Facile transmetalation of a pyridyl-phosphine ligand from ruthenium to gold and silver

Article abstract of DOI:10.1016/j.jorganchem.2012.12.027

Treatment of [RuCl₂(η⁶-p-cymene) {κ¹-(P)-PPh₂(py-6-tert-amyl)}] (1a) and [RuCl ₂(η³:η³-C₁₀H ₁₆){κ¹-(P)-PPh₂(py-6-tert-amyl)}] (1b) with [AuCl(SMe₂)], in dichloromethane at room temperature, resulted in the formation of the dimethyl sulfide adducts [RuCl₂(η ⁶-p-cymene)(SMe₂)] (3a) and [RuCl₂(η ³:η³-C₁₀H₁₆)(SMe₂)] (3b), and the Au(I) complex [AuCl{κ¹-(P)-PPh ₂(py-6-tert-amyl)}] (4). Transmetalation of the pyridyl-phosphine PPh₂(py-6-tert-amyl) (2) was also observed when dichloromethane solutions of 1a-b were treated with AgSbF₆ in the presence of SMe₂, the reactions leading to 3a-b and the dinuclear Ag(I) derivative [Ag₂{μ-PPh₂(py-6-tert-amyl)} ₂][SbF₆]₂ (5). In the absence of SMe ₂ transmetalation of the phosphine to silver was not observed. Instead, the unexpected protonation of the pyridyl group by HF, generated by partial hydrolysis of the SbF₆^- anion, occurred. Compounds [AuCl{κ¹-(P)-PPh₂(py-6-tert-amyl)}] (4) and [Ag₂{μ-PPh₂(py-6-tert-amyl)}₂][SbF ₆]₂ (5) were independently synthesized by reacting 2 with [AuCl(SMe₂)] and AgSbF₆, respectively, and their structures confirmed by means of single-crystal X-ray diffraction techniques, along with those of the protonated species [RuCl₂(η⁶- p-cymene){κ¹-(P)-PPh₂(pyH-6-tert-amyl)}][SbF ₆] (6a) and [RuCl₂(η³:η³- C₁₀H₁₆){κ¹-(P)-PPh₂(pyH-6- tert-amyl)}][SbF₆] (6b).

Full text of DOI:10.1016/j.jorganchem.2012.12.027

Journal of Organometallic Chemistry 727 (2013) 1e9
Contents lists available at SciVerse ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Facile transmetalation of a pyridyl-phosphine ligand from ruthenium
to gold and silver
Eder Tomás-Mendivil, Rocío García-Álvarez, Sergio E. García-Garrido, Josefina Díez, Pascale Crochet,
*
Victorio Cadierno
Laboratorio de Compuestos Organometálicos y Catálisis (Unidad Asociada al CSIC), Departamento de Química Orgánica e Inorgánica, Instituto Universitario de Química
Organometálica “Enrique Moles”, Universidad de Oviedo, Julián Clavería 8, 33006 Oviedo, Spain
a r t i c l e i n f o
a b s t r a c t
Treatment of [RuCl2(h k :h k
6-p-cymene){ 1-(P)-PPh2(py-6-tert-amyl)}] (1a) and [RuCl2(h3 3-C10H16){ 1-(P)-
Article history:
Received 18 October 2012
Received in revised form
28 November 2012
PPh2(py-6-tert-amyl)}] (1b) with [AuCl(SMe2)], in dichloromethane at room temperature, resulted in the
formation of the dimethyl sulfide adducts [RuCl2(
6-p-cymene)(SMe2)] (3a) and [RuCl2(h3 h3
C10H16)(SMe2)] (3b), and the Au(I) complex [AuCl{
1-(P)-PPh2(py-6-tert-amyl)}] (4). Transmetalation of
h
: -
k
Accepted 13 December 2012
the pyridyl-phosphine PPh2(py-6-tert-amyl) (2) was also observed when dichloromethane solutions of
1aeb were treated with AgSbF6 in the presence of SMe2, the reactions leading to 3aeb and the dinuclear
Keywords:
Ag(I) derivative [Ag2{
phosphine to silver was not observed. Instead, the unexpected protonation of the pyridyl group by HF,
generated by partial hydrolysis of the SbFꢀ6 anion, occurred. Compounds [AuCl{ 1-(P)-PPh2(py-6-tert-
amyl)}] (4) and [Ag2{ -PPh2(py-6-tert-amyl)}2][SbF6]2 (5) were independently synthesized by reacting 2
with [AuCl(SMe2)] and AgSbF6, respectively, and their structures confirmed by means of single-crystal X-
m-PPh2(py-6-tert-amyl)}2][SbF6]2 (5). In the absence of SMe2 transmetalation of the
Gold complexes
Silver complexes
P,N-ligands
Transmetalation processes
Dimethyl sulfide
k
m
ray diffraction techniques, along with those of the protonated species [RuCl2(h k
6-p-cymene){ 1-(P)-
PPh2(pyH-6-tert-amyl)}][SbF6] (6a) and [RuCl2(h3
:h
3-C10H16){
k
1-(P)-PPh2(pyH-6-tert-amyl)}][SbF6] (6b).
Ó 2012 Elsevier B.V. All rights reserved.
1. Introduction
intense research in this field [3]. Related works by Oshiki and co-
workers have also demonstrated the high potential of pyridyl-
phosphines for the design of effective bifunctional catalysts for
nitrile hydration reactions [5]. In this context, and in line with our
current studies on this catalytic transformation [6], we have
recently described the catalytic behaviour of the novel arene-
Heteroditopic (2-pyridyl)-phosphines are versatile and easily
tunable ligands which can coordinate to metal fragments in mon-
odentate, chelate or bridge form, depending on the requirements at
the metal centre (Fig. 1) [1]. Owing to the different properties of the
P- and N-donor groups, they also represent typical examples of
hemilabile ligands able to reversibly undergo chelate ring-opening
processes [2]. In this way, a coordination site can be temporarily
liberated for substrate binding, a property that has been widely
exploited in the stoichiometric and catalytic chemistry of many
transition-metals [1].
ruthenium(II) and bis(allyl)-ruthenium(IV) derivatives [RuCl2(h6
-
-
p-cymene){
C10H16){
k :
1-(P)-PPh2(py-6-tert-amyl)}] (1a) and [RuCl2(h3 h3
k
1-(P)-PPh2(py-6-tert-amyl)}] (1b) (C10H16 ¼ 2,7-dimeth
ylocta-2,6-diene-1,8-diyl) [7]. A remarkable property of these
complexes, which were readily prepared through classical chloride
bridges-splitting reactions of the dimeric precursors [{RuCl(
m-
The ability of the nitrogen atom of the pyridyl unit to establish
hydrogen bonds, or to participate in proton transfer processes, has
also been tapped for the development of new “bifunctional cata-
Cl)(h
6-p-cymene)}2] and [{RuCl( -Cl)(h3 3-C10H16)}2] with the
m
:h
commercially available 2-(diphenylphosphino)pyridine ligand
PPh2(py-6-tert-amyl) (2) [8], is the fact that they do not form the
lysts” based on metal complexes with
k
1-(P)-coordinated pyridyl-
corresponding cationic chelate species [RuCl(
(P,N)-PPh2(py-6-tert-amyl)}]þ and [RuCl(h3 3-C10H16){
PPh2(py-6-tert-amyl)}]þ, even in the presence of
h -
6-p-cymene){k2
phosphines [3]. Pioneering reports by Grotjahn and co-workers of
enhanced activities and selectivities in the ruthenium-catalyzed
anti-Markovnikov hydration of alkynes [4] have stimulated an
:h
k
2-(P,N)-
chloride
a
abstractor such as NaSbF6 [7]. Steric hindrance between the bulky
tert-amyl substituent adjacent to the nitrogen atom and the coor-
dinated p-cymene or 2,7-dimethylocta-2,6-diene-1,8-diyl ligands is
behind this behaviour.
