Two in one: Charged tertiary phosphines held together by ionic or covalent interactions as bidentate phosphorus ligands for synthesis of half-sandwich Ru(II)-complexes

Article abstract of DOI:10.1016/j.poly.2013.05.008

Ion pairs consisting of N-substituted derivatives of 1,3,5-triaza-7- phosphaadamantane (pta-R; R = benzyl, butyl, hexyl) as cations and monosulfonated triphenylphosphine (mtppms) as anion were synthesized and characterized (including X-ray diffraction, to

Full text of DOI:10.1016/j.poly.2013.05.008

Polyhedron 60 (2013) 1–9
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Polyhedron
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Two in one: Charged tertiary phosphines held together by ionic or
covalent interactions as bidentate phosphorus ligands for synthesis
of half-sandwich Ru(II)-complexes
Antal Udvardy a, Attila Csaba Bényei a,b, Péter Juhász a, Ferenc Joó a,c, Ágnes Kathó a,
⇑
a Department of Physical Chemistry, University of Debrecen, P.O. Box 7, Debrecen H-4010, Hungary
b Department of Pharmaceutical Chemistry, Medical and Health Science Centre, University of Debrecen, P.O. Box 70, Debrecen H-4010, Hungary
c MTA-DE Research Group of Homogeneous Catalysis and Reaction Mechanisms, P.O. Box 7, Debrecen H-4010, Hungary
a r t i c l e i n f o
a b s t r a c t
Article history:
Ion pairs consisting of N-substituted derivatives of 1,3,5-triaza-7-phosphaadamantane (pta-R; R = benzyl,
butyl, hexyl) as cations and monosulfonated triphenylphosphine (mtppms) as anion were synthesized
and characterized (including X-ray diffraction, too). These ion pairs act as bidentate phosphorus ligands
Received 28 March 2013
Accepted 4 May 2013
Available online 13 May 2013
in reactions with [(
Bisphosphine 3 of good water-solubility was synthesized in reaction of pta with 1,4-bis(chloro-
methyl)benzene and used for the synthesis of the water-soluble dinuclear complex [{(
6-C10H14)-
RuCl2}2( -3)]Cl2.
g
6-C10H14)RuCl2]2, yielding mononuclear or dinuclear half sandwich Ru(II) complexes.
Keywords:
1,3,5-Triaza-7-phosphaadamantane
Sulfonated
g
l
Ó 2013 Elsevier Ltd. All rights reserved.
Phosphines
Ion pairs
Bidentate ligand
1. Introduction
dentate ones. Construction of a number of complex structures from
simple building units via association by secondary interactions can
be faster, more versatile and economic than synthesis of ligands of
similar size and complexity based on covalent bonding.
Bi- or multidentate ligands play important role in coordination
chemistry and homogeneous catalysis. Since the two or more do-
nor atoms are held together by covalent bonds of appropriate con-
nectivity in several cases synthesis of such ligand molecules
requires time-consuming, multistep reactions.
Some important steps are already taken on this novel field
including studies of transition metal complexes with supramolecu-
lar bidentate ligands produced by self-organization [1]. For exam-
ple, wheel-and-axle-type organometallic complexes were
synthesized having two half-sandwich Ru(II)-units as wheels, while
the axle was formed by H-bonding between the non-coordinated
The essence of homogeneous catalysis is in the tuning of elec-
tronic, steric and coordination properties of the catalytically active
metal complex species to make it possible to roll along the path of
the catalytic cycle and perform the required electron and/or atom
transfer between the substrate molecules, mostly within the coor-
dination sphere of the metal. Multidentate ligands provide the nec-
essary versatility in terms of coordination mode and steric
requirements to assist catalysis. Capitalizing on secondary interac-
tions instead of covalent bonding to connect the appropriate donor
atoms represent a supramolecular approach for the delicate tuning
of the catalytic metal complex. Moreover, this is one of the working
principles of enzyme catalysis where secondary interactions are
crucial to held together the active site where electron and atom
transfer to the substrate molecule(s) occur. This is why it has been
conceived that instead of the traditional synthetic procedures
bidentate ligands may also be obtained by self-assembly of mono-
carboxylic acid groups in the two [(
zoic acid)] complexes [2]. Similar phenomena were described with
[(
6-C10H14)RuCl2(L)] complexes having iso-nicotinic acid or 4-
g
6-C10H14)RuCl2(4-aminoben-
g
aminocinnamic acid [2] as well as Ph2CH2NHC6H4COOH [3] ligands.
Association of ligands may lead not only to bridging units but to
chelating ligands, too. In the presence of transition metal ions 6-
diphenylphosphinopyridone forms an H-bridged associate with
its own tautomer. Bidentate character of this self-organized mole-
cule was established both in solution (NMR) and in the solid phase
(X-ray) [4].
Gulyás et al obtained bidentate phosphorus ligands held to-
gether by ionic interactions. Triphenylphosphine derivatives with
ꢀ
oppositely charged substituents (–SO3 and –NH3+, respectively)
formed ion pairs even in polar media. In the investigated Rh- and
Pd-complexes, both phosphorus donor atoms of such strongly held
ion pairs coordinated to the same metal ion [5].
⇑
Corresponding author. Tel.: +36 52 512900; fax: +36 52 512915.
E-mail address: katho.agnes@science.unideb.hu (Á. Kathó).
0277-5387/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2013.05.008

2
A. Udvardy et al. / Polyhedron 60 (2013) 1–9
+
Cl2
P
P
-
P
P
SO3
R
N
N
N
N
N
R
N
N
N
N
R
2
R= CH2-C6H5;
R= (CH2)nCH3; n = 5:
n = 3: 5
3
( )Cl2
R= H; mtppms: 1
R= SO3- ; mtppts
4
Scheme 1. Water-soluble phosphines used in this study.
We have also reported on formation of stable ion pairs formed
on a BRUKER BioTOF II ESI-TOF spectrometer. Elemental analyses
were carried out using Elementar Vario Micro instrument.
