)]PF6 (2)·PF6
4.4. [Ru(Me3tacn)(PMe3)(L%)(O2CCF3)]PF6 (3)·PF6
A mixture of [Ru(Me3tacn)(H2O)2(O2CCF3)](OTf)2
(0.10 g, 0.15 mmol), t-BuNC (1.0 cm3) and zinc amal-
gam (1 g) in 1,2-dichloroethane (10 cm3) was stirred at
ambient temperature under a nitrogen atmosphere for
12 h. The solution was filtered and concentrated to ca.
5 cm3. A saturated solution of NH4PF6 in 1,2-
dichloroethane was added to give a pale yellow precipi-
tate, which was filtered and washed with diethyl ether
A
mixture of [Ru(Me3tacn)(PMe3)2(O2CCF3)]PF6
(0.10 g, 0.14 mmol) and L% (0.05 g, 0.24 mmol) in
1,2-dichloroethane (10 cm3) was refluxed under a nitro-
gen atmosphere for 12 h. After cooling, the solvent was
removed in vacuo. The solid residue was washed with
diethyl ether (10 cm3×5) and dried to give a pale
yellow solid. Recrystallization by diffusion of diethyl

F.-W. Lee et al. / Journal of Organometallic Chemistry 595 (2000) 114–125
123
ether into an acetone solution gave a yellow crystal-
line solid. Yield=0.07 g (85%). Anal. Calc. for
C28H46N5F9O2P2Ru: C, 41.08; H, 5.61; N, 8.55.
Found: C, 41.27; H, 5.62; N, 8.35. 1H-NMR (500
MHz, CDCl3): 1.24 (d, JHH=6.8 Hz, 12H, C(CH3)2),
1.50 (d, JHH=8.5 Hz, 9H, P(CH3)3), 2.91–3.40 (m,
13.6, 22.5 (NCH3), 30.5 (C(CH3)3), 31.4 (NCH3), 52.2
(C(CH3)3), 59.1, 61.7, 63.4 (NCH2), 152.2 (–NꢀC).
Infrared (Nujol, cm−1): w(–NꢀC) 2115, 2158. FAB
MS (m/z): 498, [M2+]; 413, [M–t-BuNC]2+. UV–vis
umax, nm (log mmax) in CH3CN: 236 (3.77), 280 (3.04),
338 (2.86).
21H, Me3tacn), 3.55 (septet,
JHH=6.8 Hz, 2H,
CH(CH3)2), 7.48 (s, 2H, Haryl). 13C{1H}-NMR (500
MHz, CDCl3): 17.8 (d, JPC=29.2 Hz, P(CH3)3), 22.3
(C(CH3)2), 23.8 (C(CH3)2), 52.9, 58.4, 59.3, 59.4, 59.9,
60.6, 60.7, 62.2, 64.0 (Me3tacn), 111.8 (–CꢀN), 118.2
(Caryl), 118.3, 118.4 (O2CCF3), 127.5, 128.1, 147.0
(Caryl), 173.1 (–NꢀC). 31P{1H}-NMR (202 MHz,
CD2Cl2): 0.37. Infrared (Nujol, cm−1): w(–NꢀC)
2048s, w(–CꢀN) 2233w; w(CꢁO) 1698s. FAB MS (m/
z): 674, [M+]; 598, [M–PMe3]+. UV–vis umax, nm
(log mmax) in CH3CN: 239 (4.43), 317 (4.22), 539 (0.81).
4.7. [Ru(TPP)(t-BuNC)2] (6)
This complex was prepared by a modified procedure
[24]. To a suspension of [Ru(TPP)(CO)(MeOH)] (0.21
g, 0.27 mmol) in benzene (10 cm3) was added t-BuNC
(1.0 cm3). The resulting dark-red solution was stirred
at ambient temperature for 2 h. All volatiles were
removed in vacuo and the solid residue was washed
with n-hexane (10 cm3×5) and dried in vacuo. Purple
crystals suitable for X-ray crystallography were ob-
tained by diffusion of n-pentane into a benzene solu-
tion. Yield=0.23 (97%). Anal. Calc. for C54H46N6Ru:
C, 73.70; H, 5.23; N, 9.55. Found: C, 73.66; H, 5.26;
4.5. trans-[Ru(16-TMC)(t-BuNC)2](ClO4)2 (4)·(ClO4)2
A
mixture of [Ru(16-TMC)Cl2]Cl (0.1 g, 0.20
1
mmol), t-BuNC (1.0 cm3) and zinc amalgam (1 g) in
methanol (10 cm3) was refluxed under a nitrogen at-
mosphere for 12 h. After cooling, the solution was
filtered and concentrated to ca. 5 cm3. A saturated
solution of NaClO4 in methanol was added to afford a
pale yellow solid. Diffusion of diethyl ether into an
N, 9.51. H-NMR (300 MHz, CDCl3): −0.44 (s, 18H,
C(CH3)3), 7.66 (dd, JHH=1.7, 3.2 Hz, 12H, Hm and
Hp), 8.13 (d, JHH=3.7 Hz, 8H, Ho), 8.40 (s, 8H, Hi).