* Corresponding author.
E-mail address: vcm@uniovi.es (V. Cadierno).
0022-328X/$ e see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jorganchem.2012.12.027

2
E. Tomás-Mendivil et al. / Journal of Organometallic Chemistry 727 (2013) 1e9
purification over silica gel using dichloromethane as eluent (ca.
0.300 g; 53% yield). In contrast, all attempts to isolate complexes
3aeb by column chromatography failed. Thus, although further
elution with a dichloromethane/methanol (2/1) mixture gave rise,
in both cases, to a new brown band, their 1H NMR spectra (CDCl3)
showed a complex mixture of decomposition products. Character-
ization data for complex [AuCl{k
1-(P)-PPh2(py-6-tert-amyl)}] (4)
Fig. 1. The most common coordination modes of (2-pyridyl)-phosphine ligands.
are as follows: 31P{1H} NMR (CD2Cl2):
d
¼ 31.3 (s) ppm; 1H NMR
3
(CD2Cl2):
d
¼ 0.60 (t, JHH ¼ 7.5 Hz, 3H, CH2CH3), 1.27 (s, 6H,
The reluctance of PPh2(py-6-tert-amyl) (2) to adopt a chelating
2-(P,N) coordination mode in these systems prompted us to study
3
C(CH3)2), 1.68 (q, JHH ¼ 7.5 Hz, 2H, CH2CH3), 7.42e7.58 (m, 6H,
k
CHarom), 7.72e7.96 (m, 7H, CHarom) ppm; 13C{1H} NMR (CD2Cl2):
the reactivity of complexes 1aeb towards [AuCl(SMe2)], as a po-
tential entry for the preparation of unprecedented heterobimetallic
Ru/Au derivatives bridged by a (2-pyridyl)-phosphine ligand [9].
Although this goal could not be achieved, as the reader will see in
this article, a series of unusual transmetalation processes have been
disclosed throughout our study.
d
¼ 8.8 (s, CH2CH3), 26.9 (s, C(CH3)2), 35.6 (s, CH2CH3), 41.2 (s,
2 3
C(CH3)2), 122.1 (d, JPC ¼ 2.4 Hz, CHarom), 128.7 (d, JPC ¼ 11.8 Hz,
CHarom), 129.1 (s, CHarom), 129.4 (d, 1JPC ¼ 63.5 Hz, Carom), 131.7 (d,
4JPC ¼ 2.6 Hz, CHarom), 134.5 (d, JPC ¼ 13.3 Hz, CHarom), 136.7 (d,
2
3JPC ¼ 11.8 Hz, CHarom), 151.8 (d, JPC ¼ 86.6 Hz, Carom), 169.9 (d,
1
3JPC ¼ 14.2 Hz, Carom) ppm; Anal. Calcd for AuC22H24ClNP (565.83 g/
mol): C, 46.70; H, 4.28; N, 2.48. Found: C, 46.57; H, 4.23; N, 2.32%.
2. Experimental
2.3. Synthesis of complex [RuCl2(h3
:
h
3-C10H16)(SMe2)] (3b)
2.1. General information
A solution of the dimeric precursor [{RuCl(
m
-Cl)(h3 3-C10H16)}2]
:h
All manipulations were performed under an atmosphere of dry
nitrogen using vacuum-line and standard Schlenk techniques.
Solvents were dried by standard methods and distilled under ni-
trogen before use. All reagents were obtained from commercial
suppliers and used without further purification, with the exception
(0.100 g, 0.16 mmol) in dichloromethane (10 mL) was treated with
dimethyl sulfide (24 L, 0.33 mmol) at room temperature for 15 min
m
(the solution turned from violet to orange within a few minutes)
and then evaporated to dryness. The resulting orange solid residue
was washed with hexanes (5 mL) and vacuum-dried. Yield: 95%
of compounds [{RuCl(
Cl)(h3 3-C10H16)}2] [11], [RuCl2(
tert-amyl)}] (1a) [7], [RuCl2(h3
amyl)}] (1b) [7], [AuCl(SMe2)] [12] and [RuCl2(
m
-Cl)(
h
6-p-cymene)}2] [10], [{RuCl(
6-p-cymene){ 1-(P)-PPh2(py-6-
3-C10H16){ 1-(P)-PPh2(py-6-tert-
6-p-cyme-
m-
(0.113 g); 1H NMR (CD2Cl2):
d
¼ 2.32 and 2.35 (s, 6H each, CH3 and
:h
h
k
S(CH3)2), 2.62 (m, 2H, H4 and H6), 3.94 (m, 2H, H5 and H7), 3.81 (s,
2H, H2 and H10), 4.59 (s, 2H, H1 and H9), 4.90 (m, 2H, H3 and H8)
:
h
k
h
ppm; 13C{1H} NMR (CD2Cl2):
d
¼ 20.2 and 21.9 (s, CH3 and S(CH3)2),
ne)(SMe2)] (3a) [13], which were prepared by following the
methods reported in the literature. The C, H, and N analyses were
carried out with a PerkineElmer 2400 microanalyzer. NMR spectra
were recorded on Bruker DPX300 or AV400 instruments. Chemical
shifts are given in ppm, relative to internal tetramethylsilane (1H
and 13C), and external 85% aqueous H3PO4 solutions (31P). DEPT
experiments have been carried out for all the compounds reported
in this paper. The numbering for protons and carbons of the 2,7-
dimethylocta-2,6-diene-1,8-diyl skeleton is as follows:
35.3 (s, C4 and C5), 74.1 (s, C1 and C8), 99.4 (s, C3 and C6), 125.8 (s, C2
and C7) ppm; Anal. Calcd for RuC12H22Cl2S (370.34 g/mol): C, 38.92;
H, 5.99. Found: C, 38.98; H, 6.02%.
2.4. Synthesis of complex [AuCl{k
1-(P)-PPh2(py-6-tert-amyl)}] (4)
starting from [AuCl(SMe2)] and PPh2(py-6-tert-amyl) (2)
A solution of [AuCl(SMe2)] (0.088 g, 0.3 mmol) in dichloro-
methane (10 mL) was treated with the phosphine ligand 2 (0.100 g,
0.3 mmol) at room temperature for 1 h, and then concentrated to
ca. 3 mL. Addition of hexanes (30 mL) led to the precipitation of
a white solid, which was washed with hexanes (5 mL) and vacuum-
dried. Yield: 91% (0.154 g).
