Structural studies on tribenzylphosphane sulfide complexes of copper(I) and silver(I)

Article abstract of DOI:10.1016/j.poly.2015.12.010

Tribenzylphosphane sulfide (SPBn₃) reacts with [Cu(CH₃CN)₄]PF₆ in a 2:1 ratio to give [Cu(CH₃CN)(SPBn₃)₂]PF₆ whereas with [Ag(CH₃CN)₄]PF₆

Full text of DOI:10.1016/j.poly.2015.12.010

Accepted Manuscript
Structural studies on tribenzylphosphane sulfide complexes of copper(I) and
silver(I)
Eric W. Ainscough, Andrew M. Brodie, Graham H. Freeman, Paul G. Plieger
PII:
S0277-5387(15)00760-3
DOI:
http://dx.doi.org/10.1016/j.poly.2015.12.010
POLY 11709
Reference:
Polyhedron
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Accepted Date:
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7 December 2015
Please cite this article as: E.W. Ainscough, A.M. Brodie, G.H. Freeman, P.G. Plieger, Structural studies on
tribenzylphosphane sulfide complexes of copper(I) and silver(I), Polyhedron (2015), doi: http://dx.doi.org/10.1016/
j.poly.2015.12.010
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Structural studies on tribenzylphosphane sulfide
complexes of copper(I) and silver(I)
Eric W, Ainscough,* Andrew M. Brodie,* Graham H. Freeman, Paul G.
Plieger
Chemistry - Institute of Fundamental Sciences, Massey University, Private Bag 11 222,
Palmerston North, New Zealand 4442
*
Corresponding authors. Tel.: +64-6-3569099; fax: +64-6-3505682.
E-mail addresses: e.ainscough@massey.ac.nz (E.W. Ainscough), a.brodie@massey.ac.nz (A.M. Brodie).
1

ABSTRACT
Tribenzylphosphane sulfide (SPBn3) reacts with [Cu(CH3CN)4]PF6 in a 2:1 ratio to give
[Cu(CH3CN)(SPBn3)2]PF6 whereas with [Ag(CH3CN)4]PF6 in the same ratio it forms
[Ag2(SPBn3)3](PF6)2. The crystal structure of the Cu(I) complex shows it to contain
discrete 3-coordinate [Cu(CH3CN)(SPBn3)2]+ cations and [PF6]− anions with the Cu atom
lying in the plane formed by the two coordinated sulfur atoms and the nitrogen from the
coordinated acetonitrile molecule. The Ag complex is a dinuclear species with the one
silver atom being 3-coordinate and the other 4-coordinate. Each of the SPBn3 molecules
forms a Ag-C η1-bond with one of the aromatic rings thus blocking the coordination of
further SPBn3 ligands. The two Ag centres are linked by a bridging sulfur and a weaker
interaction with carbon from the aromatic ring of the same tribenzylphosphane sulfide.
Keywords: Tribenzylphosphane sulfide; Copper(I); Silver(I); Ag(I)-C bond; X-ray
crystallography
1. Introduction
The parent molecule to tribenzylphosphane sulfide (C6H5CH2)3PS (SPBn3) is the
bulky tribenzylphosphane (PBn3) which forms two coordinate complexes of the type
[Cu(PBn3)2]X (X = CuCl2, CuBr2, PF6) [1] and [Ag(PBn3)2]PF6 and [Ag(PBn3)2]BF4 [2]
where the driving force for the formation of the linear cations was attributed to
interligand ‘embraces’ which prevent secondary coordination of the counter ion to the
metals. Here the phenyl groups of PBn3 swing back over the Ag or Cu in the [M(PBn3)2]+
cations to generate a six-fold phenyl embrace. Silver also forms the cluster
[Ag13I13(PBn3)6], the non-stoichiometric compounds Ag~11.5Br~11.5(PBn3)16·~5.5H2O and
2