All reagents and solvents were commercially available and used
as received with the exception of Na(mtppms) [27], Na3(mtppts)
[28], pta [29], (pta-Me)I [17], (pta-Me)CF3SO3 [16], (pta-R)Br
by oppositely charged water-soluble tertiary phosphines [6]. As
anions we used mono-sulfonated triphenylphosphine (mtppms,
1; well known from aqueous organometallic catalysis [7]) while
the cation was N-benzyl-1,3,5-triaza-7-phosphaadamantane, 2
(Scheme 1).
1,3,5-Triaza-7-phosphaadamantane (pta) is often used in aque-
ous organometallic catalysis [8]. [RuCl2(pta)4] has been studied in
hydrogenation of aldehydes [9] and this complex was found active
also in hydrogenation of bicarbonate [10] and in hydration of ni-
triles [11]. These reactions are also catalyzed by the half-sandwich
complexes formed in reactions of [(arene)RuCl2]2 and pta [12–14].
Half-sandwich Ru(II)-pta complexes with the general name RAPTA
are subject to scrutiny not only because of their catalytic effect but
also of their anticancer activity [15].
(R = Et, nPr, nBu [20]), (pta-Bn)Cl [25], [(
g
6-C10H14)RuCl2]2 [30],
6-C10H14)RuCl2(pta-
Na[( g
g
6-C10H14)RuCl2(mtppms)] [31] and [(
Bn)]Cl, 6 [14] which were prepared according to the literature.
2.2. Synthesis of ligands
2.2.1. 1,10-[1,4-phenylenebis(methylene)]bis-3,5-diaza-1-azonia-7-
phosphatricyclo[3.3.1.1]decane dichloride
A
suspension of 100.0 mg (0.637 mmol) pta and 55.7 mg
(0.318 mmol) of 1,4-bis(chloromethyl)benzene in acetone (3 mL)
was refluxed for 3 h. The mixture was cooled to room temperature
and the precipitate was collected on a frit. The solid was washed
with a small amount of cold acetone and vacuum-dried. The white
compound is soluble in water. Yield 115 mg (74%). Anal. Calc. for
P2Cl2N6C20H32 (M = 489.36): C, 49.08; H, 6.59; N, 17.17. Found: C,
48.54; H, 6.21; N, 16.95%. Electrospray MS (in H2O): observed m/
N-Alkyl derivatives of pta can also be used as ligands in half-
sandwich Ru-complexes [14,16]. Already at the time of the first
synthesis of pta it was established that it could be methylated on
one of the N-atoms by MeI [17]. In addition, several cationic pta-
R derivatives were obtained by longer chain alkyl iodides (EtI
[18], nPrI [19], nBuI [20], I(CH2)4I [21]) as well as with various bro-
momethyl compounds (BrCH2Y, where Y = C6H4N [22], C6H5,
COOMe, CN [23,24]). With benzyl chloride 1-benzyl-1-azonia-
3,5-diaza-7-phosphaadamantyl cation, pta-Bn (2) is formed [25]
z
209.107, calcd. 209.100 for P2N6C20H32 = M2+ 1H NMR
.
(360 MHz, D2O, 25 °C): d/ppm 3.85 (m, 8H, PCH2N), 4.20 (s, 4H,
PCH2N+), 4.54 (m, 8H, PCH2N+, NCH2N), 4.98 (m, 8H, NCH2N+),
7.64 (s, 4H, HPh). 13C{1H} NMR (90 MHz, D2O, 25 °C): d/ppm
while
1,4-bis(chloromethyl)benzene
[6]
and
bis(bromo-
methyl)benzene are able to alkylate and connect two pta mole-
cules. Attempts to use the bisphosphine ligand, 1,10-[1,4-
phenylenebis(methylene)]bis-3,5-diaza-1-azonia-7-phosphatricy-
clo[3.3.1.1] decane, 3 (as its bromide salt) for synthesis of a binu-
clear complex in reaction with cis-[PtBr2(cod)] did not yield well
defined products [26].
1
1
45.56 (d, JPC = 22 Hz, PCH2N), 52.89 (d, JPC = 33 Hz, PCH2N+),
65.83 (s, PhCH2N+), 69.38 (s, NCH2N), 78.90 (s, NCH2N+), 127.38
(s, CHPh), 133.68 (s, CPh). 31P{1H} NMR (145 MHz, D2O, 25 °C):
d = ꢀ82.03 ppm (s). 31P{1H} NMR (145 MHz, MeOD, 25 °C):
d = ꢀ79.5 ppm (s).
In this paper we report successful syntheses of dinuclear and
chelate complexes obtained from Ru(II) precursors and ionic phos-
2.2.2. 1-Hexyl-1-azonia-3,5-diaza-7-phosphaadamantyl bromide,
(4)Br
phine ligands. We show that reaction of (3)Cl2 and [(g
6-C10H14)-
RuCl2]2 yields a binuclear complex in which 3 serves as bridging
ligand between the two half-sandwich Ru(II)-arene units. Synthe-
sis of (pta-R)(mtppms) ion pairs (R = benzyl, hexyl or butyl) is de-
scribed for the first time as well as their use for synthesis of
binuclear wheel-and-axle complexes. It is also demonstrated, that
(pta-Bn)(mtppms) is able to coordinate to the same Ru(II) center,
and this way half-sandwich Ru(II)-complexes with two different
phosphine ligands can be synthesized in a single step.
A solution of pta (150 mg, 0.95 mmol) and 1-bromo-hexane
(0.33 mL, 2.34 mmol) in 10 mL acetone was refluxed for 1 h. The
mixture was cooled to room temperature and the precipitate was
separated by filtration. The white solid was washed with acetone
(2 ꢁ 5 mL) and Et2O (3 ꢁ 5 mL) and dried. Yield 202 mg (60%). Anal.
Calc. for C12H24N3PBr (M = 320.31): C, 44.92; H, 7.55; N, 13.11.