2.5. Reactions of complexes [RuCl2(
h
6-p-cymene){
k
1-(P)-PPh2(py-
6-tert-amyl)}] (1a) and [RuCl2(h3 3-C10H16){
:
h
k
1-(P)-PPh2(py-6-
tert-amyl)}] (1b) with AgSbF6 in the presence of SMe2
2.2. Reactions of complexes [RuCl2(
6-tert-amyl)}] (1a) and [RuCl2(h3 3-C10H16){
tert-amyl)}] (1b) with [AuCl(SMe2)]
h
6-p-cymene){
k
1-(P)-PPh2(py-
To a solution of the corresponding rutheniumephosphine
complex 1aeb (1 mmol) in dichloromethane (10 mL) were added
SMe2 (734 mL, 10 mmol) and AgSbF6 (0.343 g, 1 mmol), and the
:h
k
1-(P)-PPh2(py-6-
resulting mixture stirred at room temperature, and in the absence
of light, for 48 (1a) or 12 h (1b). The volatiles were then removed
under vacuum to give a brown solid residue. The 31P{1H} and 1H
NMR spectra (CDCl3) of this solid indicated the presence of a mix-
A solution of the corresponding ruthenium complex 1ae
(1 mmol) in dichloromethane (10 mL) was treated with
b
[AuCl(SMe2)] (0.294 g, 1 mmol) at room temperature for 48 (1a) or
12 h (1b). The solvent was then removed under vacuum to give an
orange solid residue. The 31P{1H} and 1H NMR spectra (CDCl3) of
this solid indicated the presence of a mixture containing the Au(I)
ture containing the dinuclear Ag(I) complex [Ag2{
amyl)}2][SbF6]2 (5) and the corresponding dimethyl sulfide adduct
[RuCl2(
6-p-cymene)(SMe2)] (3a) or [RuCl2(h3 3-C10H16)(SMe2)]
(3b), along with a minor amount of the corresponding ruth-
enium dimer [{RuCl( -Cl)( : -
6-p-cymene)}2] or [{RuCl( -Cl)(h3 h3
m-PPh2(py-6-tert-
h
:h
complex [AuCl{
sponding dimethyl sulfide adduct [RuCl2(
(3a) or [RuCl2(h3 3-C10H16)(SMe2)] (3b), along with a minor
amount of the corresponding ruthenium dimer [{RuCl( -Cl)(
6-p-
cymene)}2] or [{RuCl(
-Cl)(h3 3-C10H16)}2]. Complex 4 could be
isolated from these mixtures, as a white solid, by chromatographic
k
1-(P)-PPh2(py-6-tert-amyl)}] (4) and the corre-
h
6-p-cymene)(SMe2)]
m
h
m
:
h
C10H16)}2]. Complex 5 could be isolated in pure form, as a white
solid, from these mixtures by successive recrystallizations from
dichloromethaneediethyl ether (ca. 0.450 g; 66% yield). Charac-
m
h
m
:h
terization data for [Ag2{m-PPh2(py-6-tert-amyl)}2][SbF6]2 (5) are as

E. Tomás-Mendivil et al. / Journal of Organometallic Chemistry 727 (2013) 1e9
3
Table 1
Crystal data and structure refinement for compounds 4, 5, 6a and 6b.
4
5
6a
6b
Empirical formula
Formula weight
Temperature (K)
Wavelength (A)
Crystal system
Space group
Au2C44H48Cl2N2P2$CH2Cl2
AgC44H48 F12N2P2Sb2$2THF
1498.25
123(2)
1.5418
Monoclinic
P21/n
RuC32H39F6Cl2NPSb
876.33
293(2)
1.5418
Monoclinic
P21/c
RuC32H41F6Cl2NPSb
878.35
293(2)
1.5418
Orthorhombic
P212121
1216.55
150(2)
1.5418
Triclinic
P-1
ꢀ
Unit cell dimensions
ꢀ
a (A)
11.8931(3)
12.2165(3)
16.2110(5)
93.884(2)
106.566(3)
92.453(2)
2247.6(1)
2
1.798
15.211
14.8922(1)
20.1499(2)
19.0288(2)
90
97.915(1)
90
5655.70(9)
4
1.760
9.6331(2)
11.7154(2)
34.0624(7)
90
91.152(2)
90
3843.4(1)
4
1.514
8.0090(2)
11.2794(3)
38.0033(10)
90
90
90
3433.1(2)
4
1.699
12.167
1752
ꢀ
b (A)
ꢀ
c (A)
a
b
g
(ꢂ)
(ꢂ)
(ꢂ)
3
ꢀ
Volume (A )
Z
Calculated density (g cmꢀ3
)
Absorption coefficient (mmꢀ1
F(000)
)
14.202
2960
10.868
1744
1180
Crystal size (mm)
0.123 ꢁ 0.174ꢁ 0.314
3.63e69.65
ꢀ14 ꢃ h ꢃ 14
ꢀ13 ꢃ k ꢃ 14
ꢀ19 ꢃ l ꢃ 18
24,440
0.090ꢁ 0.110ꢁ 0.200
3.21e74.37
ꢀ18 ꢃ h ꢃ 18
ꢀ24 ꢃ k ꢃ 25
ꢀ23 ꢃ l ꢃ 22
40,886
0.112ꢁ 0.039ꢁ 0.025
3.99e74.67
ꢀ11 ꢃ h ꢃ 11
ꢀ13 ꢃ k ꢃ 14
ꢀ29 ꢃ l ꢃ 42
14,642
0.130ꢁ 0.076ꢁ 0.037
4.09e74.34
ꢀ9 ꢃ h ꢃ 9
ꢀ13 ꢃ k ꢃ 13
ꢀ46 ꢃ l ꢃ 44
9344
Theta range for data collection (ꢂ)
Index ranges
Reflections collected
Independent reflections
Completeness to theta max.
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Weight function (a, b)
8328 [R(int) ¼ 0.032]
11,343 [R(int) ¼ 0.064]
7521 [R(int) ¼ 0.032]
5741 [R(int) ¼ 0.038]
99.4%
99.9%
95.5%
96.3%
Full-matrix least-squares on F2
8328/2/490
1.059
0.0609, 6.1316
0.0362
0.1023
0.0399
0.1056
11,343/1/655
1.031
0.1183, 64.6386
0.0840
0.2116
0.0964
7521/0/371
1.013
0.1183, 0.0000
0.0597
0.1623
0.0716
93,440/13/451
1.051
0.0811, 6.4463
0.0514
0.1381
0.0582
R1a [I > 2
wR2a [I > 2
R1 (all data)
wR2 (all data)
Largest difference peak/hole (eA
s
(I)]
(I)]
s
0.2263
3.19 and ꢀ5.93
0.1729
1.33 and ꢀ1.04
0.1452
1.00 and ꢀ1.26
ꢀꢀ3
)
1.74 and ꢀ1.67
P
P
P
P
a
½
R1 ¼ (jFoj ꢀ jFcj)/ jFoj; wR2 ¼ { [w(F2o ꢀ Fc2)2]/ [w(Fo2)2]}
.
follows: 31P{1H} NMR (CD2Cl2):
d
3
¼ 21.1 and 25.4 (br signals) ppm;
and in the absence of light, for 24 h. The resulting suspension was
filtered over Kieselguhr and the filtrate concentrated to ca. 5 mL.
