Syntheses and structures of ruthenium(II) complexes bearing hybrid phosphine-thioether ligands, Me2PCH2CH2SR

Article abstract of DOI:10.1016/S0022-328X(99)00334-4

Hybrid phosphine-thioether ligands Me₂PCH₂CH₂SR (L) reacted with [RuCl₂(cym)]₂ (cym = p-cymene) to produce 11 new ruthenium(II) complexes; [RuCl₂(cym)(L)] (1-3 for R = CH₃(Me), C

Full text of DOI:10.1016/S0022-328X(99)00334-4

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 587 (1999) 290–298
Syntheses and structures of ruthenium(II) complexes bearing
hybrid phosphine-thioether ligands, Me2PCH2CH2SR
Norihiko Taguchi a, Kazuo Kashiwabara a,*, Kiyohiko Nakajima b,
Hiroyuki Kawaguchi a, Kazuyuki Tatsumi a,1
a Research Center for Materials Science and Department of Chemistry, Graduate School of Science, Nagoya Uni6ersity, Nagoya 464-8602, Japan
b Department of Chemistry, Aichi Uni6ersity of Education, Kariya 448-8542, Japan
Received 2 March 1999; received in revised form 2 June 1999
Abstract
Hybrid phosphine-thioether ligands Me2PCH2CH2SR (L) reacted with [RuCl2(cym)]2 (cym=p-cymene) to produce 11 new
ruthenium(II) complexes; [RuCl2(cym)(L)] (1–3 for R=CH3(Me), C2H5(Et) and C6H5(Ph), respectively) in toluene, [Ru-
Cl(cym)(L)]+ (4–6 for R=Me, Et and Ph, respectively) in ethyl alcohol and [RuCl2(L)2] (7 and 8 for R=Me and Et, respectively
and 9–11 for R=Ph) in refluxing n-butanol. Complexes 1–3 in which L acts as a monodentate ligand through phosphorus led
to complexes 4–6 where L binds to Ru through phosphorus and sulfur in ethyl alcohol at room temperature. Complexes 9–11
were separated into three of five possible geometrical isomers by fractional crystallization, trans(Cl,Cl%)trans(P,P%) (9),
cis(Cl,Cl%)cis(P,P%) (10) and trans(Cl,Cl%)cis(P,P%) (11), whereas complexes 7 and 8 afforded only the trans(Cl,Cl%)trans(P,P%)
isomer. The crystal structures of complexes 5, 8, 9 and 11 were determined by an X-ray diffraction method, suggesting stronger
trans influence of the dimethylphosphino group than those of the thioether and p-cymene moieties. 31P-{H}- and 1H- or
13C-{H}-NMR spectral data are used to characterize the structures of the complexes. The hydride complex [RuH(-
cym)(Me2PCH2CH2SEt)]+ was also prepared by the treatment of NaBH4 with complex 5. © 1999 Elsevier Science S.A. All rights
reserved.
Keywords: Crystal structure; Phosphine-thioether ligands; Ruthenium(II) complexes
the dimethylphosphino moiety carries sterically unde-
manding and strongly electron-donating methyl groups
and found that these molecules act as either monoden-
tate or bidentate ligands depending on transition metal
fragments [4–7].
1. Introduction
While complexes with phosphine-ether hybrid donor
ligands have been extensively studied for various transi-
tion metals [1], analogous phosphine-thioether ligands
have received less attention [2]. Thioethers are consid-
ered to be poor donors upon coordination at transition
metals [3] and they may act as a hemilabile ligand
which provides a potential vacant site for incoming
substrates. Most of phosphine-thioether hybrid ligands
In this paper we report the syntheses of new ruthen-
ium(II) complexes containing Me2PCH2CH2SR (L: R
=Me, Et and Ph) and their structural characterization
1
by an X-ray diffraction method and 31P-{1H}- and H-
or 13C-{1H}-NMR spectra. These complexes can be
grouped into the three types, [RuCl2(cym)(L)] (cym=
p-cymene), [RuCl(cym)(L)]+ and [RuCl2(L)2]. To our
best knowledge, there is only one structural report of a
ruthenium(II) complex containing a P,S hybrid donor
ligand, namely, cis-[RuCl2{(p-tolyl)2P(4-DBT)}2] ((p-
tolyl)2P(4-DBT)=4-(di-p-tolylphosphino)dibenzothio-
phene) [8]. Palladium complexes of dialkylphosphine-
so far reported are limited to those having
a
diphenylphosphino group as the phosphine moiety. We
have been interested in phosphorus-sulfur mixed-donor
ligands Me2PCH2CH2SR (R=H and CH3) in which
* Corresponding author. Fax: +81-52-7892943.
1 Also corresponding author.
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(99)00334-4

N. Taguchi et al. / Journal of Organometallic Chemistry 587 (1999) 290–298
291
i
thioether [PdCl2(R2PCH2CH2SEt)] (R=Et, Pr) have
also appeared [9]. We have communicated a prelimi-
nary result on the crystal structure of [Ru-
Cl(cym)(Me2PCH2CH2SMe)]BPh4·0.5CH2Cl2 [10].
2. Results and discussion
2.1. Synthesis and structure determination by NMR
spectroscopy
Fig. 1. Five possible geometrical isomers for [RuCl2(L)2].
The preparation of Me2PCH2CH2SR (R=Me: mt-
dmp, R=Et: etdmp and R=Ph: ptdmp) was always
accompanied by the contamination of 1,2-bis-
(dimethylphosphino)ethane (dmpe) in 5–20% yields.
Mtdmp or etdmp could not be separated from dmpe by
distillation because their boiling points are similar.
Since the mixtures were used for the preparation of
ruthenium complexes, the reactions with [RuCl2(cym)]2
afforded [RuCl2(cym)]2(m-dmpe) as a by-product, which
was removed by fractional crystallization. On the other
hand, the phenyl derivative, ptdmp, was successfully
separated from dmpe by distillation.
The reaction of [RuCl2(cym)]2 with Me2PCH2CH2SR
(L) resulted in the formation of three different types of
complexes depending upon the choice of solvents
(Scheme 1). The reaction (a) in toluene at room temper-
ature afforded [RuCl2(cym)(L)] (1–3 for R=Me, Et
and Ph, respectively), while reaction (b) in ethyl alcohol
at room temperature [RuCl(cym)(L)]X (X=BPh4 or
PF6) (4–6 for R=Me, Et and Ph, respectively). Com-
plexes 1–6 are air stable in the solid and even in
solution. The phosphorus signals in the 31P-{1H}-NMR
spectra appear at ca. −50, 10 and ca. 51 ppm for the
free ligands (L; mtdmp, etdmp and ptdmp),
[RuCl2(cym)(L)] and [RuCl(cym)(L)]X, respectively.