Found: C, 44.72; H, 7.69; N, 13.04%. Electrospray MS (in MeOH):
observed m/z 241.310, Calc. 241.316 for PN3C12H25 = M+. 1H NMR
1
(360 MHz, MeOD, 25 °C): d/ppm 0.93 (t, 3H, JHH = 7 Hz, CH3),
2. Experimental
1.01–1.30 (m, 6H, N+–CH2CH2CH2CH2CH2CH3), 1.65–1.74 (m, 2H,
N+–CH2CH2), 2.84 (m, 2H, N+–CH2CH2), 3.76–4.04 (m, 4H, PCH2N),
4.32 (d, 2H, JPH = 6 Hz, PCH2N+), 4.37–4.64 (m, 2H, NCH2N), 4.71-
5.09 (m, 4H, N+CH2N). 13C{1H} NMR (90 MHz, MeOD, 25 °C): d/
ppm 13.00 (s, CH3), 19.31 (s, CH2CH3), 19.34 (s, CH2CH2CH3),
21.30 (s, N+–CH2CH2CH3), 24.60 (s, N+–CH2CH2), 45.77 (d, JPC = 22 -
Hz, PCH2N), 53.11 (d, JPC = 33 Hz, PCH2N+), 62.99 (s, N+CH2CH2),
70.01 (s, NCH2N), 78.12 (s, N+CH2N). 31P{1H} NMR (145 MHz,
D2O, 25 °C): d = ꢀ83.7 ppm (s).
2.1. Materials and methods
All reactions and manipulations were carried out under an ar-
gon or nitrogen atmosphere with use of standard Schlenk tech-
niques. 1H, 31P and 13C NMR spectra were recorded on a Bruker
Avance 360 MHz spectrometer and referenced to 3-(trimethyl-
silyl)propanesulfonic acid Na-salt (DSS). Mass data were collected

A. Udvardy et al. / Polyhedron 60 (2013) 1–9
3
2.2.3. General procedure for the preparation of salts containing N-
alkylated pta as a cation and monosulfonated triphenylphosphine as
an anion
C, 41.95; H, 5.29; N, 7.00%. Electrospray MS (in H2O): observed m/z
515.051; Calc. 515.059 for [C40H60 N6P2Cl4Ru2]2+ = M2+ 1H NMR
.
(360 MHz, MeOD, 25 °C): d/ppm 1.07 (d, 12H, J = 7.0 Hz, CH(CH3)2),
1.89 (m, 6H, C–CH3), 2.46 (m, 2H, CH(CH3)2), 3.92 (m, 8H, PCH2N,
4H PCH2N+, 4H, N+CH2), 4.54 (m, 4H, NCH2N), 4.97 (m, 8H, NCH2N+),
5.76 (m, 8H, CHPh of p-cymene), 7.57 (s, 4H, HPh of 3). 13C{1H} NMR
(90 MHz, D2O, 25 °C): d/ppm 17.95 (s, CH3), 21.18 (s, CH(CH3)2),
30.61 (s, CH(CH3)2), 48.45 (d, J = 22 Hz, PCH2N), 51.08 (d,
J = 33 Hz, PCH2N+), 65.12 (s, N+CH2Ph, 69.31 (s, NCH2N), 79.46 (s,
NCH2N+), 86.24 and 88.78 (s, CHPh of p-cymene), 99.00 and
108.07 (s, CPh of p-cymene), 127.10 (s, CH of CPh), 133.62 (s, C of
0.075 mmol of (pta-R)X {21.3 mg for (pta-Bn)Cl, 22.0 mg for
(pta-butyl)Br, and 24.0 mg for (pta-hexyl)Br} was dissolved in
0.5 mL of water and it was added to a solution of 0.075 mmol
(30 mg) of Na-mtppms in 3.0 mL water. White precipitate was
formed almost immediately what was filtered out and washed
with small amount of water and Et2O (3 ꢁ 6 mL). The salt dissolves
well in CHCl3 and CH2Cl2 but poorly in water, hexane, acetone and
Et2O.
C
Ph). 31P{1H} NMR (145 MHz, D2O, 25 °C): d/ppm ꢀ17.9 ppm (s).
2.2.3.1. (pta-Bn)(mtppms), (2)(1). Yield: 31.1 mg (70%). Anal. Calc.
for C31H33N3O3P2S (M = 589.62): C, 63.14; H, 5.60; N, 7.12. Found:
C, 63.48; H, 5.92; N, 7.07%. 1H NMR (360 MHz, MeOD, 25 °C): d/
ppm 3.54–3.87 (m, 4H, PCH2N), 4.18–4.63 (m, 2H, PCH2N+ and d,
2H NCH2N, s, 2H, N+CH2Ph), 5.03–5.30 (m, 4H, N+CH2N), 7.57–
2.3.2. [(
g
6-C10H14)RuCl2(pta-Bn)(mtppms)]Cl
6-C10H14)RuCl2(pta-Bn)]Cl,
6 (100.0 mg,
A
solution of [(
g
0.169 mmol) and Na(mtppms) (67.8 mg, 0.169 mmol) in methanol
(15 mL) was refluxed for 10 h. After cooling to room temperature
the solution was filtered through a pad of Hyflo Supercel and the
filtrate was evaporated to dryness. The oily residue was cooled in
ice and triturated with Et2O several times. The resulting yellow
powder was washed at room temperature with Et2O (3x10 mL)
and dried. The complex dissolves well in water, methanol and eth-
anol but poorly in chloroform. Yield: 112 mg (76%). Anal. Calc. for
7.46 (m, 5HPh
and 14Hmtppms). 13C{1H} NMR (90 MHz, CDCl3,
of
2
25 °C): d/ppm 46.87 (d, JPC = 21 Hz NCH2P), 52.41 (d, JPC = 33 Hz,
N+CH2P), 65.22 (s, N+CH2Ph), 70.47 (s, NCH2N), 79.12 (s, N+CH2N),
125.39-146.69 (m, 4 CPh
and 10 Cmtppms). 31P{1H} NMR
of
2
(145 MHz, CDCl3, 25 °C): d = ꢀ84.0 ppm (s), ꢀ4.3 d = ppm (s).
2.2.3.2. (pta-hexyl)(mtppms), (4)(1). Yield: 22.3 mg (51%). Anal.