[Ag(PBn3)2]8[AgCl3]Cl6 6H2O. The strength of the driving force of the six-fold phenyl
embrace, even in complex clusters, is seen in the latter two non-stoichiometric
compounds which also contain discrete [Ag(PBn3)2]+ cations with linear P-Ag-P
coordination [2]. With this unusual display of behaviour with PBn3 as a ligand we were
interested to observe whether any of these features extended to the chemistry of SPBn3 or
if new ones appeared.
Lewis basicity data is not available for SPBn3 but proton affinity measurements[3]
show that triphenylphosphane is more basic than triphenylphosphane sulfide (SPPh3).
Also it was found that by measuring the decrease in the I-C stretching frequency of the
linear triatomic molecule ICN as it forms iodine-bonded complexes with phosphine
chalcogenides, the soft Lewis base SPPh3 is more basic than triphenylphosphane
oxide[4]. Using the same scale, the basicity of SPPh3 is not as high as
trimethylphosphane sulfide (SPMe3) (as expected) which is more basic than
trimethylphosphane oxide. From these data it is reasonable to extrapolate that SPBn3
would be less basic than SPMe3 but more basic than SPPh3 [4].
Previously it has been shown that SPMe3 forms the complex [Cu(SPMe3)3]ClO4
which has a trigonal-planar arrangement of sulfur atoms around the copper atom [5], and
the trinuclear complex [CuCl(SPMe3)]3 where three-coordination of the copper is
achieved by sulfur atoms bridging, the copper and sulfur atoms forming a six-membered
ring and chlorine atoms occupying the third coordination position on the copper atoms
[6]. Other compounds with the same stoichiometry [CuX(SPMe3)]n (X = Br-, I-, [SCN]-)
are known and for X = Br- or I- the structures are not trinuclear [7, 8]. With SPPh3 the 1:1
compounds CuX(SPPh3) (X = Cl-, Br-) are known [9] as well as the 1:2 complex
3

[Cu(dmp)(SPPh3)2]ClO4 (dmp = 2,9-dimethyl-1,10-phenanthroline) [10] where the
copper has a pseudo-tetrahedral structure. Interplanar interactions between the phenyl
groups on the sulfide ligand and the phenanthroline exist, but are quite less than those
reported for the Cu(I) triphenylphosphane analog. The complex displays emission from a
single metal-centered charge-transfer state at 77 K which was in contrast to the
triphenylphosphane complex which exhibited dual luminescence from a charge-transfer
and a intraligand state at 77 K [10].
Triphenylphosphane sulfide reacts with silver trifluoroacetate in a 4:6 ratio to give the
complex ([CF3C(O)OAg]6(SPPh3)4) which contains a 24 membered (AgOCO)6 ring built
from TPPS as a template molecule, where each sulfur atom caps a triangle of silver
atoms providing each silver atom with two Ag-S contacts in addition to its two Ag-O
contacts. The µ3- coordination of the sulfide was unique. The six silver atoms are
connected via argentophilic bonding to give a 6-membered metallacycle in a twisted boat
conformation that experiences, as shown by NMR studies, great fluxionality in solution
suggesting that TPPS can undergo facile intra or intermolecular ‘ring hopping’ to other
silver triangles [11].
2. Experimental
2.1. Materials and instrumentation
4

Analytical grade solvents were used without further purification with all reactions
being carried out under nitrogen. [Cu(MeCN)4]PF6 and [Ag(MeCN)4]PF6 were made
according to a literature method [12]. Microanalyses were performed by the Campbell
Microanalytical Laboratory, University of Otago. IR data were run as KBr discs on a
Perkin-Elmer FT-IR Paragon 1000 spectrometer and 31P NMR spectra recorded at 400
MHz with a Bruker Advance 400 spectrometer. 31P NMR spectra were recorded in
CD2Cl2 solution at room temperature and chemical shifts were referenced to a 85%
H3PO4 standard. Mass spectra were obtained using a Varian VG70-250S double-focusing
magnetic sector spectrometer by the method of liquid secondary ion mass spectroscopy
(LSIMS) using m-nitrobenzyl alcohol as the matrix. Peaks quoted are for the most
abundant isotopomer; percentages are relative intensities.
2.2. Syntheses
2.2.1. SPBn3
To a solution of 1.5 g (4.93 mmol) of tribenzylphosphane (PBn3) in 30 mL of
toluene was added 0.17 g (5.3 mmol) of sulfur washed in with a further 10 mL of toluene.
The reaction mixture was refluxed, under dinitrogen, for 2 h then cooled on ice. The
resulting white powder was filtered, washed with cold toluene and then hexane to give
1.3 g of the crude product in 78 % yield. Recrystallization from hot toluene gave fluffy
white crystals, mp. 278-279o C (lit. 274 o C [13], 282-283.3o C [14]). Anal. Calc. for
C21H21PS: C, 74.97; H, 6.29. Found : C. 75.24; H, 6.53 %.
5

