Solution and mechanochemical syntheses, and spectroscopic and structural studies in the silver(i) (bi-)carbonate: Triphenylphosphine system

Article abstract of DOI:10.1039/c1dt10416k

Syntheses of a number of adducts of silver(i) (bi-)carbonate with triphenylphosphine, both mechanochemically, and from solution, are described, together with their infra-red spectra, ³¹P CP MAS NMR and crystal structures. Ag(HCO₃):PPh₃ (1:4) has been isolated in the ionic form [Ag(PPh₃)₄](HCO₃) ·2EtOH·3H₂O. Ag₂CO₃:PPh ₃ (1:4) forms a binuclear neutral molecule [(Ph₃P) ₂Ag(O,μ-O′·CO)Ag(PPh₃)₂] (·2H₂O), while Ag(HCO₃):PPh₃ (1:2) has been isolated in both mononuclear and binuclear forms: [(Ph₃P) ₂Ag(O₂COH)] and [(Ph₃P)₂Ag(μ- O·CO·OH)₂Ag(PPh₃)₂] (both unsolvated). A more convenient method for the preparation of the previously reported copper(i) complex [(Ph₃P)₂Cu(HCO₃)] is also reported.

Full text of DOI:10.1039/c1dt10416k

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PAPER
Solution and mechanochemical syntheses, and spectroscopic and structural
studies in the silver(I) (bi-)carbonate: triphenylphosphine system†
Graham A. Bowmaker,*a Effendy,b,c John V. Hanna,d Peter C. Healy,e Scott P. King,d Claudio Pettinari, f
Brian W. Skeltonb and Allan H. Whiteb
Received 14th March 2011, Accepted 28th April 2011
DOI: 10.1039/c1dt10416k
Syntheses of a number of adducts of silver(I) (bi-)carbonate with triphenylphosphine, both
mechanochemically, and from solution, are described, together with their infra-red spectra, 31P CP
MAS NMR and crystal structures. Ag(HCO3):PPh3 (1 : 4) has been isolated in the ionic form
[Ag(PPh3)4](HCO3)·2EtOH·3H2O. Ag2CO3:PPh3 (1 : 4) forms a binuclear neutral molecule
[(Ph3P)2Ag(O,m-O¢·CO)Ag(PPh3)2](·2H2O), while Ag(HCO3):PPh3 (1 : 2) has been isolated in both
mononuclear and binuclear forms: [(Ph3P)2Ag(O2COH)] and [(Ph3P)2Ag(m-O·CO·OH)2Ag(PPh3)2]
(both unsolvated). A more convenient method for the preparation of the previously reported copper(I)
complex [(Ph3P)2Cu(HCO3)] is also reported.
Introduction
Experimental
While adducts of univalent coinage metal carboxylates with Group
15 donor ligands have been widely studied, those of the parent
carbonate species are much more limited and, in particular, for
donors beyond the initial member nitrogen. Thus, for systems
combining M/CO3/ER3 (M = Cu, Ag, Au; E = P, As, Sb), the
only adducts for which crystal structure determinations have been
hitherto recorded appear to be the complexes [{(Ph3P)2Cu}2(CO3)]
and [{(Ph3P)2Cu}(m-O·CO·OH)2].1 The ready accessibility of a
number of novel species and/or forms by way of mechanochem-
ical synthesis2 has led us to explore the disilver(I) carbon-
ate/tertiary phosphine system in this manner, resulting in a
number of new and interesting complexes of this anion for
which we record structural and spectroscopic characterization,
and which extend those forms which we have accessed from
solution.
Synthesis
[{(Ph3P)2Ag}2(CO3)]·2H2O. Disilver(I) carbonate (0.138 g,
0.5 mmol) was added to a solution of triphenylphosphine (0.787 g,
3.0 mmol) dissolved in warm acetonitrile (15 ml) and the
mixture was stirred at ambient temperature in an open flask
for 3 h, resulting in the formation of a voluminous off-white
microcrystalline solid. Further acetonitril◦e (10 ml) was added and
the mixture was gently heated to ca. 60 C to dissolve the solid
product. The resulting solution was filtered while hot to remove
a small amount of black residue, and colourless crystals formed
upon slow cooling of the filtrate in a covered flask. The product
was collected by vacuum filtration. Yield 0.32 g (94%). Anal.
Calcd for C73H64Ag2O5P4: C, 64.43; H, 4.74. Found: C, 64.2; H,
4.7%.