Calc. for C30H39N3O3P2S (M = 583.66): C, 61.73; H, 6.73; N, 7.19;
S, 5.49. Found: C, 60.85; H, 6.89; N, 7.16; S, 5.46%. 1H NMR
(360 MHz, MeOD, 25 °C): d/ppm 0.82 (m, 3H, CH3), 1.13–1.35 (m,
6H, N+–CH2CH2CH2CH2CH2CH3), 1.52–1.70 (m, 2H, N+–CH2CH2),
2.63–2.82 (m, 2H, N+–CH2CH2), 3.67–3.94 (m, 4H, PCH2N), 4.13–
4.55 (m, 2H, PCH2N+ and 2H, NCH2N), 4.60–4.99 (m, 4H, N+CH2N),
6.93–7.78 (m, 14 H, aromatic). 13C{1H} NMR (90 MHz, MeOD,
25 °C): d/ppm 14.29 (s, CH3), 20.68 (s, CH2CH3), 23.49 (s, CH2CH2-
CH3), 27.38 (s, N+CH2CH2CH2), 32.34 (s, N+CH2CH2), 47.38 (d,
JPC = 21 Hz, NCH2P), 54.01 (d, JPC = 33 Hz, N+CH2P), 63.68 (s, N+–
CH2CH2), 71.38 (s, NCH2N), 80.93 (s, N+CH2N). 31P{1H} NMR
(145 MHz, MeOD, 25 °C) d = ꢀ82.9 (s), d = ꢀ4.4 ppm (s). 31P{1H}
NMR (145 MHz, CDCl3, 25 °C) d = ꢀ85.0 ppm (s), d = ꢀ4.3 ppm (s).
C
41H47N3O3P2SCl2RuꢂH2O (M = 913.81): C, 53.89; H, 5.40; N, 4.59;
S, 3.50; found: C, 53.29; H, 5.35; N, 4.44; S, 3.06. Electrospray MS
(in H2O): observed m/z: 860.154; Calc. 860.154 for [C41H47N3O3P2-
SClRu]+ = M+. 1H NMR (360 MHz, MeOD, 25 °C): d/ppm 1.23 (m, 6H,
CH(CH3)2), 2.04 (m, 3H, –CH3), 2.64 (m, 1H, CH(CH3)2), 4.01–5.02
(m, 14H, PCH2N, PCH2N+, N+CH2Ph, NCH2N, NCH2N+), 5.73 (m,
4HPh for p-cymene), 6.83–8.90 (m, 5H, HPh
2, 14H, Hmtppms).
of
13C{1H} NMR (90 MHz, D2O, 25 °C): d/ppm 16.99 (s, CH3), 20,35
(d, J = 22 Hz CH(CH3)2), 30,63 (s, CH(CH3)2), 48.43 (d, J = 17 Hz,
PCH2N), 50.71 (d, J = 19 Hz, PCH2N+), 64.91 (s, N+CH2Ph), 68.60 (s,
NCH2N), 79.88 NCH2N+), 89.04 and 92,52 (s, CHPh of p-cymene),
94,25 and 103,71 (s, C of p-cymene),127.25-144 (m, CPh of 2 and Cm-
tppms). 31P{1H} NMR (145 MHz, D2O, 25 °C) d = 28.1 ppm (d,
J
PP = 46 Hz) and d = ꢀ24.1 ppm (d, JPP = 53 Hz). 31P{1H} NMR
(145 MHz, MeOD, 25 °C) d = 27.6 ppm (d,
d = ꢀ24.7 ppm (d, JPP = 53 Hz).
JPP = 46 Hz) and
2.2.3.3. (pta-Bu)(mtppms), (5)(1). Yield: 27.1 mg (64%). Anal. Calc.
for C28H35N3O3P2S (M = 555.66): C, 60.53; H, 6.34; N, 7.56; S,
5.77. Found: C, 59.92; H, 6.48; N, 7.56; S, 5.82%. 1H NMR
(360 MHz, MeOD, 25 °C): d/ppm 0.89 (t, JHH = 7 Hz, 3H, CH3), 1.26
(sextet, JHH = 7 Hz, 2H, CH2CH3), 1.50–1.74 and 2.62–2.91 (m, 4H,
N+–CH2CH2CH2CH3), 3.67–4.02 (m, 4H, PCH2N), 4.15–4.57 (m, 2H,
PCH2N+, 2H, NCH2N), 4.61–5.03 (m, 4H, N+CH2N), 7.07–7.82 (m,
14 H, aromatic). 13C{1H} NMR (90 MHz, MeOD, 25 °C): d/ppm
13.94 (s, CH3), 21.04 (s, CH2CH3), 22.70 (s, CH2CH2CH3), 46.85 (d,
JPC = 21 Hz, PCH2N), 54.00 (d, JPC = 33 Hz, PCH2N+), 63.44 (s, N+–
CH2CH2), 71.36 (s, NCH2N), 80.91 (s, N+CH2N), 127.45–146.87 (m,
aromatic). 31P{1H} NMR (145 MHz, MeOD, 25 °C): d = ꢀ82,9 ppm
(s) d = ꢀ4.4 ppm (s). 31P{1H} NMR (145 MHz, CDCl3, 25 °C):
d = ꢀ85.2 ppm (s), d = ꢀ4.3 ppm (s).
2.3.3. [(
g
6-C10H14)RuCl2(pta-Bn)][(
g
6-C10H14)RuCl2(mtppms)]
6-C10H14)RuCl2]2
A
solution of the dimeric precursor [(
g
(100.0 mg, 0.163 mmol) and an equimolar amount of (pta-
Bn)(mtppms) (96.2 mg, 0.163 mmol) in methanol (8 mL) was stir-
red at room temperature for 1 h. The solvent was evaporated under
vacuum and the residue was washed with 2 mL of water. The or-
ange solid was washed with Et2O (3 ꢁ 10 mL) and dried under vac-
uum. The compound dissolves well in methanol, ethanol and
chloroform but poorly in water. Yield: 139 mg (70%). Anal. Calc.
for C51Cl4H61N3O3P2Ru2S (M = 1201.99): C, 50.96; H, 5.11; N,
3.49. Found: C, 50.77; H, 4.95; N, 3.38%. Spectral parameters for
[(g
6-C10H14)RuCl2(pta-Bn)]+ 1.23 (d, J = 7 Hz, 6 H, CH(CH3)2), 2.05
(s, 3H, CH3), 2.69 (m, CH(CH3)2), 4.30 (m, 4H, PCH2N and 2H, PCH2-
N+), 4.35 (s, 2H, N+CH2Ph), 4.60 (m, 2H NCH2N), 5.12 (m, 4H, NCH2-
N+), 5.87 (m, 4H CHPh of p-cymene), 7.30–8.54 (m, aromatic).