2.2.2. [Cu(CH3CN)(SPBn3)2]PF6
[Cu(MeCN)4]PF6 (0.200 g, 0.536 mmol) was dissolved in 20 mL of 2:1
CH2Cl2/methanol and a further 30 mL of CH2Cl2 was added. Solid SPBn3 (0.361 g, 1.073
mmol) was added and the reaction mixture refluxed for 10 min then cooled and filtered.
The filtrate was reduced in volume and the resulting white precipitate was filtered and
air-dried to give a white crystalline product. Yield 0.41 g (83 % yield). Crystals suitable
for X-ray analysis were grown by slow evaporation of the filtrate. The compound has a
tendency to lose the occluded solvent molecules. mp. 211- 213 oC. Anal. Calc. for
C44H45CuF6NP3S2·0.5CH2Cl2: C, 55.39; H, 4.81; N, 1.45%. Found: C, 55.51; H, 4.84; N,
1.48%.
2.2.3. [Ag2(SPBn3)3](PF6)2
[Ag(MeCN)4]PF6 (0.124 g, 0.297 mmol) was dissolved in 20 mL of 2:1 CH2Cl2
/methanol and a further 30 mL of CH2Cl2 was added. Solid SPBn3 (0.200 g, 0.595 mmol)
was added and the reaction mixture refluxed for 10 min. Hexane was added until the
solution became slightly cloudy and the flask was placed in a refrigerator to cool for 30
min. The resulting precipitate was filtered and air-dried to give 0.146 g (65 % yield) of
crude product. Diffusion of diethyl ether vapor into a concentrated acetonitrile solution of
the crude product afforded white needles suitable for X-ray analysis. mp. 194-198 oC.
Anal. Calc. for C63H63Ag2F12P5S3: C, 49.95; H, 4.19%. Found: C, 49.99; H, 4.08%.
2.3. X-ray Crystallography
X-ray data were collected on a Siemens SMART diffractometer using graphite-
6

monochromated Mo-Kα radiation (λ = 0.71073 Å ). The data were corrected for
Lorentz and polarization effects and semiempirical absorption corrections (SADABS)
were applied. The structures were solved by direct methods and refined against F2
using all data by full matrix least-squares techniques (SHELXTL) [15]. In the
refinement of the structures all non-hydrogen atoms were made anisotropic. Hydrogen
atoms were inserted at calculated positions with isotropic thermal parameters at 1.2
times the equivalent isotropic displacement parameters of the atoms to which they are
attached. Disordered solvent regions in [Cu(CH3CN)(SPBn3)2]PF6 were treated in the
manner described by van der Sluis and Spek [16], as 109 e- per cell, approximating
0.7(CH2Cl2) (= 116 e-) per formula unit. The carbon aton (C3A) on the methyl group
on the bound acetonitrile molecule was postionally disordered over two sites in the
ratio of 0.71:0.29.
Crystal data for [Cu(CH3CN)(SPBn3)2]PF6 C44H45CuF6NP3S2, Mr = 922.38,
colourless prism, 0.40 x 0.20 x 0.18 mm, monoclinic, P21/n, a = 14.687(2), b =
18.931(3), c = 17.290(3) Å, β = 102.653(1)°, U = 4690.7(13) Å3, Z = 4, µ = 0.711
mm-1, F(000) = 1904, T =203(2) K. A total of 21526 reflections were collected in the
range 4.64° < 2θ < 50.69°. The 8350 independent reflections [R(int) = 0.051] were
used after absorption correction (Tmin = 0.558, Tmax = 1.000). Refinement of 526
parameters converged to R1 = 0.0566 [for 8350 reflections having I > 2σ(I)], wR2 =
0.1451 and goodness-of-fit of 0.935 (for all 21526 F2 data). Peak/hole 0.83/-0.41 e Å-
3
.
Crystal data for [Ag2(SPBn3)3](PF6)2 C63H63Ag2F12P5S3, Mr = 1514.90, colourless block,
ŭ
0.65 x 0.30 x 0.18 mm, triclinic, P̊, a = 11.3370(1), b = 13.5875(2), c = 21.3610(3) Å, α
7