Addition of diethyl ether (20 mL) led to the precipitation of an or-
ange solid, which was washed with diethyl ether (3 ꢁ 10 mL) and
1H NMR (CD2Cl2):
d
¼ 0.74 (t, JHH ¼ 7.2 Hz, 6H, CH2CH3), 1.65 (s,
3
12H, C(CH3)2), 2.01 (q, JHH ¼ 7.2 Hz, 4H, CH2CH3), 7.24e7.33 (m,
10H, CHarom), 7.59 (m, 8H, CHarom), 7.75 (m, 4H, CHarom), 7.93 (d,
3JHH ¼ 7.8 Hz, 2H, CHarom), 8.10 (dd, JHH ¼ 7.8 and 7.5 Hz, 2H,
vacuum-dried. Yield: 55% (0.241 g); 31P{1H} NMR (CDCl3):
d
¼ 38.8
3
CHarom) ppm; 13C{1H} NMR (CD2Cl2):
d
¼ 8.7 (s, CH2CH3), 27.8 (s,
(s) ppm; 1H NMR (CDCl3):
d
¼ 0.66 (t, JHH ¼ 7.5 Hz, 3H, CH2CH3),
3
C(CH3)2), 38.4 (s, C(CH3)2), 41.1 (s, CH2CH3), 125.3 (d, 1JPC ¼ 40.0 Hz,
1.11 (d, JHH ¼ 6.9 Hz, 6H, CH(CH3)2), 1.48 (s, 6H, C(CH3)2), 1.87 (q,
3
Carom), 126.2, 133.2 and 141.0 (s, CHarom), 128.7 and 130.5 (br s,
3JHH
¼
7.5 Hz, 2H, CH2CH3), 1.89 (s, 3H, CH3), 2.60 (sept,
3
3
CHarom), 133.8 (d, JPC ¼ 11.8 Hz, CHarom), 155.5 (d, 1JPC ¼ 66.9 Hz,
3JHH ¼ 6.9 Hz, 1H, CH(CH3)2), 5.40 and 5.51 (d, JHH ¼ 6.6 Hz, 2H
3
Carom), 171.8 (d, JPC ¼ 11.5 Hz, Carom) ppm; Anal. Calcd for
each, CH of cym), 7.63e7.82 (m, 12H, CHarom), 8.40 (m, 1H, CHarom),
Ag2C44H48F12N2P2Sb2 (1354.05 g/mol): C, 39.03; H, 3.57; N, 2.07.
Found: C, 38.95; H, 3.64; N, 2.05%.
14.16 (s, 1H, NH) ppm; 13C{1H} NMR (CD2Cl2):
d
¼ 8.8 (s, CH2CH3),
17.5 (s, CH3), 21.4 (s, CH(CH3)2), 26.7 (s, C(CH3)2), 30.6 (s, CH(CH3)2),
35.3 (s, CH2CH3), 41.2 (s, C(CH3)2), 87.7 (d, 2JPC ¼ 6.0 Hz, CH of cym),
89.8 (d, 2JPC ¼ 4.5 Hz, CH of cym), 98.5 and 111.8 (s, C of cym), 126.1
2.6. Synthesis of complex [Ag2{m-PPh2(py-6-tert-amyl)}2][SbF6]2
(5) starting from AgSbF6 and PPh2(py-6-tert-amyl) (2)
1
and 133.0 (s, CHarom), 128.8 (d, JPC ¼ 46.0 Hz, Carom), 129.7 (d,
3JPC ¼ 11.3 Hz, CHarom), 130.0 (d, JPC ¼ 22.0 Hz, CHarom), 133.8 (d,
3
2JPC ¼ 10.6 Hz, CHarom), 145.3 (d, JPC ¼ 4.0 Hz, CHarom), 153.2 (d,
2
AgSbF6 (0.172 g, 0.5 mmol) was added to a dichloromethane
solution (10 mL) of the phosphine ligand 2 (0.167 g, 0.5 mmol). The
mixture was stirred at r.t. for 1 h, filtered over Kieselguhr, and the
filtrate concentrated to ca. 3 mL. Addition of hexanes (50 mL) led to
the precipitation of a white solid, which was washed with hexanes
(2 ꢁ 5 mL) and vacuum-dried. Yield: 94% (0.318 g).
1JPC ¼ 36.2 Hz, Carom), 165.5 (s, Carom) ppm; Anal. Calcd for
RuC32H39F6Cl2NPSb (876.36 g/mol): C, 43.86; H, 4.49; N, 1.60.
Found: C, 44.01; H, 4.57; N, 1.77%.
:h k
2.8. Synthesis of complex [RuCl2(h3 3-C10H16){ 1-(P)-PPh2(pyH-6-
tert-amyl)}][SbF6] (6b)
2.7. Synthesis of complex [RuCl2(h k
6-p-cymene){ 1-(P)-PPh2(pyH-6-
tert-amyl)}][SbF6] (6a)
A solution of complex [RuCl2(h3 3-C10H16){ 1-(P)-PPh2(py-6-
:h k
tert-amyl)}] (1b) (0.100 g, 0.156 mmol) in dichloromethane (10 mL)
was treated with AgSbF6 (0.054 g, 0.156 mmol) at room tempera-
ture, and in the absence of light, for 24 h. The resulting suspension
was filtered over Kieselguhr and the filtrate concentrated to ca.
A solution of complex [RuCl2(h k
6-p-cymene){ 1-(P)-PPh2(py-6-
tert-amyl)}] (1a) (0.320 g, 0.5 mmol) in dichloromethane (20 mL)
was treated with AgSbF6 (0.172 g, 0.5 mmol) at room temperature,

4
E. Tomás-Mendivil et al. / Journal of Organometallic Chemistry 727 (2013) 1e9
Scheme 1. Reactivity of the ruthenium complexes 1aeb towards [AuCl(SMe2)].