31P{1H} NMR (145 MHz, in MeOD, 25 °C) d = ꢀ18.6 (s).
2.3. Synthesis of half sandwich Ru-complexes
2.3.1. [{(
solution of the dimeric precursor [(
g l-3)] Cl2
6-C10H14)RuCl2}2(
A
g
6-C10H14)RuCl2]2
Spectral parameters for [(g
6-C10H14)RuCl2(mtppms)]ꢀ: 1H NMR
(100.0 mg, 0.163 mmol) and an equimolar amount of (3)Cl2
(80.0 mg, 0.163 mmol) in methanol (10 mL) was refluxed for
20 min. After cooling to room temperature, the volume was re-
duced to approximately 5 mL by vacuum-evaporation what led
to the precipitation of an orange solid. The product was washed
with EtOH (3 ꢁ 3 mL) and Et2O (3 ꢁ 10 mL) and vacuum-dried.
The complex dissolves well in water, methanol and ethanol but
poorly in chloroform. Yield: 91.0 mg (51%). Anal. Calc. for Ru2C40-
H60Cl6N6P2 ꢂ2H2O (M = 1138.01): C, 42.22; H, 5.67; N, 7.38. Found:
(360 MHz, MeOD, 25 °C): d/ppm 1.13 (d, J = 7 Hz, 6H, CH(CH3)2),
1.94 (s, 3 H, CH3), 2.69 (m, 2H, CH(CH3)2), 5.33 (d, J = 6.0 Hz, 4H,
CHPh of p-cymene), 7.30–8.54 (m, aromatic).
31P{1H} NMR (145 MHz, in MeOD, 25 °C) d = 26.1 ppm (s).
2.4. X-ray crystallographic studies
A summary of crystallographic data for (2)(1), (4)(1), (5)(1) and
6.2H2O are collected in Table 1. Crystals of (2)(1), (4)(1), and (5)(1)

4
A. Udvardy et al. / Polyhedron 60 (2013) 1–9
Table 1
Crystallographic data and structure refinement results for (pta-Bn)(mtppms), (2)(1); (pta-hexyl)(mtppms), (4)(1); (pta-butyl)(mtppms),
(5)(1) and [(
g
6-C10H14)RuCl2(pta-Bn)]Clꢂ2 H2O, 6ꢂ2 H2O.
(2)(1)
Structure
Formula
(4)(1)
(5)(1)
6
C
31H33N3O3P2S
C28H35N3O3P2S
555.59
C30H39N3O3P2S
583.64
C23H37Cl3N3O2PRu
625.95
monoclinic
P21/c (No. 14)
10.6944(10)
10.0645(10)
25.5048810)
90
97.66(1)
90
2720.7(4)
4
Formula weight
Crystal system
Space group
a (Å)
b (Å)
c (Å)
589.6
monoclinic
P21/n (No. 14)
11.1885(10)
8.9866(10)
29.5232(10)
90
97.71(1)
90
2941.7(4)
4
triclinic
triclinic
ꢀ
ꢀ
P1 (No. 2)
P1 (No. 2)
8.827(1)
10.891(1)
15.466(1)
74.97(1)
84.12(1)
85.28(1)
1426.0(2)
2
8.812(11)
10.865(5)
16.399(5)
100.82(2)
100.20(4)
93.44(7)
1511(2)
2
a
(°)
b (°)
c
(°)
V (Å3)
Z
Dcalc (g cmꢀ3
F(000)
)
1.331
1240
0.26
1.294
588
0.26
1.283
620
0.25
1.528
1288
0.96
l
(mmꢀ1
)
T (K)
293
293
293
293
Reflections collected
5396
5737
6135
5355
Unique reflections with I > 2
Parameters refined
r(I)
3938
361
1.05
0.076
0.019
0.247
0.63, ꢀ0.81
2186
335
0.96
0.088
0.026
0.231
0.38, ꢀ0.31
2660
355
1.49
0.157
0.05
0.211
0.37, ꢀ0.37
2253
313
1.00
0.086
0.027
0.245
0.95, ꢀ0.74
Goodness-of-fit (GOF) on F2
R[F2 > 2
Rint
r
(F2)]
wR(F2)
d
q
max, dqmin (e Åꢀ3
)
were obtained by slow evaporation of MeOH from methanolic
solutions of the corresponding salts. A suitable crystal of 6 was pre-
pared by layering its CH2Cl2 solution with Et2O. X-ray quality crys-
tals of (2)Cl were obtained both from aqueous and methanolic
solutions by slow evaporation of solvents (a summary of crystallo-
graphic data for (2)ClꢂH2O, (2)ClꢂMeOH are collected in the Supple-
mentary Table S1).
Data were collected using Enraf Nonius MACH3 diffractometer
for (2)(1), (4)(1), (5)(1) and 6.2H2O, Bruker GADDS diffractometer
for (2)Cl.H2O and Bruker SMART diffractometer for (2)Cl.MeOH using
3. Results and discussion
3.1. Synthesis and crystallographic analysis of (pta-R)(mtppms) salts
1-Benzyl-1-azonia-3,5-diaza-7-phosphaadamantyl chloride,
(2)Cl was obtained by known methods in reaction of pta and ben-
zyl chloride [25]. Since the solid state structure of this compound,
(2)Cl was hitherto not determined single crystals of them were iso-
lated from both methanolic and aqueous solutions and subjected
to X-ray analysis. On addition of an equivalent amount of
Na(mtppms) to an aqueous solution of (2)Cl a white precipitate
separated (Scheme 2).
Mo
Ka
radiation (k = 0.71073 Å) or Cu
K
a
radiation
(k = 1.541847 Å) in case of (2)Cl.H2O. Crystals of (2)ClꢂH2O and
(4)(1) had very low quality. The structures were routinely solved
using the SIR-92 software [32a] and refined on F2 using SHELX-97
program [32b], publication material was prepared with the
WINGX-97 suite [32c]. Hydrogen atoms were placed into geometric
positions except O–H protons which could be found at the differ-
ence electron density map and the oxygen-hydrogen distances as
well as 1,3 H distances were constrained. The hexyl side chain in
(pta-hexyl)(mtppms) structure shows high anisotropic motion be-
cause of positional disorder. The occupancy of the other position
was approximately 6% so according to literature recommandation
[33] the carbon atoms have been refined in a single position. Addi-
tional crystallographic information is provided in the deposited CIF
file and in Supplementary material.