13C{1H}-NMR (500 MHz, CD2Cl2): 29.0 (C(CH3)3),
53.5 (C(CH3)3), 121.1, 126.2, 126.7, 131.2, 134.1,
143.4, 143.5 (Caryl). Infrared (KBr, cm−1): w(–NꢀC)
2119. FAB MS (m/z): 880, [M+]; 797, [M–t-BuNC]+.
UV–vis umax, nm (log mmax) in CH2Cl2: 263 (4.74), 399
(4.82), 417 (5.62), 527 (4.18).
acetone solution gave
a yellow crystalline solid.
Yield=0.08 (53%). Anal. Calc. for C26H54-
g
N6Cl2O8Ru: C, 41.60; H, 7.25; N, 11.19. Found: C,
41.64; H, 7.21; N, 11.17. 1H-NMR (300 MHz,
CD3CN): 1.94 (m, 16H, NCH2), 2.12 (s, 18H,
C(CH3)3), 2.53 (s, 12H, NCH3), 3.00–3.20 (m, 8H,
CH2). 13C{1H}-NMR (500 MHz, CD3CN): 20.3
(NCH2CH2), 29.3 (C(CH3)3), 51.1 (NCH3), 61.47,
70.06 (NCH2). Infrared (Nujol, cm−1): w(–NꢀC)
2120s. FAB MS (m/z): 552, [M2+]; 469, [M–t-
BuNC]2+. UV–vis umax, nm (log mmax) in CH3CN: 236
(4.55).
4.8. [Ru(4-MeO–TPP)(L%)2] (7)
[Ru(4-MeO–TPP)(CO)(MeOH)] (0.09 g, 0.10 mmol)
was suspended in benzene (10 cm3) under an argon
atmosphere. L% (0.05 g, 0.25 mmol) was added and the
resulting solution was stirred at ambient temperature
for 18 h. All volatiles were removed in vacuo and the
solid residue was washed with n-hexane (20 cm3×3).
Red crystals were obtained by diffusion of n-pentane
into a benzene solution. Yield=0.10 g (81%). Anal.
Calc. for C76H68N8O4Ru: C, 72.55; H, 5.41; N, 8.90.
Found: C, 72.52; H, 5.36; N, 8.86. 1H-NMR (300
4.6. cis-[Ru(2,2,2-tet-Me6)(t-BuNC)2](PF6)2 (5)·(PF6)2
A mixture of cis-[Ru(2,2,2-tet-Me6)Cl2]PF6 (0.1 g,
0.18 mmol), t-BuNC (1.0 cm3) and zinc amalgam (1 g)
in methanol (10 cm3) was stirred at ambient tempera-
ture under a nitrogen atmosphere for 8 h. The pale
yellow solution was filtered and evaporated to dryness.
The residue was washed with n-hexane (10 cm3×2)
and dried in vacuo. Recrystallization by diffusion of
diethyl ether into an acetone solution gave a yellow
crystalline solid. Yield=0.08 g (56%). Anal. Calc. for
C22H48N6F12P2Ru: C, 33.55; H, 6.10; N, 10.67. Found:
C, 33.49; H, 6.14; N, 10.63. 1H-NMR (300 MHz,
CD2Cl2): 0.86 (s, 6H, NCH3), 0.87 (s, 6H, NCH3),
1.27 (s, 6H, NCH3), 1.62 (s, 18H, C(CH3)3), 2.64–3.15
(m, 12H, CH2). 13C{1H}-NMR (500 MHz, CD2Cl2):
MHz, CD2Cl2): −0.12 (d,
JHH=6.80 Hz, 24H,
C(CH3)2), 0.15 (m, 4H, CH(CH3)2), 4.05 (s, 12H,
OCH3), 6.54 (s, 4H, Haryl), 7.22 (d, JHH=8.6 Hz, 8H,
Hm), 7.97 (d, JHH=8.6 Hz, 8H, Ho), 8.54 (s, 8H, Hi).