[Ag(PPh3)4](HCO3)·2EtOH·3H2O. Disilver(I)
carbonate
(0.276 g, 1.0 mmol) was added to a solution of triphenylphosphine
(1.128 g, 4.3 mmol) dissolved in warm ethanol (10 ml) and the
mixture was stirred at ambient temperature in an open flask for
3 h, resulting in the formation of a colourless microcrystalline
solid together with some black residue. The mixture was gently
heated to dissolve the colourless product. The resulting solution
was filtered while hot to remove the undissolved black residue
(0.25 g), and colourless crystals formed upon slow cooling of
the filtrate in a covered flask. A small sample of the product
was removed, dried with filter paper, and examined under the
microscope, revealing that the crystals slowly fragment to a
white powder on standing in the air. Because of this instability,
crystals for the X-ray work were taken directly from the reaction
aSchool of Chemical Sciences, University of Auckland, Private Bag 92019,
Auckland, New Zealand. E-mail: ga.bowmaker@auckland.ac.nz
bSchool of Biomedical, Biomolecular and Chemical Sciences, Chemistry
M313, The University of Western Australia, Crawley, 6009, Western
Australia
cJurusan Kimia, FMIPA Universitas Negeri Malang, Jalan Semarang 5,
Malang, 65145, Indonesia
dDepartment of Physics, University of Warwick, Gibbet Hill Rd., Coventry,
UK, CV4 7AL
eSchool of Biomolecular and Physical Sciences, Griffith University, Nathan,
4111, Queensland, Australia
f
School of Pharmacy, Universita` degli Studi di Camerino, S Agostino 1,
62032, Camerino MC, Italy
† CCDC reference numbers 795571–795574. For crystallographic data in
CIF or other electronic format see DOI: 10.1039/c1dt10416k
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mixture and kept wet with mother liquor until transferred to the
low-temperature stream of the diffractometer.
ellipsoids, hydrogen atoms, where shown, having arbitrary radii
˚
of 0.1 A.
[(Ph3P)2Ag(HCO3)]. Method 1. To a boiling solution of triph-
enylphosphine (1.574 g, 6.0 mmol) in ethanol (30 ml) was added,
with stirring, a hot solution of silver nitrate (0.510 g, 3.0 mmol) in
water (5 ml). The resulting hot solution was immediately added,
with rapid stirring, to a solution of sodium bicarbonate (1.05 g,
12.5 mmol) in water (30 ml) at ambient temperature. A white,
flocculent precipitate formed immediately. The mixture was stirred
until cool and the product was collected by vacuum filtration and
washed with 1 : 1 EtOH/H2O. Yield 2.013 g (97%). A portion
of this product (1.0 g) was dissolved in acetonitrile by stirring
and heating to 75 ◦C in a water bath. The resulting solution was
filtered while hot to remove a small amount of black residue, and
colourless crystals formed upon cooling of the filtrate in an open
beaker and evaporation of about half of the solvent. Colourless
crystals of the product were collected and dried on a piece of filter
paper. Anal. Calcd for C37H31AgO3P2: C, 64.08; H, 4.51. Found: C,
63.9; H, 4.5%; N, < 0.2%. In view of the potential co-crystallization
of nitrate with bicarbonate, we note specifically the absence of N
in the elemental analysis, and the absence of nitrate bands in the
IR spectrum of this and the corresponding copper(I) complex
[(Ph3P)2Cu(HCO3)] (see below). Method 2. Disilver carbonate
(0.069 g, 0.25 mmol) and triphenylphosphine (0.262 g, 1.0 mmol)
were ground together with a mortar and pestle, first dry and then
after addition of ethanol (0.5 ml). As the grinding progressed the
mixture formed an off-white paste, which was allowed to dry in
the air before sampling for IR spectroscopy. This process was
repeated six times with addition of ethanol (0.3 ml) each time.
The IR spectrum of the final product was the same as that of the
product obtained by Method 1 above.
Crystal/refinement data
[{(Ph3P)2Ag}2(CO3)]·2H2O ∫ C73H64Ag2O5P4, Mr = 1360.9.
1
¯
Triclinic, space group P1(Ci , No. 2), a = 12.1730(3), b =
˚
13.1340(6), c = 21.6602(10) A, a = 88.890(4), b = 82.094(3), g =
◦
3
-3
˚
62.430(4) , V = 3036.7(2) A . Dc (Z = 2) = 1.488 g cm . mMo = 0.80
mm-1; specimen: = 0.17 ¥ 0.11 ¥ 0.06 mm; ‘T’min,max = 0.91, 0.97.
2qmax = 59◦; Nt = 28935, N = 12361 (Rint = 0.083), No = 8081. R1 =
-3
˚
0.064, wR2 = 0.158 (a = 0.075); S = 0.93. |Drmax| = 2.4 e A .