The precipitate dissolves well in methanol; slow evaporation of
such solutions yielded single crystals of (2)(1) suitable for X-ray
structure determination (Fig. 1).
The most important structural parameters of (2)(1) are shown
in the legend to Fig. 1, whereas structures of (2)ClꢂH2O and
(2)ClꢂMeOH are presented in the Supplementary as Figs. S1 and
S2, respectively. The covalent structure of the studied ligands is
rather rigid as it is evidenced by the P–C and C–N bond length data
shown. CSD [34] search (Cambridge Structural Database Ver. 5.33
May, 2012) gave an average P–C distance for free pta derivative li-
gands (15 hits) and their metal complexes (267 hits) as 1.845(17)
and 1.84(2) Å, respectively, which also shows the conformational
rigidity of the pta ligand. However, versatility was expected
X
R
R
NaO3S
P
P
H2O
N
N
-O3S
PPh2
+ Na+ + X-
+
PPh2
N
N
N
N
2
R = CH2C6H5 ( ); X = Cl
=C6H11 (4); X = Br
5
= C4H9 ( ); X = Br
Scheme 2. Formation of salts containing water-soluble phosphines both as cation and anion.

A. Udvardy et al. / Polyhedron 60 (2013) 1–9
5
Fig. 1. ORTEP view of compound (2)(1) at 50% probability level with partial numbering scheme. Selected bond lengths (Å), angles (°) and torsion angles (°) with estimated
standard deviations: P1–C1: 1.844(5); P1–C2: 1.836(5); P1–C3: 1.852(5); P2–C11: 1.846(4); P2–C21: 1.838(5); P2–C31: 1.835(5); P1–C1–N1: 114.6(3); C1–N1–C47: 111.9(3);
C1–N1–C47–C41: ꢀ67.0(1); N1–C47–C41–C42: 91.9(1); N1–C47–C41–C46: ꢀ89.9(1).
Fig. 2. ORTEP view of compound (4)(1) at 50% probability level with partial numbering scheme. Selected bond lengths (Å), angles (°) and torsion angles (°) with estimated
standard deviations: P1–C1: 1.761(7); P1–C2: 1.807(7); P1–C3: 1.807(9); P2–C11: 1.827(6); P2–C21: 1.819(6); P2–C31: 1.830(7); P1–C1–N1: 115.2(4); C1–N1–C41: 113.0(5);
C1–N1–C41–C42: ꢀ68.4(1).
and found in the supramolecular architecture of the studied ion
pairs.
Monosulfonated triphenylphosphine was prepared already in
1958 [35], however, due to the poor crystallization properties of
Na(mtppms) X-ray structure determinations of the mtppms anion
were made on benzyltriethylammonium [36], guanidinium [37],
imidazolium [38], and potassium [39] salts. In contrast, (2)(1),
(4)(1) and (5)(1) are the first structurally characterized mtppms
salts containing water-soluble phosphines both as cation and
anion.
Secondary interactions can be tuned to prepare bidentate phos-
phorous ligands by fixing phosphorus atoms in appropriate posi-
tions for coordination to the same metal center. Note that even a
small difference in the lattice interactions such as changing a side
chain (butyl to hexyl) causes significant changes in conformation
and P–P distances (see Fig. S4), hence in the coordination proper-
ties of the mixed tertiary phosphorous ligand.
For further studies on (pta-R)(mtppms) salts we have prepared
several (pta-R)X derivatives, among them the known ones with
R = {CH2}n-CH3, n = 0, X = I or MeOTf; n = 1–3, X = Br}. The new 1-
hexyl-1-azonia-3,5-diaza-7-phosphaadamantyl cation, (4), was ob-
tained by refluxing pta and 1-Br-hexane in acetone.
Mixing equivalent quantities of alkyl-pta salts and mtppms in
aqueous solutions led to the formation of precipitates in the case
of pta-hexyl (4) and pta-butyl (5). Similarly to (2)(1) single crystals
of (4)(1) and (5)(1) for X-ray analysis could be obtained from meth-
anolic solutions by slow evaporation (Figs. 2 and 3).
Cations obtained by N-alkylation of pta with shorter chain al-
kyl halides or triflates did not yield precipitates with mtppms. It
is noteworthy that with trisulfonated triphenylphosphine
(mtppts) none of the alkyl-pta cations gave water-insoluble
products.
Though salts (2)(1), (4)(1) and (5)(1) were found insoluble in
water they dissolve well in chlorinated solvents or alcohols. The

6
A. Udvardy et al. / Polyhedron 60 (2013) 1–9
Fig. 4. ORTEP view of [(
g
6-C10H14)RuCl2(pta-Bn)]Clꢂ2 H2O with partial numbering
scheme. Selected bond lengths (Å) and angles (°) with estimated standard
deviations: P1–C1: 1.886(13); P1–C2: 1.813(14); P1–C3: 1.822(11); P1–Ru1:
2.295(3); Cl1–Ru1: 2.418(4); Cl2–Ru1: 2.406(4); P1–Ru1–Cl1: 83.3(1); P1–Ru1–
Cl2: 83.9(1); Cl1–Ru1–Cl2: 88.4(1)°.
cleanly performed directly from [(g
6-C10H14)RuCl2(pta-Bn)]Cl and
Fig. 3. ORTEP view of compound (5)(1) at 50% probability level with partial
numbering scheme. Selected bond lengths (Å), angles (°) and torsion angles (°) with
estimated standard deviations: P1–C1: 1.730(9); P1–C2: 1.761(13); P1–C3:
1.793(10); P2–C11: 1.827(7); P2–C21: 1.815(8); P2–C31: 1.828(8); P1–C1 N1:
114.2(6); C1–N1–C41: 112.7(8); C1–N1–C41–C42: ꢀ160.8(1).