= 75.0200(9), β = 87.5080(10), γ = 83.0180(10)°,U = 3154.85(7) Å3, Z = 2, µ = 0.922
mm-1, F(000) = 1532, T =203 (2) K. A total of 29491 reflections were collected in the
range 3.20° < 2θ < 55.2°. The 13595 independent reflections [R(int) = 0.019] were used
after absorption correction (Tmin = 0.774, Tmax = 0.935). Refinement of 766 parameters
converged to R1 = 0.0339 [for 13595 reflections having I > 2σ(I)], wR2 = 0.0823 and
goodness-of-fit of 1.03 (for all 13595 F2 data). Peak/hole 0.56/-0.91 e Å-3.
3. Results and Discussion
3.1. Syntheses and characterization
Reaction of SPBn3 with [Cu(MeCN)4]PF6 afforded the 1:2 complex,
[Cu(CH3CN)(SPBn3)2]PF6, whereas its reaction with [Ag(MeCN)4]PF6 gave a 2:3,
compound, viz. [Ag2(SPBn3)3](PF6)2, regardless of the ratio of ligand to metal used. In
the infrared spectra both complexes showed the expected downward shift of the ν(P=S)
stretching frequency in the free ligand from 577 cm-1 to 558 cm-1 consistent with sulfur
coordination [17]. For [Cu(CH3CN)(SPBn3)2]PF6, the positive ion liquid secondary
ionization mass spectrum showed the most intense peak at m/z 399 (100%) assignable to
[Cu(SPBn3)]+ with weaker peaks at m/z 735 (64%) and 217 (22%) due to the
[Cu(SPBn3)2]+ and ([Cu(SPBn)]+ ions. Similarly [Ag2(SPBn3)3](PF6)2 exhibits peaks at
m/z 781 (83%), 445 (100%) and 261 (20%) assignable to the [Ag(SPBn3)2]+,
[Ag(SPBn3)]+ and [Ag(SPBn)]+ respectively indicating dissociation of the solid state
dimer in the gas phase. Similarly, apart from the expected [PF6]− septet at 145 ppm,
solution 31P NMR spectra (in CD2Cl2) exhibit a sharp resonance at 54 ppm for both
8

complexes (cf 45 ppm for the uncomplexed ligand [18]) indicating that the solid state
structure is maintained in solution.
3.2. Molecular structures
3.2.1. [Cu(CH3CN)(SPBn3)2]PF6
The crystal structure of [Cu(CH3CN)(SPBn3)2]PF6 shows it to contain discrete 3-
coordinate [Cu(CH3CN)(SPBn3)2]+ cations and [PF6]− anions (Fig. 1 and Table 1). The
Cu atom lies in the plane formed by the two coordinated sulfur atoms and the nitrogen
from the coordinated acetonitrile molecule. The two Cu-S bond lengths at 2.2825(11) and
2.2453(12) Å are similar to those found in the trigonal-planar trimethylphosphane sulfide
complex, [Cu(SPMe3)3]ClO4 [2.253(5)-2.264(5) Å][5] and to those in the complex,
[CuCl(SPMe3)]3, where the sulfide is bridging [2.264(1)-2.267(2) Å][7]. Cu(I)
coordinated acetonitrile complexes are not uncommon [19] [20] [21]. Not unexpectedly,
the Cu-N1A bond distance at 1.975(4) Å is shorter than the range [2.054(3) – 2.097(1) Å]
observed for the 4-coordinate copper(I) acetonitrile complexes where triphenylphosphane
is the co-ligand viz. for the complexes [Cu(CH3CN)(PPh3)3]X (X = ClO4, BF4, SiF5 and
PF6) [21]. Possibly due to steric crowding in the SPBn3 case, the Cu1-N1A-C2A angle at
−
−
167.2(4)°, is close to the Cu-N-C angles found for the SiF5 and PF6 complexes
−
−
[165.8(1) and 166.1(1)°] rather than the essentially linear angles in the ClO4 and BF4
complexes [178.0(2) and 176.6(3)°].
9

Fig. 1. Solid state structure of [Cu(CH3CN)(SPBn3)2]PF6. The hydrogen atoms and the
−
PF6 anion have been removed for clarity. Ellipsoids are drawn at the 50% probability
level.
10