The down-field shift of the 31P signals in this order and
the difference of chemical shifts (Dl ca. 41 ppm) be-
tween [RuCl2(cym)(L)] and [RuCl(cym)(L)]X suggested
that coordination occurs at phosphorus and that L in
[RuCl2(cym)(L)] binds to Ru in a monodentate manner
while L in [RuCl(cym)(L)]X chelates Ru [11]. Recently
a similar trend of 31P signals has been noted for
[RuCl2(h6-1,2,3,4-Me4C6H2)(PPh2{(C6H3(OMe)2-2,6})]
(31P-{1H}-NMR: 19.7 ppm) and [RuCl(h6-1,2,3,4-
Me4C6H2){PPh2(2-o-C6H3-6-OMe)}] (31P-{1H}-NMR:
55.4 ppm), the former bearing a monodentate phos-
phine and the latter a bidentate one [12]. The chemical
shift difference of Dl=35.7 ppm is close to our obser-
vation for [RuCl2(cym)(L)] and [RuCl(cym)(L)]X.
Complexes 1–3 are transformed into complexes 4–6,
respectively, in ethyl alcohol or methyl alcohol at room
temperature (reaction (d) in Scheme 1), while they are
intact in toluene, dichloromethane or chloroform.
These reactions were monitored by absorption spectra
which show isosbestic points. Since the rates of the
reactions are independent of the kind of R and the
concentration of the complexes and since the addition
of excess LiCl does not affect the rates, we propose the
1
mechanism to be an intramolecular ring closure. H-
NMR spectra are also consistent with the structures,
exhibiting one set of signals for the methyl groups of L
and cym in [RuCl2(cym)(L)], whereas two sets of signals
appear for the corresponding methyl groups in [Ru-
Cl(cym)(L)]X due to the presence of a chiral center at
ruthenium.
The
crystal
structure
of
[Ru-
Cl(cym)(etdmp)]PF6 was determined by an X-ray dif-
fraction method (see below).
Complexes of the type [RuCl2(L)2] (7: R=Me, 8:
R=Et and 9–11: R=Ph) were obtained by reactions
of L with [RuCl2(cym)]2 or [RuCl(cym)(L)]+ in reflux-
ing n-butanol (reactions (c) and (e) in Scheme 1). For
L=mtdmp or etdmp, [RuCl2(L)(dmpe)] occured as a
by-product. Use of [RuCl2(dmso)4] (dmso=dimethyl
sulfoxide) in refluxing n-butanol instead of
[RuCl2(cym)]2 gave 7–11 in 10–15% yields, while the
reactions did not proceed in refluxing ethyl alcohol or
methyl alcohol. All the complexes are air stable in
solution and in the solid state. Of the five possible
geometrical isomers (Fig. 1) of [RuCl2(ptdmp)2], tran-
s(Cl,Cl%)trans(P,P%) (9), cis(Cl,Cl%)cis(P,P%) (10) and
trans(Cl,Cl%)cis(P,P%) (11) isomers were isolated by frac-
tional crystallization and two of them (9 and 11) were
characterized by the X-ray diffraction study. The 31P-
{1H}-NMR spectra of complexes 9 and 11 are consis-
Scheme 1. Synthetic routes of the complexes. (a) 3–4 L, in toluene at
room temperature, (b) 4 L, in ethyl alcohol at room temperature, (c)
6–8 L, reflux in n-butanol, (d) 1–2 L, reflux in n-butanol.

292
N. Taguchi et al. / Journal of Organometallic Chemistry 587 (1999) 290–298
tent with the X-ray-derived structures, exhibiting one
singlet at 38.81 for 9 and 48.90 ppm for 11.
Complex 10 exhibits two doublets at 51.69 and 48.49
ppm with J=32.6 Hz in the 31P-{1H}-NMR spectrum,
suggesting the cis(Cl,Cl%)cis(P,P%) configuration. The
UV–vis absorption spectra of the three isomers (9–11)
differ in the lowest-energy region (19 000–25 000 cm−1
)
as shown in Fig. 2. The absorption peaks in this region,
which are assigned to the d–d transition bands of
low-spin d6 metal complexes [13], shift to higher energy
in the order 9B11B10. The absorption peaks at
26 170 and 30 630 cm−1 of 11 may overlap with charge-
transfer bands.
Only a trans(Cl,Cl%)trans(P,P%) isomer was produced
for [RuCl2(mtdmp)2] (7) and [RuCl2(etdmp)2] (8) and
the structure of 8 was determined by the X-ray analysis.
The 31P-{1H}-NMR (38.42 ppm (s)) and absorption
spectra of the etdmp complex (8) are quite similar to
those of the trans(Cl,Cl%)trans(P,P%) isomer of
[RuCl2(ptdmp)2]. The 13C-{1H}-NMR spectrum of 8
exhibits a virtual triplet (l 11.5) and a singlet (l 13.3)
for the methyl groups of PMe2 and SCH2CH3, respec-
tively, indicating that the inversion at the sulfur atom
occurs rapidly and the gauche chelate conformation of
etdmp is also flexible. The 31P-{1H}, 13C-{1H}-NMR
and UV–vis spectra of 7 are quite similar to those of 8.
In contrast to the trans(Cl,Cl%)trans(P,P%) geometry of
the Ru(II) complexes, [CoCl2(L)2]+(L=mtdmp, et-
dmp) was isolated as a trans(Cl,Cl%)cis(P,P%) isomer [6].
The origin of the different geometrical choice for the
Ru(II) and Co(III) complexes is not clear at present.
The hydride complex [RuH(cym)(etdmp)]+ prepared
by the treatment of NaBH4 with [RuCl(cym)(etdmp)]+
in ethyl alcohol exhibits a doublet at l −11.18 with
Fig. 3. ORTEP drawing of 5.
1
J=48 Hz in the H-NMR and an absorption peak at
1933 cm−1 in the IR spectrum due to RuH. The
spectral data are comparable to those for
[RuHCl(PPh3)(C6Me6)] (l −8.93 (J=53 Hz), 1950
cm−1) [14] and [RuH(cym)(dippe)]BPh4 (dippe=1,2-
bis(diisopropylphosphino)ethane) (l −12.82 (J=36.6
Hz),
2045
cm−1
)
[15].