Na(mtppms) in methanol at reflux temperature when no interme-
diate precipitate formed. In the 31P NMR spectrum the singlets
characteristic for mtppms (d = ꢀ4.4 ppm) and for 6 (d = ꢀ18.6 ppm)
were gradually replaced by two doublets of the same intensity at
d = 27.6 ppm (d, Jpp = 46 Hz) and at d = ꢀ24.7 ppm (d, Jpp = 53 Hz).
After 10 h reflux these latter were the only signals in the spectrum,
31P NMR spectra of these solutions display only singlets of cation,
pta-R (R = Bn: d = ꢀ84.0 ppm and R = butyl or hexyl:
d = ꢀ82.9 ppm) and anion, mtppms (d = ꢀ4.4 ppm) with equal
intensity (Figs. S5–7).
characteristic for [g
6-C10H14)RuCl(pta-Bn)(mtppms)]Cl.
The complex was isolated as yellow powder and was character-
ized also by 1H and 13C NMR spectroscopy, elemental analysis and
mass spectroscopy. The strongest signal in the ESI MS spectrum be-
longs to [(g
6-C10H14)RuCl(pta-Bn)(mtppms)]+ = (M)+ (observed m/
z: 860.154; calcd. 860.154 with correct isotope distribution;
3.2. Half sandwich Ru-complexes with homo- and heterobidentate
ligands
Fig. S9). All these data agree well with the suggested composition
of [(g
6-C10H14)RuCl(pta-Bn)(mtppms)]Cl (Scheme 3).
The desired mixed-phosphine complex could also be prepared
3.2.1. Synthesis of [(g
6-C10H14)RuCl(pta-Bn)(mtppms)]Cl
in a one-step procedure. In this case, a methanolic solution of
To our knowledge there are only two half sandwich Ru-com-
plexes known which contain both anionic (mtppms) and cationic
(pta-Me) phosphine ligands. Both [CpRu(pta-Me)(mtppms)2] and
[CpRu(pta-Me)(PPh3)(mtppms)]+ were obtained in two-step proce-
dures by stepwise replacement of PPh3 in [CpRuCl(PPh3)2] with
pta-Me and mtppms [16].
[(
in MeOH to obtain a reaction mixture with [Ru2+] = [2] = [1]. Two
strong doublet signals of
6-C10H14)RuCl(pta-Bn)(mtppms)]Cl
g
6-C10H14)RuCl2]2 was added to a solution of (pta-Bn)(mtppms)
[
g
was observed already after 2 h reflux. Nevertheless, at this reaction
time singlet signals of the free phosphines 2 and 1 as well as those
of
6
(d = ꢀ18.6 ppm)
and
[(g
6-C10H14)RuCl2(mtppms)]ꢀ
Similarly, [(
sized by stepwise complex formation. First, [(
pta-Bn)]Cl, 6 was prepared in reaction of (pta-Bn)Cl with [(g6
10H14)RuCl2]2. The resulting complex has already been described
g
6-C10H14)RuCl(pta-Bn)(mtppms)]Cl was synthe-
(d = 26.1 ppm) were still seen. In 4 h the signals of the free phos-
g
6-C10H14)RuCl2(-
phines disappeared, however, only 10 h reflux produced solutions
-
with clean 31P NMR spectrum of [( 6-C10H14)RuCl(pta-
g
C
Bn)(mtppms)]Cl (Fig. S10). During the reaction the color of the
solution gradually changed from orange to lemon yellow. The
product was isolated as yellow powder and analyzed by the same
techniques used for identification of the product of the stepwise
synthetic procedure; all parameters were found identical.
in the literature [14], however, its solid state molecular structure
was not determined. By layering hexane on top of a dichlorometh-
ane solution of 6 we obtained good quality crystals which were
subjected to single crystal X-ray diffraction analysis.
Search of CSD (Version 5.33 May, 2012) gave 268 hits for aryl-
RuCl2P complexes. Average values for Ru–Cl: 2.41(2) Å, Ru–P:
2.33(3) Å, Cl–Ru–Cl angle 88(4)°, Cl–Ru–P angle 86(4)°. It can be
seen from data at Fig. 4. that our observation completely agrees
with these data.
3.2.2. (pta-R)(mtppms) as bridging ligand
In contrast to the above synthesis of the mononuclear [(
g
6-C10-
H14)RuCl(pta-Bn)(mtppms)]Cl, when equimolar amounts of [(g6
-
In water, reaction of [(
Na(mtppms) immediately gives a white precipitate what can be
formulated as [(
6-C10H14)RuCl2(pta-Bn)](mtppms) according to
its 31P NMR spectrum (Fig. S8). This precipitate could be trans-
formed to [
6-C10H14)RuCl(pta-Bn)(mtppms)]Cl via reflux in meth-
anol. Nevertheless, synthesis of the latter complex was more
g
6-C10H14)RuCl2(pta-Bn)]Cl and
C10H14)RuCl2]2 and (pta-Bn)(Na-mtppms), (2)(1) were reacted in
MeOH (concentration ratio [Ru2+]:[2]:[1] = 2:1:1) a different prod-
uct was obtained (Scheme 3). In addition to signals of 2 and 1, the
g
31P NMR spectrum of the solution displayed only singlets of [(g6
-
g
C
10H14)RuCl2(pta-Bn)]+ (d = ꢀ18.6 ppm) and [(
g
6-C10H14)RuCl2(-
mtppms)]ꢀ (d = 26.1 ppm) with equal intensity (Fig. S11). After

A. Udvardy et al. / Polyhedron 60 (2013) 1–9
7
Cl
Cl
Cl
Cl
2 (pta-Bn)(mtppms)
Ru
Ru
Ru
MeOH reflux, 10 h, 82 %
P
N
Ph2P
Cl
Cl
N
N
PhH2C
SO3
-
(pta-Bn)(mtppms)
MeOH rt., 1 h
70%
2 (pta-Bn)Cl
MeOH rt., 20 min
74 %
Na(mtppms)
MeOH reflux, 10 h
76 %
Cl
CH2Ph
Ru
Cl
Ru
P
N
Cl
Ru
PPh2 Cl
CH2Ph
N
-O3S
Cl
Cl
Cl
P
N
N
N
N
Scheme 3. Synthesis of half-sandwich Ru(II)-complexes using (pta-Bn)(mtppms) as a ligand.