2 mL. Addition of diethyl ether (20 mL) led to the precipitation of
6a was solved by Patterson interpretation and phase expansion
using DIRDIF [18]. Isotropic least-squares refinement on F2 using
SHELXL97 [19] was performed. During the final stages of the re-
finements, all the positional parameters and the anisotropic tem-
perature factors of all the non-H atoms were refined. The H atoms
were geometrically located and their coordinates were refined
riding on their parent atoms. In the case of complex 6b, the H(1n)
atom was found from the Fourier map and included in a refinement
with isotropic parameters. In the crystal of 4 one CH2Cl2 molecule
of solvation per formula unit of the complex was found, and in that
of 5 two THF molecules of solvation per formula unit of the complex
were found coordinated to silver atoms. In the crystal 6a all the
fluorine atoms of the anion [SbF6]ꢀ were disordered and, con-
sequently, refined as isotropic and located in two positions with
occupancy of 50% each. In the crystal 6b the Cl(2) atom was dis-
ordered, and it was located in two positions with occupancy of 75%
and 25%. Also, all the atoms of the [SbF6]ꢀ anion of 6b were dis-
ordered and located with occupancies of 62% and 38%. In all the
cases, the maximum residual electron density was located near to
a yellow solid, which was washed with diethyl ether (3 ꢁ 10 mL)
and vacuum-dried. Yield: 83% (0.114 g); 31P{1H} NMR (CD2Cl2):
3
d
¼ 16.1 (s) ppm; 1H NMR (CD2Cl2):
d
¼ 0.73 (t, JHH ¼ 7.4 Hz, 3H,
CH2CH3), 1.31 and 1.32 (s, 3H each, C(CH3)2), 1.68 (q, 3JHH ¼ 7.4 Hz,
2H, CH2CH3), 2.02 and 2.30 (s, 3H each, CH3), 2.60 (d, 3JPH ¼ 3.1 Hz,
1H, H2 or H10), 2.82 (m, 1H, H4 or H6), 2.98 (m, 1H, H4 or H6), 3.04 (d,
3JPH ¼ 2.4 Hz, 1H, H2 or H10), 3.71 (m, 2H, H5 and H7), 4.21 (d,
3JPH ¼ 9.2 Hz, 1H, H1 or H9), 4.33 (m, 1H, H3 or H8), 4.69 (d,
3JPH ¼ 10.5 Hz, 1H, H1 or H9), 5.36 (m, 1H, H3 or H8), 7.27e7.94 (m,
13H, CHarom), 15.45 (s, 1H, NH) ppm; 13C{1H} NMR (CD2Cl2):
d
¼ 9.1
(s, CH2CH3), 19.6 and 19.8 (s, CH3), 27.2 and 27.3 (s, C(CH3)2), 36.1,
36.2 and 36.3 (s, CH2CH3, C4 and C5), 41.6 (s, C(CH3)2), 70.1 (d,
2JPC ¼ 5.6 Hz, C1 or C8), 70.4 (d, JPC ¼ 3.7 Hz, C1 or C8), 108.4 (d,
2
2JPC ¼ 7.4 Hz, C3 and C6), 117.8 (d, 3JPC ¼ 10.7 Hz, CHarom), 124.3 (s, C2
3
3
and C7), 128.7 (d, JPC ¼ 10.0 Hz, CHarom), 128.9 (d, JPC ¼ 10.4 Hz,
CHarom), 129.6 and 130.8 (s, CHarom), 131.0 (d, 4JPC ¼ 2.6 Hz, CHarom),
133.3 (d, 2JPC ¼ 8.1 Hz, CHarom), 133.7 (d, 1JPC ¼ 42.3 Hz, Carom), 134.9
(d, 1JPC ¼ 45.4 Hz, Carom), 135.3 (d, 2JPC ¼ 13.4 Hz, CHarom), 135.7 (d,
P
P
2JPC ¼ 8.2 Hz, CHarom), 158.9 (d, JPC ¼ 58.5 Hz, Carom), 167.4 (d,
heavy atoms. The function minimized was [
u
Fo2 ꢀ F2c)/
u
(Fo2)]1/2
1
3JPC ¼ 11.2 Hz, Carom) ppm; Anal. Calcd for RuC32H41F6Cl2NPSb
(878.37 g/mol): C, 43.76; H, 4.70; N, 1.59. Found: C, 43.68; H, 4.72;
N, 1.54%.
where
u
¼ 1/[
s
2(Fo2) þ (aP)2 þ bP] (a and b values are collected in
Table 1) with
s
(Fo2) from counting statistics and P ¼ (Max (Fo2 þ 2F2c)/
3. Atomic scattering factors were taken from the International
Tables for X-Ray Crystallography [20]. Geometrical calculations
were made with PARST [21]. The crystallographic plots were made
with ORTEP-3 [22].
2.9. X-ray diffraction measurements
Crystals suitable for X-ray diffraction analysis were obtained by
slow diffusion of n-pentane into saturated solutions of the com-
plexes in CH2Cl2 (4 and 6aeb) or THF (5). The most relevant crystal
and refinement data are collected in Table 1. Data collections were
3. Results and discussion
Contrary to our expectations, the treatment of dichloromethane
performed on an Oxford Diffraction Xcalibur Nova single-crystal
solutions of complexes [RuCl2(
h k
6-p-cymene){ 1-(P)-PPh2(py-6-
:h k
diffractometer using Cu-Ka radiation (
l
¼ 1.5418 A). Images were
tert-amyl)}] (1a) and [RuCl2(h3 3-C10H16){ 1-(P)-PPh2(py-6-tert-
ꢀ
collected at a 70 (4) or 63 mm (5 and 6aeb) fixed crystal-detector
distance using the oscillation method, with 1ꢂ oscillation and 1.5 s
(4e5) exposure time, or variable 5e30 s (6a) or 1.5e6 s (6b), per
image. Data collection strategy was calculated with the program
CrysAlis Pro CCD [14]. Data reduction and cell refinement was
performed with the program CrysAlis Pro RED [14]. Empirical ab-
sorption correction was applied using the SCALE3 ABSPACK algo-
rithm as implemented in the program CrysAlis Pro RED [14].
In all the cases, the software package WINGX [15] was used for
space group determination, structure solution and refinement. For
4 the structure was solved by direct methods using SIR2004 [16],
for 5 and 6b was solved by direct methods using SIR92 [17], and for
amyl)}] (1b) with one equivalent of [AuCl(SMe2)] did not result in
the coordination of the pendant pyridyl unit of the PPh2(py-6-tert-
amyl) ligands to the AuCl fragment. Instead, formation of the novel
Au(I)-phosphine complex [AuCl{k
1-(P)-PPh2(py-6-tert-amyl)}] (4)
was in both cases observed after 48 (starting from 1a) or 12 h
(starting from 1b) of stirring at room temperature (Scheme 1). The
generation of the same phosphorus-containing product in both
experiments was readily evidenced by monitoring the course of the
reactions by 31P{1H} NMR spectroscopy (CH2Cl2 solutions refer-
enced with a capillary of D2O), which showed the gradual dis-
appearance of the singlet signals corresponding to 1a (dP ¼ 21 ppm)
and 1b (dP ¼ 25 ppm), and the appearance in both spectra of a new

E. Tomás-Mendivil et al. / Journal of Organometallic Chemistry 727 (2013) 1e9
5
one at dP ¼ 31 ppm. Purification of the reaction mixtures by column
chromatography over silica gel allowed the isolation of [AuCl{k1
(P)-PPh2(py-6-tert-amyl)}] (4) as an air-stable white solid, albeit
only in a modest yield (ca. 53%) due to its partial decomposition
during the chromatographic work-ups.