We
treated
[Ru-
Cl(cym)(etdmp)]+ with PhCCH, CO and CH3CN to
find that no reaction took place.
2.2. Description of the crystal structures
The crystal structures of complexes 5, 8, 9 and 11
have been determined by the X-ray diffraction study.
The ORTEP drawings of these complexes are shown in
Figs. 3–6 and the selected bond lengths and bond
angles are summarized in Table 1.
Fig. 2. Absorption spectra of complexes 9 (—), 10 (– · –) and 11
(– – –), in CH2Cl2.
Fig. 4. ORTEP drawing of 8.

N. Taguchi et al. / Journal of Organometallic Chemistry 587 (1999) 290–298
293
R(Ru)S(S) or S(Ru)R(S) like those in the analogous
mtdmp complex. The molecular model study indicates
that the observed diastereomer is sterically favoured
over the alternative S(Ru)S(S) or R(Ru)R(S) isomer,
where steric repulsion is expected to occur between cym
and a SEt or SMe moiety.
As shown in Fig. 4, the geometry of complex 8 is a
slightly distorted octahedron in
a
trans(Cl,Cl%)-
trans(P,P%) configuration, where an inversion center sits
at Ru. Two etdmp ligands coordinate to Ru as biden-
tate chelates with a common bite angle of 86.38(2)°.
The conformation is gauche with the PꢀCꢀCꢀS dihedral
Fig. 5. ORTEP drawing of 9.
,
angle of 51.9(2)°. The RuꢀP bond length, 2.3267(6) A,
,
is comparable to those in complex 5 (2.313(1) A) and
Complex 5 has a three-legged piano stool structure in
which etdmp acts as a didentate ligand to form a
five-membered chelate ring with a bite angle of
84.52(4)°. The angles at Ru with the three legs do not
deviate from a right angle, indicating that the structure
is also viewed as a distorted octahedron as cym is
regarded as a tridentate ligand. The structural parame-
ters around Ru are quite similar to those for [Ru-
Cl(cym)(mtdmp)] [10]. The RuꢀP bond lengths of the
trans-[Ru(SPh)2(dmpe)2] (dmpe=Me2PCH2CH2PMe2)
,
,
(average 2.334 A) [16]. However, it is longer by 0.10 A
,
than that (average 2.229(2) A) in trans(Cl,Cl%)cis(P,P%)-
[RuCl2{PPh2(C6H3(OMe)2-2,6}] [12], probably due to
the stronger trans influence of the PMe2 group than
,
that of OMe. The RuꢀS bond length (2.349(1) A) in
complex 8 is fairly shorter than that (average 2.469(1)
,
A) in trans-[Ru(SPh)2(dmpe)2].
The ligand arrangements of the slightly distorted
octahedral complexes, 9 and 11, are trans(Cl,Cl%)-
trans(P,P%) and trans(Cl,Cl%)cis(P,P%), respectively (Figs.
5 and 6). The intriguing feature of the structure of 9 is
,
etdmp and mtdmp complexes are shorter by ca. 0.03 A
,
than that (2.342(3) A) of [RuCl(cym){PPh(2-o-C6H3-6-
OMe)(C6H3(OMe)2-2,6}] [12]. This shortening may re-
sult from less steric congestion at the phosphorus atoms
in the former complexes and/or the fact that the
methyl-substituted phosphine moiety is a stronger
donor than the aryl-substituted phosphine group. The
,
the elongation (by 0.06 A) of the RuꢀP bond and the
,
concomitant shortening (0.07 A) of the RuꢀS bond,
compared with those of complex 11. This is probably
caused by the stronger trans influence of the PMe2
group than the SPh group. The RuꢀCl bond lengths are
similar in these complexes. The structural parameters of
9 are also similar to those in 8. The SꢀRuꢀP* angles of
9 and S(1)ꢀRuꢀS(2) and P(1)ꢀRuꢀP(2) angles of 11 are
slightly larger than a right angle and the cis-positioning
of the bulky donor groups may be the reason behind
the trend. The five-membered chelates assume a dis-
torted gauche or envelope conformation.
,
RuꢀCl bond length (2.403(1) A) in the etdmp complex
is comparable to those in the mtdmp complex (2.389
,
(2) A) and [RuCl(cym){PPh(2-o-C6H3-6-OMe)(C6H3-
,
(OMe)2-2,6}] (2.401(4) A). The absolute configurations
of the Ru and S atoms in the etdmp complex are
3. Experimental
All reactions were handled under a dinitrogen atmo-
sphere using Schlenk techniques until such time that
air-stable ruthenium complexes were formed. All sol-
vents, used in the preparation of phosphines and their
complexes, were deaerated by bubbling dinitrogen gas
1
for 20 min immediately before use. The H, 31P-{1H}
and 13C-{1H}-NMR spectra were recorded on Jeol
JNM-A600, Bruker AMX-400 and Hitachi R-90H
spectrometers using tetramethylsilane as an internal
1
reference for H and 13C-{1H} and 85% H3PO4 as an
external reference for 31P-{1H}-NMR. Absorption spec-
tra were obtained on a Hitachi U3400 spectro-
photometer.
Fig. 6. ORTEP drawing of 11.