Table 1
Selected bond lengths (Å) and angles (°) for the complexes.
[Cu(CH3CN)(SPBn3)2]PF6
Atoms
Cu1 - S1
Cu1 - S2
Cu1 - N1A 1.975(4)
S1 - P1
S2 - P2
Bond lengths
2.2854(11)
2.2453(12)
Atoms
Angles
128.05(4)
104.80(11)
127.10(11)
107.56(6)
104.92(6)
167.2(4)
S1- Cu1 - S2
S1 – Cu1 - N1A
S2 – Cu1 - N1A
Cu1 - S1 - P1
Cu1 - S2 - P2
Cu1 -N1A - C2A
1.9930(14)
2.0008(13)
[Ag2(SPBn3)3](PF6)2
Atoms
Ag1 - S1
Ag1 - S3
Bond lengths
2.4819(7)
2.4834(7)
Atoms
S1 - Ag1 - S3
S1 - Ag1 - C136 101.93(6)
S3 - Ag1 - C136 125.02(6)
Angles
131.82(2)
Ag1 - C136 2.633(3)
Ag2 - S2
Ag2 - S3
Ag2 - C236 2.594(2)
Ag2 - C316 2.691 (3)
S1 - P1
S2 - P2
S3 - P3
2.4650(7)
2.5535(6)
S2 - Ag2 - S3
126.34(2)
S2 - Ag2 - C236 104.28(6)
S3 - Ag2 - C236 105.45(6)
S2 - Ag2 - C316 117.23 (6)
S3 - Ag2 - C316 87.72 (6)
1.9887(9)
1.9951(9)
2.0205(8)
3.2.2. [Ag2(SPBn3)3](PF6)2
The silver complex is a dinuclear species with the one silver atom (Ag1) being 3-
coordinate and the other (Ag2) 4-coordinate (Fig. 2 and Table 1). An interesting feature
of the structure is the way in which each terminal tribenzylphosphane sulfide forms a Ag-
C η1-bond [2.594(2) and 2.633(3) Å] with one of the aromatic ring carbon atoms thus
blocking the coordination of further SPBn3 ligands. The two Ag centres are linked by a
bridging sulfur (S3) and a weaker η1-interaction [2.691(3) Å] with carbon (C316) from
11

the aromatic ring of the same tribenzylphosphane. The Ag(1) atom is at the centre of a
near 'S2C' trigonal-planar coordination sphere while the coordination sphere of the Ag(2)
is in approximately 'S2C2' tetrahedral. There are numerous examples in the literature for
Ag-C η1-interactions with aromatic carbon atoms but few have a sulfur atom as a co-
ligand [22-25]. The Ag-C η1-bond lengths observed for [Ag2(SPBn3)3](PF6)2 are similar
to that observed [2.619(5) Å] in a compound where the ligated sulfur atom is in an
aliphatic-S from an S2O3 macrocycle [24].
-
Fig. 2. Solid state structure of [Ag2(SPBn3)3](PF6)2. The hydrogen atoms and the two PF6
anions have been removed for clarity. Ellipsoids are drawn at the 50% probability level.
4. Conclusions
Tribenzylphosphane sulfide reacted with [Cu(MeCN)4]PF6 to give the 1:2
complex, [Cu(CH3CN)(SPBn3)2]PF6, rather than a complex with three phosphane sulfides
coordinated. It appears that the coordination of a third phosphane sulfide is blocked by
the bulkiness of the other two. In contrast the reaction of the sulfide with the larger Ag(I)
12

centre afforded a 2:3, compound, viz. [Ag2(SPBn3)3](PF6)2, which contains both 3- and 4-
coordinate Ag(I) centres achieved via bridging sulfur atoms and Ag-C η1-bonds. If it can,
silver(I) readily increases its coordination sphere by interacting with other donor groups.
For example, with diphenyl(2-pyridyl)phosphane sulfide, SPPh2py, the Ag complex,
[Ag(SPPh2py)2]BF4, is not 2-coordinated but lies in a quasi-tetrahedral sphere with both
S and both N atoms bound [26]. In contrast the parent phosphane, PBn3, forms two-
coordinate complexes of the type [Cu(PBn3)2]PF6 and [Ag(PBn3)2]PF6 since the ligand
can block further coordination by non-covalent interactions between the phenyl groups of
the two ligands which sweep back over the metal to an intramolecular form of the sixfold
phenyl embrace.
Acknowledgements
We thank Massey University for financial support and Dr A.K. Burrell (Argonne
National Laboratory, USA) for preliminary X-ray studies.
Appendix A. Supplementary material
CCDC 1406094 and 1406095 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 or from the
CCDC, 12 Union Road, Cambridge, CB21EZ,UK; E-mail: deposit@ccdc.cam.ac.uk.
13

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Graphical Abstract
The bulky tertiary phosphane sulfide, SPBn3, reacts with Cu(I) to form 3-coordinate
[Cu(CH3CN)(SPBn3)2]PF6 whereas with Ag(I) it forms dinuclear [Ag2(SPBn3)3](PF6)2
which contains both 3- and 4-coordinated Ag. The Ag atoms are linked by a bridging
sulfur and a carbon from the aromatic ring of the same SPBn3.
16