observed transmetalation processes may be triggered by the for-
mation of complexes 3aeb. In favour of this hypothesis is the fact
that partial displacement of PPh2(py-6-tert-amyl) (2) by SMe2
-
takes place when complexes [RuCl2(
h
6-p-cymene){
k
1-(P)-PPh2(py-
6-tert-amyl)}] (1a) and [RuCl2(h3 3-C10H16){
:h
k
1-(P)-PPh2(py-6-tert-
The characterization of complex 4, which can be alternatively
synthesized in an excellent 91% yield from the direct reaction of
[AuCl(SMe2)] with one equivalent of the phosphine ligand PPh2(py-
6-tert-amyl) (2) in dichloromethane at r.t. (Scheme 1), was
straightforward following its analytical and spectroscopic data
(details are given in the Experimental section). In addition, its
structure was unambiguously confirmed by means of a single-
crystal X-ray diffraction analysis. X-ray quality crystals were
obtained by slow diffusion of n-pentane into a saturated solution of
4 in dichloromethane. An ORTEP-type view, along with selected
structural parameters, is shown in Fig. 2. Two independent mole-
cules were found in the asymmetric unit cell, connected through
amyl)}] (1b) were dissolved in a 1:1 mixture of dichloromethane/
dimethyl sulfide, as readily evidenced by 31P{1H} NMR spectro-
scopy. However, we must note that the quantity of free PPh2(py-6-
tert-amyl) present in solution never exceeded 30%, even after
leaving the NMR tubes for 4 days at room temperature. This fact
indicates that the equilibrium shown in Eq. (1) is set in solution.
a
short
intermolecular
aurophilic
contact
(Au(1)e
ꢀ
Au(2) ¼ 3.1638(4) A) [23]. The coordination around both gold
Trapping of PPh2(py-6-tert-amyl) (2) by coordination to AuCl
centres is almost linear with CleAueP angles of 174.37(6) and
would shift the equilibrium to the right, thus leading to the total
ꢂ
consumption of the starting complexes [RuCl2(
h -
6-p-cymene){k1
ꢀ
173.09(6) , and bond distances AueP of 2.234(1) and 2.231(2) A,
and AueCl of 2.288(2) and 2.291(2) A. These intramolecular
(P)-PPh2(py-6-tert-amyl)}] (1a) and [RuCl2(h3 3-C10H16){ 1-(P)-
:h k
ꢀ
bonding parameters compare well with those previously found in
PPh2(py-6-tert-amyl)}] (1b), as observed in the reactions depicted
in Scheme 1. At this point we must note that the displacement of
a coordinated phosphine by dimethyl sulfide is rather surprising
since SMe2 is usually considered as a highly labile ligand [13,25].
Steric hindrance between the bulky tert-amyl substituent and the
p-cymene (1a) or the 2,7-dimethylocta-2,6-diene-1,8-diyl (1b)
fragments may be again responsible of this unexpected fact, pro-
voking the easy dissociation of PPh2(py-6-tert-amyl) from 1aeb. In
favour of this hypothesis is the fact that no displacement of the
parent PPh2py ligand was observed by 31P{1H} NMR spectroscopy
the solid-state structure of the related Au(I) complex [AuCl{k
1-(P)-
PPh2py}] (PPh2py
¼
2-(diphenylphosphino)pyridine; CleAue
ꢂ
ꢀ
ꢀ
P ¼ 178.0(2) , AueP ¼ 2.286(4) A and AueCl ¼ 2.234(4) A) for
which, on the contrary, no intermolecular Au/Au interactions
were found [24].
Transmetalation of the pyridyl-phosphine ligand from com-
plexes [RuCl2(
[RuCl2(h3 3-C10H16){
unit is accompanied by the formation of the dimethyl sulfide ad-
ducts [RuCl2(
6-p-cymene)(SMe2)] (3a) [13] and [RuCl2(h3 h3
C10H16)(SMe2)] (3b), respectively, along with minor amounts of the
parent ruthenium dimers [{RuCl( -Cl)(
6-p-cymene)}2] and
[{RuCl(
-Cl)(h3 3-C10H16)}2]. Although complexes 3aeb could not
h k
6-p-cymene){ 1-(P)-PPh2(py-6-tert-amyl)}] (1a) and
:
h
k
1-(P)-PPh2(py-6-tert-amyl)}] (1b) to the AuCl
when the related complex [RuCl2(h k
6-p-cymene){ 1-(P)-PPh2py}]
h
: -
was dissolved in a 1:1 mixture of dichloromethane/dimethyl sul-
m
h
fide. Only the chelation of the 2-(diphenylphosphino)pyridine
ligand to afford [RuCl(h k
6-p-cymene){ 2-(P,N)-PPh2py}][Cl] took
m
:h
be isolated in pure form during the chromatographic work-ups,
they were clearly identified in the crude reaction mixtures by 1H
NMR spectroscopy, by comparison of the spectra with those of pure
place with time (both compounds are known; see Ref. [7]).
Transmetalation of the pyridyl-phosphine ligand PPh2(py-6-
tert-amyl) was also observed when dichloromethane solutions of
complexes 1aeb were treated with one equivalent of AgSbF6 in the
presence of SMe2 (10 equiv.). The reactions, performed at r.t. and in
the absence of light, led to the formation of the dimethyl sulfide
samples of 3aeb generated by cleavage of [{RuCl(
m-Cl)(h
6-p-cym-
ene)}2] and [{RuCl(
m
-Cl)(h3 3-C10H16)}2] with SMe2 (details on the
:h
synthesis and characterization of the novel bis(allyl)-ruthenium(IV)
derivative 3b can be found in the Experimental section). The
adducts 3aeb and the novel dinuclear Ag(I) derivative [Ag2{m-
Fig. 2. ORTEP-type view of the structure of complex [AuCl{
clarity. Thermal ellipsoids are drawn at the 30% probability level. Selected bond distances (A) and angles (deg): Au(1)eCl(1) ¼ 2.288(2); Au(1)eP(1) ¼ 2.234(1); Au(2)e
Cl(2) ¼ 2.291(2); Au(2)eP(2) ¼ 2.231(2); Au(1)eAu(2) ¼ 3.1638(4); P(1)eAu(1)eCl(1) ¼ 174.37(6); P(2)eAu(2)eCl(2) ¼ 173.09(6).
k
1-(P)-PPh2(py-6-tert-amyl)}] (4) showing the crystallographic labelling scheme. Hydrogen atoms have been omitted for
ꢀ

6
E. Tomás-Mendivil et al. / Journal of Organometallic Chemistry 727 (2013) 1e9
PPh2(py-6-tert-amyl)}2][SbF6]2 (5), which could be isolated in pure
form (ca. 66%) by successive recrystallizations of the crude reaction
mixtures (Scheme 2). As expected, complex [Ag2{m-PPh2(py-6-tert-
amyl)}2][SbF6]2 (5) can be properly synthesized in 94% isolated
yield by direct reaction of AgSbF6 with one equivalent of PPh2(py-6-
tert-amyl) (2) in dichloromethane (details are given in the
Experimental section). Although the dinuclear nature of this com-
pound was predictable, since the treatment of silver(I) salts AgX
(Xꢀ ¼ NO3ꢀ, NOꢀ2 , BFꢀ4 , ClO4ꢀ, TfOꢀ) with a stoichiometric amount of
2-(diphenylphosphino)pyridine (PPh2py) has been reported to
yield dinuclear species of general composition [Ag2(m-PPh2py)2]
[X]2 [26], its structure was unambiguously confirmed by means of
X-ray diffraction methods [27]. X-ray quality crystals were grown
by slow diffusion of n-pentane into a saturated solution of 5 in
tetrahydrofuran.