13C{1H}-NMR (500 MHz, CD2Cl2): 20.5 (CH(CH3)2),
29.0 (CH(CH3)2), 55.9 (OCH3), 111.0 (–CꢀN), 112.3,
118.4, 121.1, 126.8, 128.7, 131.8, 135.3, 136.0, 144.5,
145.0, 159.5 (Caryl). Infrared (KBr, cm−1): w(–NꢀC)
2077, w(–CꢀN), 2231. FAB MS (m/z): 1258, [M+];
1046, [M–L%]+; 834, [M–2L%]+. UV–vis umax, nm
(log mmax) in CH3CN: 256 (4.86), 336 (4.42), 416 (5.60),
537 (4.15).

124
F.-W. Lee et al. / Journal of Organometallic Chemistry 595 (2000) 114–125
5. Supplementary material
4.9. [Ru(4-F–TPP)(L%)2] (8)
Crystallographic data for the structures reported in
this paper have been deposited with the Cambridge
Crystallographic Data Centre, CCDC nos. 133434,
133435, 133436 and 133437 for compounds
4·(ClO4)2·CH3CN, 6,7·3C6H6 and 8·5C6H6, respectively.
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).
The procedure was the same as that for 7 except
[Ru(4-F–TPP)(CO)(MeOH)] was used. Yield=0.12 g
(87%). Anal. Calc. for C72H56F4N8Ru: C, 71.35; H,
4.62; N, 9.25. Found: C, 71.78; H, 4.77; N, 9.09.
1H-NMR (300 MHz, CD2Cl2): −0.12 (d, JHH=6.80
Hz, 24H, C(CH3)2), 0.13 (septet, JHH=6.80 Hz, 4H,
CH(CH3)2), 6.55 (s, 4H, Haryl), 7.40 (tm, 8H, Hm), 8.01
(qm, 8H, Ho), 8.52 (s, 8H, Hi). 13C{1H}-NMR (500
MHz, CD2Cl2): 20.5 (CH(CH3)2), 29.0 (CH(CH3)2),
111.3 (–CꢀN), 113.6, 118.2, 120.5, 127.0, 128.7, 131.9,
135.6, 139.5, 144.4, 144.9, 162.0 (Caryl), 164.0 (–NꢀC).
Infrared (KBr, cm−1): w(–NꢀC) 2079, w(–CꢀN), 2234.
FAB MS (m/z): 1211, [M]+; 998, [M–L%]+; 786, [M–
2L%]+. UV–vis umax, nm (log mmax) in CH2Cl2: 261
(4.86), 326 (4.48), 417 (5.51), 538 (4.25).
Acknowledgements
We thank the University of Hong Kong and the
Hong Kong Research Grants Council for financial
support.
4.10. Structural determination of 4·(ClO4)2·CH3CN
and 6–8·5C6H6
References
Crystals of 4·(ClO4)2·CH3CN and 6–8·5C6H6 were
grown by diffusion of diethyl ether or n-pentane into
an acetone or a benzene solution, respectively. The
crystals were mounted on a glass fibre and diffraction
data were collected at 301 K on a MAR (6) or Rigaku
AFC7R (4·(ClO4)2·CH3CN, 7·3C6H6 and 8·5C6H6) dif-
fractometer using graphite monochromatized Mo–Kh
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,
radiation (u=0.71073 A). All the structures were
solved by direct methods (SIR92) [25], expanded by
Fourier techniques and refined by full-matrix least-
squares using the teXsan [26] program on a Silicon
Graphics Indy computer. Crystal data and details of
collection and refinement are shown in Table 3.
For 4·(ClO4)2·CH3CN, all non-H atoms were refined
anisotropically and H atoms at calculated positions
with thermal parameters equal to 1.3 times that of the
attached C atoms were not refined. The H atoms of the
CH3CN solvent molecule in 4·(ClO4)2·CH3CN were not
included. For 6, one crystallographic asymmetric unit
consists of two halves of a molecule with Ru(1) and
Ru(2) at special positions at 0, 0, 0 and 1/2, 1/2, 1/2,
respectively. All 62 non-H atoms were refined an-
isotropically and 46 H atoms at calculated positions
with thermal parameters equal to 1.3 times that of the
attached C atoms were not refined. Starred atoms have
coordinates at –x, –y, –z. For both 7·3C6H6 and
8·5C6H6, one crystallographic asymmetric unit consists
of half of one formula unit. One of the benzene
molecules is generated by a centre of symmetry. In the
least-squares refinement, all non-H atoms of the por-
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