294
N. Taguchi et al. / Journal of Organometallic Chemistry 587 (1999) 290–298
Table 1
,
Selected bond lengths (A) and angles (°) for the complexes
Complex 5
RuꢀCl
RuꢀC(1)
RuꢀC(4)
2.403(1)
2.231(3)
2.244(3)
RuꢀS
RuꢀC(2)
RuꢀC(5)
2.377(1)
2.267(3)
2.206(4)
RuꢀP(1)
RuꢀC(3)
RuꢀC(6)
2.313(1)
2.273(3)
2.198(3)
ClꢀRuꢀS
RuꢀSꢀC(11)
RuꢀP(1)ꢀC(14)
C(14)ꢀP(1)ꢀC(15)
SꢀC(11)ꢀC(12)
90.89(4)
112.3(2)
107.4(2)
103.3(3)
113.4(3)
ClꢀRuꢀP(1)
RuꢀSꢀC(13)
RuꢀP(1)ꢀC(15)
C(14)ꢀP(1)ꢀC(16)
SꢀC(13)ꢀC(14)
86.68(4)
106.0(2)
119.2(2)
105.7(3)
117.2(5)
SꢀRuꢀP(1)
84.52(4)
102.2(3)
116.6(1)
103.2(3)
115.7(4)
C(11)ꢀSꢀC(13)
RuꢀP(1)ꢀC(16)
C(15)ꢀP(1)ꢀC(16)
P(1)ꢀC(14)ꢀC(13)
Complex 8
RuꢀCl
2.4336(7)
RuꢀS
2.3485(6)
RuꢀP
2.3267(6)
ClꢀRuꢀCl’
ClꢀRuꢀS
ClꢀRuꢀP’
180.0
84.29(2)
88.88(2)
SꢀRuꢀS’
ClꢀRuꢀS’
SꢀRuꢀP
180.0
95.71(2)
86.38(2)
PꢀRuꢀP’
ClꢀRuꢀP
SꢀRuꢀP’
180.0
91.12(2)
93.62(2)
Complex 9
RuꢀCl
2.435(2)
RuꢀS
2.344(2)
RuꢀP
2.335(2)
ClꢀRuꢀCl*
ClꢀRuꢀP
SꢀRuꢀP
180.0
90.04(7)
83.82(7)
ClꢀRuꢀS
ClꢀRuꢀP*
SꢀRuꢀP*
85.96(5)
89.96(7)
96.18(7)
ClꢀRuꢀS*
SꢀRuꢀS*
PꢀRuꢀP*
94.04(5)
180.0
180.0
Complex 11
RuꢀCl(1)
RuꢀS(2)
2.429(2)
2.414(3)
RuꢀCl(2)
RuꢀP(1)
2.433(2)
2.276(3)
RuꢀS(1)
RuꢀP(2)
2.416(2)
2.271(3)
Cl(1)ꢀRuꢀCl(2)
Cl(1)ꢀRuꢀP(1)
Cl(2)ꢀRuꢀS(2)
S(1)ꢀRuꢀS(2)
S(2)ꢀRuꢀP(1)
178.58(10)
91.55(9)
93.56(8)
96.34(9)
176.79(10)
Cl(1)ꢀRuꢀS(1)
Cl(1)ꢀRuꢀP(2)
Cl(2)ꢀRuꢀP(1)
S(1)ꢀRuꢀP(1)
S(2)ꢀRuꢀP(2)
93.66(8)
89.49(9)
89.54(9)
84.70(10)
84.77(10)
Cl(1)ꢀRuꢀS(2)
Cl(2)ꢀRuꢀS(1)
Cl(2)ꢀRuꢀP(2)
S(1)ꢀRuꢀP(2)
P(1)ꢀRuꢀP(2)
85.35(8)
85.54(8)
91.33(9)
176.73(10)
94.4(1)
3.1. Preparation of phosphines
3.1.3. 2-(Phenylthio)dimethylphosphinoethane (ptdmp)
To a dark-blue liquid ammonia solution (200 cm3) of
sodium metal (2.35 g, 0.102 mol), in a dry ice–ace-
tone bath, was added tetramethyldiphosphine [17]
(6.3 g, 0.052 mol) drop-wise with mechanical stirring.
After stirring for 1 h, 2-chloroethyl phenyl sulfide (17.9
g, 0.104 mol) was added portion-wise to the resul-
ting yellow orange solution, yielding a colourless solu-
tion. After stirring it for 1 h the liquid ammonia was
slowly evaporated to dryness. Diethyl ether (100 cm3)
was added to the residue with stirring and insoluble
materials were filtered off. The filtrate was first evapo-
rated at 45°C at atmospheric pressure to remove the
solvent and then at 40°C at 4 mmHg to remove the
side-product, dmpe, together with a small amount of
unreacted 2-chloroethyl phenyl sulfide (1.76 g). The
resulting oily product was found to be nearly pure
ptdmp according to the NMR spectrum and was used
for preparing metal complexes without further purifica-
tion. (13.1 g, 64%) 1H-NMR (CDCl3, 400 MHz):
l 7.2–7.4 (m, 5H, SC6H5), 2.98–3.04 (m, 2H, CH2S),
1.67–1.73 (m, 2H, PCH2), 1.04 (d, 2J(PH) 2.0 Hz,
6H, PCH3), 31P-{1H} (CDCl3, 162 MHz) −49.63 ppm
(s).
3.1.1. 2-(Methylthio)dimethylphosphinoethane (mtdmp)
Thepreparation wasdescribedpreviously [5]. 1H-NMR
(CDCl3, 90 MHz): l 2.5–2.7 (m, 2H, CH2S), 2.13 (s, 3H,
2
SCH3), 1.5–1.8 (m, 2H, PCH2), 1.04 (d, J(PH) 2.2 Hz,
6H, PCH3). 31P-{1H}(CDCl3, 36 MHz): −49.56 ppm (s).
3.1.2. 2-(Ethylthio)dimethylphosphinoethane (etdmp)
Etdmp was prepared by a method similar to that for
mtdmp using (2-chloroethyl)ethylsulfide instead of (2-
chloroethyl)methylsulfide. (90%) The crude product
was found to be a mixture of etdmp and 1,2-bis-
(dimethylphosphino)ethane (5–10%, 31P-{1H} −46.39
ppm) according to the NMR spectra. Since it was
difficult to separate etdmp from the mixture by distilla-
tion because of the similar boiling points, the crude
product was used for the preparation of complexes
without further purification. However, the isolation and
purification of the desired complexes were performed
successfully as will be described later in this section.
1H-NMR (CDCl3, 90 MHz): l 2.4–2.8 (m, 4H, CH2S,
SCH2CH3), 1.5–1.8 (m, 2H, PCH2), 1.27 (t, 3J(HH)
2
7.4, SCH2CH3), 1.05 (d, J(PH) 2.0 Hz, 6H, PCH3).
31P-{1H}-NMR (CDCl3, 36 MHz): −50.66 ppm (s).

N. Taguchi et al. / Journal of Organometallic Chemistry 587 (1999) 290–298
295
3.2. Preparation of complexes
3.2.4. [RuCl(cym)(mtdmp)]B(C6H5)4 4
To an ethyl alcohol solution (30 cm3) of
[RuCl2(cym)]2 (0.31 g, 0.50 mmol) was added mtdmp
(0.21 g, 1.5 mmol) with stirring. The solution was
stirred at r.t. for 3 h and then filtered, yielding an
orange powder of [RuCl2(cym)]2(m-dmpe) (0.06 g, 16%).