As shown in Fig. 3, solvated crystals that contain two tetrahy-
drofuran molecules per molecular unit of 5 were obtained. These
solvent molecules interact with the silver atoms as indicated by the
observed Ag(1)eO(1) and Ag(2)eO(2) distances of 2.650(8) and
ꢀ
2.719(8) A, respectively. The two silver atoms are held together by
two PPh2(py-6-tert-amyl) ligands acting as bridges through the P
and N atoms in a head-to-tail configuration, and show a slightly
distorted linear geometry (P(1)eAg(1)eN(2) and P(2)eAg(2)eN(1)
ꢂ
ꢀ
bond angles of 160.7(2) ). The Ag/Ag separation of 2.950(9) A
found in the structure of 5 is slightly shorter than those reported for
ꢀ
[Ag2(
m
ꢀ
-PPh2py)2][NO3]2 (3.145 A) [26a], [Ag2(
m
-PPh2py)2][NO2]2
ꢀ
(3.105 A) [26d] and [Ag2(m-PPh2py)2][OTf]2 (3.044 A) [26e]. We note
Fig. 3. ORTEP-type view of the structure of complex [Ag2{m-PPh2(py-6-tert-amyl)}2]
that all these values fall within the expected range for a silvere
silver interaction, for which an upper limit of 3.30 A has been
established [28].
[SbF6]2 (5) showing the crystallographic labelling scheme. Hydrogen atoms and SbF6ꢀ
ꢀ
anions have been omitted for clarity. Thermal ellipsoids are drawn at the 30% proba-
ꢀ
bility level. Selected bond distances (A) and angles (deg): Ag(1)eP(1) ¼ 2.397(2);
Interestingly, when the reactions of complexes 1aeb with
AgSbF6 were performed in the absence of SMe2, neither trans-
metalation of the pyridyl-phosphine to silver, nor abstraction of
one of the chloride ligands from ruthenium was observed. Instead,
the unexpected protonation of the pyridyl group slowly occurred
(Scheme 2) [29,30]. We were thus able to isolate the new com-
plexes 6aeb in 55e83% yield, which were characterized by stan-
dard spectroscopic techniques and elemental analyses (details are
given in the Experimental section). Protonation of the pyridyl unit
was clearly evidenced in their 1H NMR spectra by the appearance of
Ag(1)eN(2)
N(1)
¼
2.228(8); Ag(1)eO(1)
¼
2.650(8); Ag(2)eP(2)
¼
2.414(2); Ag(2)e
¼
2.270(8); Ag(2)eO(2)
¼
2.719(8); Ag(1)eAg(2)
¼
2.950(9); P(1)eAg(1)e
N(2) ¼ 160.7(2); N(2)eAg(1)eO(1) ¼ 108.8(3); P(1)eAg(1)eO(1) ¼ 90.5(2); P(2)e
Ag(2)eN(1) ¼ 160.7(2); N(1)eAg(2)eO(2) ¼ 110.3(3); P(2)eAg(2)eO(2) ¼ 89.0(2).
for the NH protons. Further structural confirmation was obtained
through X-ray diffraction studies on monocrystals of 6ae
b generated by slow diffusion of n-pentane into saturated solu-
tions of the complexes in dichloromethane. ORTEP views of the
molecules, along with selected structural parameters, are shown in
Figs. 4 and 5.
a characteristic low-field singlet resonance at
d 14.16e15.45 ppm
Scheme 2. Reactivity of the ruthenium complexes 1aeb towards AgSbF6.

E. Tomás-Mendivil et al. / Journal of Organometallic Chemistry 727 (2013) 1e9
7
Fig. 5. ORTEP-type view of the structure of [RuCl2(h3
:h
3-C10H16){
k
1-(P)-PPh2(pyH-6-
tert-amyl)}][SbF6] (6b) showing the crystallographic labelling scheme. Hydrogen
atoms, except that on N(1), and SbFꢀ6 anion have been omitted for clarity. Thermal
ꢀ
ellipsoids are drawn at 20% probability level. Selected bond distances (A) and angles
(deg): Ru(1)eCl(1) ¼ 2.124(6); Ru(1)eCl(2) ¼ 2.379(3); Ru(1)eP(1) ¼ 2.410(2); Ru(1)e
C* ¼ 2.0009(7); Ru(1)eC** ¼ 2.0015(7); Ru(1)eC(1) ¼ 2.22(1); Ru(1)eC(2) ¼ 2.26(1);
Fig. 4. ORTEP-type view of the structure of complex [RuCl2(h k
6-p-cymene){ 1-(P)-
Ru(1)eC(4)
¼
2.27(1); Ru(1)eC(7)
¼
2.22(1); Ru(1)eC(8)
¼
2.28(1); Ru(1)e
PPh2(pyH-6-tert-amyl)}][SbF6] (6a) showing the crystallographic labelling scheme.
C(10) ¼ 2.248(8); C(1)eC(2) ¼ 1.43(1); C(2)eC(4) ¼ 1.33(2); C(7)eC(8) ¼ 1.41(2); C(8)e
C(10) ¼ 1.41(2); Cl(1)eRu(1)eCl(2) ¼ 168.9(5); Cl(1)eRu(1)eP(1) ¼ 89.4(2); Cl(1)e
Ru(1)eC* ¼ 87.9(2); Cl(1)eRu(1)eC** ¼ 89.4(2); Cl(2)eRu(1)eP(1) ¼ 84.2(2); Cl(2)e
Ru(1)eC* ¼ 87.1(4); Cl(2)eRu(1)eC** ¼ 101.3(5); P(1)eRu(1)eC* ¼ 117.72(6); P(1)e
Ru(1)eC** ¼ 110.77(5); C*eRu(1)eC** ¼ 131.39(3); C(1)eC(2)eC(4) ¼ 118(1); C(7)e
C(8)eC(10) ¼ 114.4(9). C* and C** denote the centroids of the allyl units (C(1), C(2) and
C(4), and C(7), C(8) and C(10), respectively).
Hydrogen atoms, except that on N(1), and SbFꢀ6 anion have been omitted for clarity.