Variata. Difference map residues were modelled as a pair of
water molecule oxygen atoms, one of which was disordered over
a pair of sites, occupancies refining to 0.73(1) and complement
˚
(O ◊ ◊ ◊ O¢ 1.36(2) A); associated hydrogen atoms were not located.
[Ag(PPh3)4](HCO3)·2EtOH·3H2O ∫ C77H79AgO8P4, Mr
=
1364.2. Monoclinic, space group C2/c (C2h6, No. 15), a =
◦
˚
18.2112(5), b = 20.6996(12), c = 20.3860(13) A, b = 108.315(5) ,
3
-3
V = 7295.5(7) A . Dc (Z = 4) = 1.241 g cm . mMo = 0.42 mm-1;
˚
specimen: = 0.50 ¥ 0.31 ¥ 0.21 mm; ‘T’min,max = 0.82, 0.95. 2qmax
=
80◦; Nt = 158838, N = 22140 (Rint = 0.056), No = 15154. R1 = 0.051,
-3
˚
wR2 = 0.149 (a = 0.089); S = 0.98. |Drmax| = 2.4 e A .
Variata. The cation was well-defined; the remainder of the com-
ponents were modelled as disordered about the crystallographic
2-axis, occupancies 0.5, attempted modelling in a lower symmetry
space group being unfruitful. Associated OH hydrogen atoms were
not located.
[(Ph3P)2Ag(O2COH)] ∫ C37H31AgO3P2, Mr = 693.4. Triclinic,
a = 10.2351(3), b = 11.9944(3), c = 13.8661(3) A, a = 85.949(2),
˚
˚
◦
3
[(Ph3P)2Cu(HCO3)]. A solution of [(Ph3P)2Cu(NO3)] (0.650 g,
1.0 mmol) in acetonitrile (10 ml) at ambient temperature was
slowly added dropwise to a rapidly stirred solution of sodium
bicarbonate (2.135 g, 25.4 mmol) in water (50 ml) at ambient tem-
perature. An initial white cloudy suspension partially coagulated
upon further addition of the [(Ph3P)2Cu(NO3)] solution, finally
resulting in a white flocculent precipitate of product. This was
collected and washed with water, followed by a small volume of
ethanol (4 ml). Yield 0.496 g (76%). Anal. Calcd for C37H31CuO3P2:
C, 68.46; H, 4.81. Found: C, 68.5; H, 4.9%; N, < 0.2%.
b = 87.989(2), g = 65.093(3) , V = 1540.05(7) A . Dc (Z = 2) =
1.495 g cm-3. mMo = 0.80 mm-1; specimen: = 0.23 ¥ 0.09 ¥ 0.08 mm;
‘T’min,max = 0.87, 0.95. 2qmax = 75◦; Nt = 52522, N = 15737 (Rint
=
0.037), No = 12086. R1 = 0.028, wR2 = 0.056 (a = 0.024); S = 0.92.
-3
˚
|Drmax| = 0.63 e A .
Variata. The bicarbonate hydrogen atom was refined in (x, y,
z, Uiso), consistent with (at the least) the bulk of the sample being
the bicarbonate, rather than the unsolvated mononuclear form of
the nitrate, which has rather similar cell dimensions.4
[(Ph3P)2Ag(O.CO.OH)2Ag(PPh3)2]. C74H62Ag2O6P4,
M
=
3
Structure determinations
1386.9. Orthorhombic, space group P21212 (D2 , No. 18), a =
3
˚
˚
˚
˚
14.990(2) A, b = 23.435(7) A, c = 9.296(3) A, V = 3266(2) A . Dc
Full spheres of CCD/area-detector diffractometer data were
measured (monochromatic Mo-Ka radiation, l = 0.71073 A, w-
(Z = 2 dimers) = 1.410 g cm-3. mMo = 0.75 mm-1; specimen: 0.31 ¥
˚
0.30 ¥ 0.28 mm; Tmin,max = 0.80, 0.84 (gaussian correction). 2qmax
=
scans; T ca. 100 K) yielding Nt(otal) reflections, these merging to N
unique after ‘analytical’/face-indexed absorption correction (Rint
cited), which were used in the full matrix least squares refinements
on F2, refining anisotropic displacement parameter forms for the
non-hydrogen atoms, hydrogen atom treatment following a riding
model. No reflections with I > 2s(I) were considered ‘observed¢;
50◦; N = 3229, No = 2669; R1 = 0.035, wR2 = 0.069 (a = 0.011, b =
-3
˚
0.69); S = 1.05 |Drmax| = 0.32 e A . xabs = 0.21(4)
Variata. A unique data set for this specimen was measured
previous to the above using a single counter instrument operating
at room temperature (ca. 296 K). (x,y,z,Uiso)H were refined for the
disordered anionic hydrogen atom, after location in a difference
map; constrained cf. unconstrained refinement resulted in no
significant differences in the model. The complex is isostructural
with its copper(I) analogue1 and with the unsolvated binuclear
P21212 nitrate.4
reflection weights were (s (Fo2) + (aP)2(+ bP))-1 (P = (Fo
+
2
2
2
2Fc )/3). Neutral atom complex scattering factors were employed