The filtrate was dried under reduced pressure. The
residue was washed with diethyl ether and extracted
with ethyl alcohol (5 cm3). The solution was mixed with
the ethyl alcohol solution saturated with NaB(C6H5)4,
yielding yellow precipitates. The powdered precipitates
were recrystallized from a mixture of acetone and water
to afford orange–yellow crystals. (0.52 g, 72%). Found:
C, 64.49; H, 6.47%. C39H47BClPRuS requires C, 64.51;
3.2.1. [RuCl2(cym)(mtdmp-sP)] 1
To a toluene solution (30 cm3) of [RuCl2] (0.31 g,
0.50 mmol) was added mtdmp (0.33 g, 2.4 mmol) with
stirring. The solution was stirred at room temperature
(r.t.) for 3 h and filtered, yielding orange precipitates
(0.09 g, 24%) which were characterized as
[RuCl2(cym)]2(m-dmpe) by the elemental analysis and
1H-NMR spectrum. Found: C, 41.18; H, 5.79.
1
C26H44Cl4P2Ru2 requires C, 40.95; H, 5.82%. H-NMR
(CD2Cl2, 90 MHz): l 5.5 (br, 8H, C6H4), 2.75 (spt,
3J(HH) 6.8, 2H, Me2CH), 2.18 (m, 4H, PCH2), 2.02 (s,
6H, C6H4CH3), 1.55 (filled-in d, J 20.6, 12H, PCH3),
3
1
1.20 (d, J(HH) 6.8Hz, 12H, (CH3)2CH). The filtrate
H, 6.52%. H-NMR (DMSO-d6, 600 MHz): l 6.40 (t,
3J(HH) 5.5, 2H, C6H4), 5.71 (d, 3J(HH) 6.2, 1H, C6H4),
was evaporated under reduced pressure to dryness. The
residue (complex 1) was washed with hexane and air-
dried. (0.32 g, 72%). Found: C, 40.89; H, 6.14%.
3
5.48 (d, J(HH) 6.2, 1H, C6H4), 2.6–2.8 (m, 3H, CH2S,
Me2CH), 2.41 (s, 3H, SCH3), 2.0–2.1 (m, 2H, PCH2),
1.95 (s, 3H, C6H4CH3), 1.84 (d, 2J(HP) 11.4, 3H,
PCH3), 1.67 (d, 2J(HP) 12.5, 3H, PCH3), 1.14 (d,
1
C15H27Cl2PRuS: requires C, 40.73; H, 6.15%. H-NMR
(CDCl3, 400 MHz): l 5.4 (br, 4H, C6H4), 2.84 (spt,
3J(HH) 6.9, 1H, Me2CH), 2.6–2.8 (m, 2H, SCH2),
2.2–2.4 (m, 2H, PCH2), 2.15 (s, 3H, SCH3), 2.08 (s, 3H,
3J(HH) 6.6, 3H, (CH3)2CH), 1.10 (d, J(HH) 7.0 Hz,
3
3H, (CH3)2CH). 31P-{1H}-NMR (CDCl3, 36 MHz):
51.24 ppm (s). The complex is soluble in dimethyl
sulfoxide, dichloromethane or acetone and insoluble in
diethyl ether, ethyl alcohol or water.
2
C6H4CH3), 1.57 (d, J(HP) 10.8, 6H, PCH3), 1.23 (d,
3J(HH) 7.0 Hz, 6H, (CH3)2CH), 31P-{1H}-NMR
(CDCl3, 162 MHz): 9.54 ppm (s). The complex is
soluble in chloroform, dichloromethane, or toluene,
slightly soluble in diethyl ether and insoluble in hexane.
3.2.5. [RuCl(cym)(etdmp)]PF6 5
The complex was prepared by a method similar to
that for complex 4, using etdmp and NaPF6. The
recrystallization was performed from a mixture of
dichloromethane and diethyl ether to afford orange–
yellow crystals. (69%) Found: C, 33.89; H, 5.12%.
C16H29ClF6P2RuS requires C, 33.96; H, 5.17%. 1H-
NMR (CDCl3, 400 MHz): l 6.12 (m, 2H, C6H4), 5.64
3.2.2. [RuCl2(cym)(etdmp-sP)] 2
The complex was prepared by a method similar to
that for 1 using etdmp (73%). Found: C, 41.82; H,
6.56%. C16H29Cl2PRuS requires C, 42.11; H, 6.40%.
1H-NMR (CDCl3, 400 MHz): l 5.5–5.6 (m, 4H, C6H4),
3
2.81 (spt, J(HH) 6.9, 1H, Me2CH), 2.7–2.8 (m, 2H,
3
CH2S), 2.59 (q, J(HH) 7.4, 2H, SCH2Me), 2.3–2.4 (m,
3
3
(d, J(HH) 6.4, 1H, C6H4), 5.49 (d, J(HH) 6.4, 1H,
C6H4), 3.0–3.2 (m, 1H, Me2CH), 2.5–2.7 (m, 4H,
CH2S, SCH2CH3), 2.0–2.2 (m, 2H, PCH2), 2.11 (s, 3H,
2H, PCH2), 2.07 (s, 3H, C6H4CH3), 1.60 (d, 2J(HP)
3
10.8, 6H, PCH3), 1.27 (t, J(HH) 7.43, 3H, SCH2CH3),
1.23 (d, 3J(HH) 7.0Hz, 6H, (CH3)2CH). 31P-{1H}-NMR
(CDCl3, 162 MHz): 10.34 ppm (s). The solubility of the
complex is similar to that of 1.
2
C6H4CH3), 1.94 (d, J(HP) 10.5, 3H, PCH3), 1.81 (d,
2J(HP) 12.0, 3H, PCH3), 1.34 (t, 3J(HH) 7.4, 3H,
3
SCH2CH3), 1.25 (d, J(HH) 6.8, 3H, (CH3)2CH), 1.21
(d, 3J(HH) 6.9 Hz, 3H, (CH3)2CH). 31P-{1H}-NMR
(CDCl3, 162 MHz) 50.96 ppm (s). The complex is
soluble in dichloromethane, chloroform or acetone,
slightly soluble in ethyl alcohol and insoluble in diethyl
ether or water.
3.2.3. [RuCl2(cym)(ptdmp-sP)] 3
To a toluene solution (30 cm3) of [RuCl2(cym)]2 (0.31
g, 0.50 mmol) was added ptdmp (0.41 g, 2.1 mmol) with
stirring. The solution was stirred at r.t. for a further 3
h, yielding an orange powder that was filtered and
washed with hexane and air-dried. (0.47 g, 93%).