ꢀ
Thermal ellipsoids are drawn at the 20% probability level. Selected bond distances (A)
and angles (deg): Ru(1)eP(1)
¼
2.339(1); Ru(1)eCl(1)
¼
2.398(1); Ru(1)e
Cl(2)
¼
2.406(2); Ru(1)eC* 1.7035(4); C*eRu(1)eP(1)
¼
¼
130.60(4); C*eRu(1)e
Cl(1) ¼ 125.49(4); C*eRu(1)eCl(2) ¼ 125.70(4); P(1)eRu(1)eCl(1) ¼ 87.36(5); P(1)e
Ru(1)eCl(2) ¼ 86.13(5); Cl(1)eRu(1)eCl(2) ¼ 87.87(5). C* denotes the centroid of the p-
cymene ring (C(1), C(2), C(3), C(4), C(5) and C(6)).
respectively), compare well with those previously observed in
Concerning the ruthenium(II) complex [RuCl2(
h
6-p-cymene){k1
-
other structures containing the “Ru(h3 3-C10H16)” moiety [7,31].
:h
(P)-PPh2(pyH-6-tert-amyl)}][SbF6] (6a) (Fig. 4), it exhibits the
expected pseudooctahedral three-legged piano-stool geometry
around the metal with values of the interligand angles P(1)eRu(1)e
Cl(1) (87.36(5)ꢂ), P(1)eRu(1)eCl(2) (86.13(5)ꢂ), and Cl(1)eRu(1)e
Cl(2) (87.87(5)ꢂ), and those between the centroid of the p-cym-
ene ring C* and the legs (125.49(4)e133.60(4)ꢂ), typical of
a pseudo-octahedron. Remarkably, the bond distances involving
the ruthenium atom and those of the pyridyl-phosphine skeleton
It is also worthy of note that an intramolecular H-bonding
interaction between the N(1)eH(1n) unit and one of the chloride
ligands was found in the crystal structure of this complex [32].
According to the classification of Jeffrey [33], the distance and angle
ꢂ
ꢀ
of the N(1)eH(1n)/Cl(1) contact of 1.989(6) A and 130.7(6) ,
respectively, allow it to be classified only as “moderate” (mostly
electrostatic) among the H-bonds considered most common in
chemical systems. However, it seems to be maintained in CD2Cl2
solution since the 1H and 13C{1H} NMR spectra of 6b recorded in
this solvent showed a doubling of some proton and carbon reso-
nances for the octadienediyl C10H16 unit (e.g. 8 different signals
were observed in the 13C{1H} NMR spectrum; see Experimental
section). A unique set of signals for the two allylic moieties (i.e. 5
carbon resonances and 6 proton resonances) is expected to appear
in the 1H and 13C{1H} NMR spectra of equatorial adducts
ꢀ
were almost identical (ꢄ0.03 A) to those previously observed in the
solid-state crystal structure of the related neutral complex
[RuCl2(
a negligible structural effect of the protonation of the pyridyl unit.
For the ruthenium(IV) complex [RuCl2(h3 3-C10H16){ 1-(P)-
h k
6-benzene){ 1-(P)-PPh2(py-6-tert-amyl)}] [7], reflecting
:
h
k
PPh2(pyH-6-tert-amyl)}][SbF6] (6b), the geometry about the metal
atom is best described as a highly distorted trigonal bipyramid by
considering the allyl groups as monodentate ligands bound to the
metal through their centres of mass (C* and C**; see caption of
Fig. 5). The chloride ligands occupy the axial positions (Cl(1)e
Ru(1)eCl(2) bond angle of 168.9(5)ꢂ), while the octadienediyl
moiety and the PPh2 unit of the pyridyl-phosphine are located at
the equatorial sites. Both allyl groups of the organic C10H16 frag-
[RuCl2(h3 3-C10H16)(PR3)] due to the local C2-symmetry for the
:h
octadienediyl chain [31,34]. The doubling of the signals for 6b in-
dicates that the two halves of the octadienediyl ligand are in
inequivalent environments. Restricted rotation around the RueP
bond, instead of the occurrence of the N(1)eH(1n)/Cl(1) H-bond
in solution, could be alternatively evoked to explain these obser-
vations. However, this end was discarded since complete equiv-
alence of the two halves of the octadienediyl ligand was previously
found in the 1H and 13C{1H} NMR spectra of the parent compound
ment are
h
3-bound to the ruthenium atom with RueC and CeC
ꢀ
distances in the ranges 2.22(1)e2.28(1) and 1.33(2)e1.43(1) A,
respectively. These values, together with the internal allylic C(1)e
C(2)eC(4) and C(7)eC(8)eC(10) angles (118(1)ꢂ and 114.4(9)ꢂ,
[RuCl2(h3 3-C10H16){ 1-(P)-PPh2(py-6-tert-amyl)}] (2b) [7].
:h k

8
E. Tomás-Mendivil et al. / Journal of Organometallic Chemistry 727 (2013) 1e9
(d) S.E. García-Garrido, J. Francos, V. Cadierno, J.-M. Basset, V. Polshettiwar,
4. Conclusion
ChemSusChem 4 (2011) 104e111;
(e) R. García-Álvarez, J. Francos, P. Crochet, V. Cadierno, Tetrahedron Lett. 52
(2011) 4218e4220;
(f) R. García-Álvarez, J. Díez, P. Crochet, V. Cadierno, Organometallics 30
(2011) 5442e5451;
(g) R. García-Álvarez, A.E. Díaz-Álvarez, J. Borge, P. Crochet, V. Cadierno, Or-
ganometallics 31 (2012) 6482e6490.
In summary, transmetalation processes of a pyridyl-phosphine
ligand from ruthenium(II) and ruthenium(IV) complexes to
gold(I) and silver(I) centres, triggered by dimethyl sulfide, have
been presented. Steric grounds are behind the unprecedented re-
sults reported herein, since the presence of the bulky tert-amyl
substituent in PPh2(py-6-tert-amyl) (2) turns it into a labile ligand
able to be partially displaced by the weak SMe2 donor. Such lability
should be taken into account in future works when designing new
metal-catalysts based on this ligand.
[7] R. García-Álvarez, S.E. García-Garrido, J. Díez, P. Crochet, V. Cadierno, Eur. J.
Inorg. Chem. (2012) 4218e4230.
[8] This ligand, developed by Hintermann and co-workers, previously proved
useful in the ruthenium-catalyzed anti-Markovnikov hydration of terminal
alkynes through bifunctional reaction pathways: (a) T. Kribber, A. Labonne,
L. Hintermann, Synthesis (2007) 2809e2818;
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(c) L. Hintermann, L. Xiao, A. Labonne, Angew. Chem. Int. Ed. 47 (2008) 8246e
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Acknowledgements
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The authors are indebted to the Ministerio de Economía y
Competitividad of Spain (Projects CTQ2010-14796/BQU, CTQ2009-
08746/BQU and CSD2007-00006) for financial support. S.E.G.-G.
and E.T.-M. also thank the Spanish Government and the European
Social Fund for the award of a “Ramón y Cajal” contract and a FPU
grant, respectively.
[9] Some examples of heterobimetallic Ru/Au complexes bridged by the related
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Appendix A. Supplementary material
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CCDC 905256 (4), 905257 (5) 905258 (6a) and 905259 (6b)
contain the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_
request/cif.
Appendix B. Supplementary data
Supplementary data associated with this article can be found, in
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12.027.
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9
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m
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