Cl2
P
P
P
Cl
acetone
+
2
N
N
N
N
N
N
reflux, 3 h
74 %
Cl
N
N
N
η6
[( -C10H14)RuCl2]2
MeOH reflux, 20 min
51 %
MeOH rt.
Cl2
Cl2
Cl
Ru
P
Cl
Cl
Cl
P
Ru
P
Cl
Ru
N
N
P
Cl
N
N
N
N
N
N
N
N
N
N
Scheme 4. Synthesis of [{(g l-3)]Cl2 containing a bisphosphine (3) obtained from pta and 1,4-bis(chloromethyl)benzene.
6-C10H14)RuCl2}2(
2 h reaction time only these two signals could be observed, and no
other species could be detected by 31P NMR spectroscopy even
upon prolonged reflux of the solution.
dissolves well in alcohols, benzene and in chlorinated solvents. Io-
nic interaction between (pta-Bn)+ and (mtppms)ꢀ, each coordi-
nated to a different Ru(II) center, makes (2)(1) a bridging ligand
between the two half sandwich Ru(II) moieties.
According to elemental analysis the isolated orange solid has
the formula of [(
g
6-C10H14)RuCl2(pta-Bn)][(
g
6-C10H14)RuCl2(-
Similar observations were made when equimolar amounts of
mtppms)]. Containing a big monovalent cation and a big monova-
lent anion, the compound has poor solubility in water, however, it
[(
g
6-C10H14)RuCl2]2 were added to methanolic solutions of (4)(1)
or (5)(1). After P2 h reaction time, the 31P NMR spectra of the solu-

8
A. Udvardy et al. / Polyhedron 60 (2013) 1–9
tions displayed only the singlet characteristic for [(
g
6-C10H14)-
water. The results demonstrate that an efficient modular approach
for synthesis of complexes containing two different phosphine li-
gands can be based on use of such ion pairs.
RuCl2(mtppms)]ꢀ (d = 26.0 ppm) and another singlet of equal
intensity at d = ꢀ20.4 ppm; the latter refers to the presence of
[(g
6-C10H14)RuCl2(pta-R)]+ ions (R = butyl, hexyl) (Figs. S12–13).
The [(g
6-C10H14)RuCl2(Ph2PCH2NHC6H4COOH)] complex [3]
Acknowledgements
mentioned in the Introduction was found to dimerize through
intermolecular H-bonds between the carboxylic acid groups.
Therefore the dimer necessarily consisted of two monomeric
half-sandwich Ru-complexes having the same phosphine substitu-
tents and consequently had a symmetric structure. In our case, the
ionic interaction between various phosphine cations and anions al-
lows formation of self-organized dimers containing different phos-
phine units in the bridge. By this way, this modular approach
makes possible the synthesis of non-symmetric wheel-and-axle-
type half sandwich Ru-dimers, too.
The authors are indebted for the support of the Hungarian Sci-
ence Fund (OTKA K101372). The research was supported by the EU
and co-financed by the European Social Fund under the projects
ENVIKUT (TÁMOP-4.2.2.A-11/1/KONV-2012-0043) and TÁMOP-
4.2.2/B-10/1/KONV-2010-0024.
Thanks are due to Dr. Attila Kiss-Szikszay for the elementary
analyzes and to Dr. Lajos Nagy for the ESI-MS measurements.
The assistance of Ms. Evelin Nagy in some experiments is gratefully
acknowledged.
3.3. Synthesis of 1,10-[1,4-phenylenebis(methylene)]bis-3,5-diaza-1-
azonia-7-phosphatricyclo[3.3.1.1]decane, (3), and its half sandwich
Ru(II)-complex
Appendix A. Supplementary data
CCDC 929756–929761 contains the supplementary crystallo-
graphic data for (pta-Bn)ClꢂH2O, (2)ClꢂH2O; (pta-Bn)ClꢂMeOH,
(2)ClꢂMeOH; (pta-Bn)(mtppms), (2)(1); (pta-hexyl)(mtppms),
The water-soluble bisphosphine 1,10-[1,4-phenylenebis(methy-
lene)]bis-3,5-diaza-1-azonia-7-phosphatricyclo[3.3.1.1]decane,
(4)(1); (pta-butyl)(mtppms), (5)(1) and [(g
6-C10H14)RuCl2(pta-
3
Bn)]Clꢂ2 H2O, 6ꢂ2 H2O. These data can be obtained free of charge
via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the
Cambridge Crystallographic Data Centre, 12 Union Road, Cam-
bridge CB2 1EZ, UK; fax: +44 1223 336 033; or e-mail: depos-
it@ccdc.cam.ac.uk. Supplementary data associated with this
article can be found, in the online version, at http://dx.doi.org/
10.1016/j.poly.2013.05.008.
(as its chloride salt) was obtained by refluxing a suspension of
pta and 1,4-bis(chloromethyl)benzene in acetone (Scheme 4).
Spectral parameters of the compound agree well with those dis-
closed for the related (3)Br2 [26].
Upon refluxing equimolar amounts of (3)Cl2 and [(g
6-C10H14)-
RuCl2]2 in methanol an orange precipitate separated. In aqueous
solution of the isolated complex a singlet 31P NMR signal was ob-
served (d = ꢀ17.9 ppm) referring to identical environments of the
two phosphorus atoms (Fig. S14). In the ESI MS spectrum (aqueous
solution) the highest intensity peaks were observed with correct
isotope distribution at m/z = 515.051 (calcd: 515.059 [C40H60 N6P2-
References
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6-C10H14)-
RuCl2}2( -3)]Cl2 in which the pta-derived bisphosphine acts as
g l-
6-C10H14)RuCl2}2(
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4. Conclusion
Until now only ion pairs of cationic and anionic derivatives of
triphenylphosphine were used as bidentate ligands in various tran-
sition metal complexes. In this work we demonstrated that Cou-
lombic interactions between monosulfonated triphenylphosphine
anion (mtppms) and various cationic alkyl and benzyl derivatives
of 1,3,5-triaza-7-phosphaadamantane (pta-R; R = benzyl, butyl,
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R)(mtppms) were crystallized and their solid state structures
determined by X-ray diffraction for the first time. Interestingly,
the (pta-Bn)(mtppms) ion pair is able to coordinate to the same
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