Found: C, 48.32; H, 5.38; S, 5.60%. C20H29Cl2PRuS
3.2.6. [RuCl(cym)(ptdmp)]B(C6H5)4 6
1
requires C, 47.62; H, 5.79; S, 6.36%. H-NMR (CDCl3,
To an ethyl alcohol solution (30 cm3) of
[RuCl2(cym)]2 (0.31 g, 0.50 mmol) was added ptdmp
(0.33 g, 1.7 mmol) with stirring. The solution was
stirred overnight and dried under reduced pressure. The
residue was extracted with ethyl alcohol (5 cm3). The
ethyl alcohol solution of NaB(C6H5)4 was added to the
extract, yielding yellow powdered precipitates. The pre-
400 MHz) l 7.1–7.4 (m, 5H, SC6H5), 5.4(br, 4H,
3
C6H4), 2.76 (spt, J(HH) 6.9, 1H, Me2CH), 3.09–3.14
(m, 2H, CH2S), 2.3–2.4 (m, 2H, PCH2), 2.01 (s, 3H,
2
C6H4CH3), 1.56 (d, J(HP) 10.8, 6H, PCH3), 1.19 (d,
3J(HH) 7.0 Hz, 6H, (CH3)2CH). 31P-{1H} (CDCl3, 162
MHz) 10.40 ppm (s). The complex is soluble in chloro-
form or dichloromethane, slightly soluble in diethyl
ether and insoluble in hexane or toluene.
cipitates were recrystallized from
a
mixture of
dichloromethane and diethyl ether to afford orange–

296
N. Taguchi et al. / Journal of Organometallic Chemistry 587 (1999) 290–298
yellow crystals. (0.56 g, 71%). 1H-NMR (DMSO-d6,
400 MHz): l 7.6–7.7 (m, 2H, SC6H5), 7.4–7.5 (m, 3H,
SC6H5), 6.4 (br, 2H, C6H4), 5.9 (br, 1H, C6H4), 5.69 (d,
3J(HH) 6.1, 1H, C6H4), 3.17 (spt, J 6.9, 1H, Me2CH),
2.5–2.7 (m, 2H, CH2S), 2.0–2.2 (m, 2H, PCH2), 1.97
refluxed condition overnight yielded red and yellow
precipitates. The suspension was allowed to stand at
−15°C overnight and filtered. The precipitates was
mixed with a small amount of ethyl alcohol to extract
yellow complex, leaving red precipitates. The red pre-
2
(d, J(HP) 12.4, 3H, PCH3), 1.96 (s, 3H, C6H4CH3),
cipitates were recrystallized from
a
mixture of
2
3
1.72 (d, J(HP) 11.4, 3H, PCH3), 1.13 (d, J(HH) 6.9,
3H, (CH3)2CH), 1.11 (d, 3J(HH) 7.0 Hz, 3H,
(CH3)2CH). 31P-{1H}-NMR (DMSO-d6, 162 MHz):
51.32 ppm (s). The complex is soluble in
dichloromethane or acetone and insoluble in diethyl
ether, ethyl alcohol, or water.
dichloromethane and diethyl ether to afford red crystals
of complex 9. (0.074 g, 13%). Found: C, 42.23; H, 5.09;
S, 11.35%. C20H30Cl2P2RuS2 requires C, 42.25; H, 5.32;
1
S, 11.28%. H-NMR (CDCl3, 90 MHz): l 7.8–8.0 (m,
2H, SC6H5), 7.2–7.4 (m, 3H, SC6H5), 2.9–3.2 (m, 2H,
CH2S), 1.6–2.0 (m, 2H, PCH2), 1.1–1.4 (m, 6H,
PCH3). 31P-{1H}-NMR (CDCl3, 162 MHz): 38.81 ppm
(s). UV–vis 513 nm (m 73): 433(44), 330(890). The
complex is soluble in dichloromethane, or chloroform
and insoluble in ethyl alcohol, n-butanol or diethyl
ether.
3.2.7. trans(Cl,Cl%)trans(P,P%)-[RuCl2(mtdmp)2] 7
The suspension of [RuCl2(cym)]2 (0.31 g, 0.50 mmol)
in n-butanol (20 cm3) was treated with mtdmp (0.64 g,
4.7 mmol) and the mixture was refluxed overnight,
yielding an orange–yellow solution. The solvent was
evaporated under reduced pressure. The residue was
extracted with diethyl ether. Removal of diethyl ether
from the solution yielded an orange powder which was
washed with hexane. The composition of the orange
complex was determined to be [RuCl2(mtdmp)(dmpe)]
based on the elemental analysis. Found: C, 29.19; H,
6.40%, C11H29Cl2P3RuS requires C, 28.83; H, 6.38%.
(0.084 g, 18%). The residue of the diethyl ether extrac-
tion was dissolved in dichloromethane and filtered. The
filtrate was evaporated to dryness and the residue was
recrystallized from a mixture of dichloromethane and
diethyl ether to afford orange–yellow crystals. (0.23 g,
52%). Found: C, 27.05; H, 5.94%. C10H26Cl2P2RuS2
requires C, 27.03; H, 5.90%. 13C-{1H}-NMR (CDCl3,
23 MHz): l 36.7(virtual t, J(PC) 21.0, CH2S), 27.2
(virtual t, J(PC) 23.8 Hz, PCH2), 18.7 (s, SCH3), 11.0
(m, PCH3). 31P-{1H}-NMR (CDCl3, 162 MHz): 39.93
ppm (s). The complex is soluble in dichloromethane,
acetone or n-butanol and insoluble in diethyl ether,
hexane or water.
The yellow ethyl alcohol extract was concentrated to
a small volume just before crystals appeared and al-
lowed to stand at −15°C to yield yellow crystals of
complex 10. (0.14 g, 25%). Found: C, 42.17; H, 5.15; S,
11.12%. C20H30Cl2P2RuS2 requires C, 42.25; H, 5.32; S,
11.28%. 31P-{1H}-NMR (CDCl3, 162 MHz): 51.69 (d,
2
2J(PP) 32.6), 48.49 (d, J(PP) 32.6 Hz). UV–vis: 456
nm (m 258), 349sh (320), 300 (2100). The complex is
soluble in dichloromethane or chloroform, slightly solu-
ble in ethyl alcohol or n-butanol and insoluble in
diethyl ether.
When the n-butanol filtrate of the starting reaction
mixture was evaporated to dryness, an orange complex
was extracted from the residue with diethyl ether. The
extract was evaporated to dryness. The residue was
washed with hexane and recrystallized from toluene to
afford orange crystals of complex 11. (0.042 g, 7%).
Found: C, 41.98; H, 5.03; S, 11.42%. C20H30Cl2P2RuS2
requires C, 42.25; H, 5.32; S, 11.28%. 1H-NMR
(CDCl3, 400 MHz): l 7.6–7.7 (m, 2H, SC6H5), 7.1–7.3
(m, 3H, SC6H5), 3.1–3.3 (m, 2H, CH2S), 2.1–2.2 (m,
2H, PCH2), 1.62(filled-in d, J(HP) 9.3 Hz, 6H, PCH3),
31P-{1H}-NMR (CDCl3, 162 MHz) 48.90 ppm (s). UV–
vis 382 nm (m 1150): 326 (1250). The complex is soluble
in dichloromethane, chloroform or n-butanol, slightly
soluble in diethyl ether and insoluble in hexane.
3.2.8. trans(Cl,Cl%)trans(P,P%)-[RuCl2(etdmp)2] 8
The complex was prepared by a method similar to
that for complex
7
using etdmp to afford
[RuCl2(etdmp)(dmpe)] (yield 18%), found C, 31.00; H,
6.65%, C11H29Cl2P3RuS requires C, 30.51; H, 6.62%
and complex 8 (yield 59%), found: C, 30.67; H, 6.30%,
C12H30Cl2P2RuS2 requires C, 30.51; H, 6.40%. 13C-
{1H}-NMR (CDCl3, 23 MHz): l 33.1 (m, CH2S), 29.0
(s, SCH2CH3), 27.8 (virtual t, J(PC) 23.6, PCH2), 13.3
(s, SCH2CH3), 11.5 (virtual t, J(PC) 25.8 Hz, PCH3).
31P-{1H}-NMR (CDCl3, 162 MHz): 38.42 ppm (s). The
solubility of complex 8 is similar to that of complex 7.
3.2.10. [RuH(cym)(etdmp)]PF6
To an ethyl alcohol solution (50 cm3) of [Ru-
Cl(cym)(etdmp)]PF6 (0.50 g, 0.89 mmol) was added an
ethyl alcohol solution (20 cm3) of NaBH4 with stirring.
The solution was stirred at r.t. for 1 h and the colour
changed from orange to red immediately. The resulting
precipitates were removed by centrifugation and the
supernatant solution was evaporated to dryness. The
residue was mixed with THF to extract an orange
brown complex. The undissolved material was removed
by centrifugation and the supernatant was evaporated
to dryness. The residue was washed with hexane and
3.2.9. trans (Cl,Cl%) trans (P,P%) - [RuCl2 (ptdmp)2] 9, cis-
(Cl,Cl%)cis(P,P%)-[RuCl2(ptdmp)2] 10 and trans(Cl,Cl%)-
cis(P,P%)-[RuCl2(ptdmp)2] 11
Treatment of [RuCl2(cym)]2 (0.31 g, 0.50 mmol) and
ptdmp (0.81 g, 4.1 mmol) in n-butanol (3 cm3) under a

N. Taguchi et al. / Journal of Organometallic Chemistry 587 (1999) 290–298
297
dried in vacuo. (0.37 g, 78%). Found: C, 36.00; H, 5.42;
S, 6.03%. C16H30F6P2RuS requires C, 36.16; H, 5.69; S,
6.03%. 1H-NMR (THF-d6, 400 MHz): l 6.06 (d,
3J(HH) 6.2, 1H, C6H4), 5.95 (d, 3J(HH) 5.9, 1H, C6H4),
AFC-7R (9 and 11) automated four-circle diffractome-
ter using graphite-monochromatized MoꢀKa radiation
,
(u=0.71069 A). The unit-cell parameters were deter-
mined by a least-squares refinement of the setting an-
gles for 25 reflections with 2q angles in the range of
29°B2qB30° (5 and 8) and 22°B2qB25° (9 and 11).
Crystallographic data and experimental details are sum-
marized in Table 2. Three standard reflections were
monitored at every 150 reflections throughout the data
collection and no significant deterioration of the crys-
tals was observed. The absorption correction was made
for 5 and 8 by a Gaussian integration method and an
empirical absorption correction was applied for 9 and
11 based on „ scan data of several suitable reflections
with  values closed to 90°. The structures of 5 and 8
were solved by direct methods [18] and a subsequent
Fourier synthesis and those of 9 and 11 were solved by
heavy-atom Patterson methods [19] and expanded using
Fourier techniques. The structures were refined on F by
full-matrix least-squares method using anisotropic ther-
mal parameters for all non-hydrogen atoms. Hydrogen
atoms were located from a difference-Fourier map or
3
3
5.64 (d, J(HH) 6.0, 2H, C6H4), 2.95 (spt, J(HH) 6.9,
1H, Me2CH), 2.6–2.9 (m, 4H, CH2S, SCH2Me), 2.1–
2.3 (m, 2H, PCH2), 2.14 (s, 3H, C6H4CH3), 1.70 (d,
2J(HP) 10.0, 3H, PCH3), 1.59 (d, 2J(HP) 11.2, 3H,
3
PCH3), 1.21 (d, J(HH) 6.3, 3H, (CH3)2CH), 1.19 (d,
3
3J(HH) 6.3, 3H, (CH3)2CH), 1.13 (t, J(HH) 7.4, 3H,
2
SCH2Me), −11.18 (d, J(HP) 48 Hz, 1H, RuH). 31P-
{1H}-NMR (CDCl3, 162 MHz): 57.77(s), −143.4 ppm
(spt, PF6). IR (KBr pellet): w(RuH) 1933, w(PF6) 836,
558 cm−1. The complex is unstable in air and decom-
poses in dichloromethane or chloroform. The complex
is soluble in ethyl alcohol, THF or DME and insoluble
in toluene or hexane.
3.3. Crystallography
All crystals selected for data collection were mounted
on the top of a glass fiber with epoxy resin. Intensity
data were collected on a Rigaku AFC-5 (5 and 8) and
Table 2
Crystallographic data and experimental details
Complex
5
8
9
11
Formula
FW
C16H29ClF6P2RuS
565.93
C12H30Cl2P2RuS2
472.41
C20H30Cl2P2RuS2
568.51
C27H38Cl2P2RuS2
660.64
Crystal system
Space group
Monoclinic
P21/n (No. 14)
12.529(2)
13.512(2)
14.097(2)
106.68(1)
4
Monoclinic
P21/n (No. 14)
8.254(2)
12.003(2)
10.034(2)
90.69(2)
2
Monoclinic
P21/a (No. 14)
8.561(3)
14.548(4)
10.264(4)
110.16(3)
2
Monoclinic
Cc (No. 9)
15.42(1)
16.733(5)
14.22(1)
122.52(4)
4
,
a (A)
,
b (A)
,
c(A)
i (°)
Z
3
,
V (A )
2286.1(5)
10.63
994.0(3)
13.95
1200.0(7)
11.88
3094(3)
9.32
v(MoꢀKa) (cm−1
)
Transmission factor
Crystal color
0.654–0.702
Orange
Prismatic
0.30×0.40×0.50
1.64
0.628–0.705
Orange
Prismatic
0.30×0.30×0.50
1.58
0.893–1.000
Red
Prismatic
0.65×0.50×0.20
1.57
0.947–1.000
Yellow
Prismatic
0.45×0.50×0.40
1.42
Crystal habit
Crystal size (mm3)
Dcalc (g cm−3
T (K)
)
298
298
296
296
Scan range (°)
Scan mode
1.50+0.50 tan q
ꢀ−2q
8
1.52+0.50 tan q
ꢀ−2q
8
1.47+0.30 tan q
ꢀ−2q
16
1.78+0.30 tan q
ꢀ−2q
16
Scan speed (° min−1
)
2q
(°)
60
60
55
50
max
No. reflections measured
7213
4894
0.040
0.047
2892
2512
0.026
0.034
2997
2386
0.071
0.095
2945
2403
0.037
0.045
No. reflections observed a
b
R
c
Rw
S
1.74
0.71
−0.90
1.52
0.56
−0.82
3.52
0.61
−2.14
2.26
0.71
−0.34
−3
,
Largest difference peak (e A
Largest difference hole (e A
)
−3
,
)
a
ꢀFoꢀ\3|(ꢀFoꢀ) for 5 and 8, ꢀIoꢀ\3|(ꢀIoꢀ) for 9 and 11.
b R=SꢀꢀFoꢀ−ꢀFcꢀꢀ/SꢀFoꢀ.
c Rw=[S wꢀꢀFoꢀ−ꢀFcꢀꢀ /S wꢀFoꢀ2]1/2, w=[|2(Fo)+{0.015(Fo)}2]−1 for 5 and 8, w=4(Fo)2{|2(Fo2)}−1 for 9, w=[|2(Fo)+{0.009(Fo)}2]−1 for 11.
2

298
N. Taguchi et al. / Journal of Organometallic Chemistry 587 (1999) 290–298
[4] M. Kita, T. Yamamoto, K. Kashiwabara, J. Fujita, Bull. Chem.
Soc. Jpn. 65 (1992) 2272.
[5] T. Suzuki, A. Morikawa, K. Kashiwabara, Bull. Chem. Soc. Jpn.
69 (1996) 2539.
[6] K. Kashiwabara, N. Taguchi, H.D. Takagi, K. Nakajima, T.
Suzuki, Polyhedron 17 (1998) 1817.
placed at the calculated positions and fixed during the
structural refinement. The calculations were performed
using XTAL 3.2 [20] (5 and 8) and TEXSAN [21] crystallo-
graphic software (9 and 11) packages.
[7] K. Matsuzaki, M.Sc. Thesis, Nagoya University, 1999, in prepa-
ration.
[8] S.M. Bucknor, M. Draganjac, T.B. Rauchfuss, C.J. Ruffing,
W.C. Fultz, A.L. Rheingold, J. Am. Chem. Soc. 106 (1984) 5379.
[9] L. Zhang, J. Yang, D. Huang, G. Li, Sci. China Ser. B 36 (1993)
513.
[10] T. Suzuki, N. Taguchi, K. Kashiwabara, Acta Crystallogr. C 52
(1996) 2982.
[11] P.E. Garrou, Chem. Rev. 81 (1981) 229.
[12] Y. Yamamoto, R. Sato, F. Matsuo, C. Sudoh, T. Igoshi, Inorg.
Chem. 35 (1996) 2329.
4. Supplementary material
Crystallographic data for the structural analysis has
been deposited with the Cambridge Crystallographic
Data Centre, CCDC Nos. 114821-114824 for complexes
5, 8, 9 and 11, respectively. Copies of this information
may be obtained free of charge from the Director,
CCDC, 12, Union Road, Cambridge CB2 1EZ (Fax:
+44-1223-336-033; email: deposit@ccdc.cam.ac.uk or
www: http://www.ccdc.cam.ac.uk).
[13] A.B.P. Lever, Inorganic Electronic Spectroscopy, 2nd ed., El-
sevier Science, Amsterdam, 1986.
[14] M.A. Bennett, T.N. Huang, A.K. Smith, T.W. Turney, J. Chem.
Soc. Chem. Commun. (1978) 582.
[15] I. de los Rios, M. Jimenez Tenorio, M.A. Jimenez Tenorio, M.C.
Puerta, P. Valerga, J. Organomet. Chem. 525 (1996) 57.
[16] L.D. Field, T.W. Hambley, B.C.K. Yau, Inorg. Chem. 33 (1994)
2009.
[17] S.A. Butter, J. Chatt, Inorg. Synth. XV (1974) 185.
[18] G.M. Sheldrick, SHELXS-86, Program for Crystal Structure De-
termination, University of Go¨ttingen, Go¨ttingen, Germany,
1986.
Acknowledgements
The present work was supported in part by a Grant-
in-Aid for Scientific Research No. 11640562 from the
Ministry of Education, Science and Culture, Japan.
[19] P.T. Beurskens, G. Admiraal, G. Beurskens, W.P. Bosman, S.
Garcia-Granda, R.O. Gould, J.M.M. Smith, C. Smykalla,
PATTY: The DIRDIF Program System: Technical Report of the
Crystallography Laboratory, University of Nijmegen, Nijmegen,
The Netherlands, 1992.
[20] S.R. Hall, H.D. Flack, J.M. Stewart, XTAL 3.2, Program for
X-Ray Crystal Structure Analysis, University of Western Aus-
tralia, Geneva and Maryland, 1992.
References
[1] (a) A. Bader, E. Lindner, Coord. Chem. Rev. 108 (1991) 27. (b)
E. Lindner, S. Pautz, M. Haustein, Coord. Chem. Rev. 155
(1996) 145.
[2] P. Leung, S. Loh, K.F. Mok, A.J.P. White, D.J. Williams, J.
Chem. Soc. Dalton Trans. (1996) 4443.
[21] TEXSAN: Crystal Structure Analysis Package, Molecular Struc-
ture Corporation, 1985–1992.
[3] S.G. Murray, F.R. Hartley, Chem. Rev. 81 (1981) 365.
.
.