within the SHELXL program.3 Pertinent results are presented
below and in the Tables and Figures, the latter showing the non-
hydrogen atoms with 50% probability amplitude displacement
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Infrared spectroscopy
in the mechanochemical experiment, prevented the formation of
an insoluble carbonate complex, but the reaction was found to
be very temperature sensitive. Heating was required to dissolve
Ag2CO3 in the ethanolic PPh3 solution, but such solutions began
to decompose, with deposition of a silver mirror in the reaction
flask, before all of the Ag2CO3 was dissolved. It was thus difficult
to prepare solutions with a sufficiently high silver content to
produce the target [(Ph3P)2Ag(HCO3)] complex. The formation
of bicarbonate in these reactions was demonstrated in one case by
the isolation of the complex [Ag(PPh3)4](HCO3)·2EtOH·3H2O,
which, however, was unstable w.r.t. loss of at least some of the
solvate ethanol or water molecules (see Experimental, Structure
determinations and IR Spectroscopy sections). As a result of these
difficulties, the target [(Ph3P)2Ag(HCO3)] complex was synthesised
by a different route, involving metathesis of the corresponding
nitrate complex with bicarbonate:
IR spectra were recorded at 4 cm-1 resolution on dry powders using
a Perkin Elmer Spectrum 400 FT-IR spectrometer equipped with
a Universal ATR sampling accessory. Far-infrared spectra were
recorded at 4 cm-1 resolution using a Perkin Elmer Spectrum 400
FT-IR spectrometer on petroleum jelly mulls between Polythene
plates.
NMR spectroscopy
31P cross-polarisation, magic-angle-spinning (CPMAS) NMR
spectroscopic data were acquired at 9.4 T on a Bruker DSX-400
spectrometer operating at a 31P frequency of 161.92 MHz. All
spectra were obtained with conventional cross-polarisation (CP)
methods and a MAS frequency of ~10 kHz using a Bruker 3.2 mm
double-air-bearing probe. The typical pulse parameters employed
1
were: a H p/2 pulse time of 3.5 ms, a Hartmann–Hahn contact
-
-
[(Ph3P)2Ag(NO3)] + HCO3 → [(Ph3P)2Ag(HCO3)] + NO3 (4)
period of 10 ms, a recycle delay of 20 s, and a 1H decoupling field
strength during acquisition of ca. 80 kHz. All data were referenced
to 85% H3PO4 via an external reference of (NH4)(H2PO4) (d 1.0
ppm), which was also used to set the Hartmann–Hahn match
condition.
This was characterized by X-ray crystallography, and shown
by IR spectroscopy to be identical to the final product of the
Ag2CO3 + 4PPh3 mechanochemical reaction. Previously published
examples of applications of solvent-assisted mechanochemical
synthesis to the preparation of coordination compounds have all
involved the use of solid- or liquid-phase reactants. The present
example of the formation of [(Ph3P)2Ag(HCO3)] from Ag2CO3 +
4PPh3 demonstrates that gas phase reactants (CO2 in this case;
eqn (3)) can also be readily incorporated by this method.
Results and discussion
Syntheses
The compound [(Ph3P)2Ag(HCO3)] was initially prepared adven-
titiously in an experiment involving the reaction of Ag2CO3 with
triphenylphosphine in contact with air. The formation of the
bicarbonate implies incorporation of CO2 and H2O from the air
during the course of the reaction:
An attempted synthesis of the copper(I) carbonate complex
[{(Ph3P)2Cu}2(CO3)] via redox reaction between basic copper(II)
carbonate CuCO3·Cu(OH)2 and triphenylphosphine:
CuCO3·Cu(OH)2 + 5Ph3P → [{(Ph3P)2Cu}2(CO3)] +
(5)
Ph3PO + H2O
Ag2CO3 + 4PPh3 + H2O + CO2 → 2[(Ph3P)2Ag(HCO3)]
In order to investigate this question further, the Ag2CO3
(1)
was unsuccessful; no reaction at all was observed between the
basic copper(II) carbonate and Ph3P, cf . the synthesis of triph-
enylphosphine copper(I) halide complexes from copper(II) halide
and triphenylphosphine. This precludes access to the copper(I)
bicarbonate complex [(Ph3P)2Cu(HCO3)] via the potential route:
+
4PPh3 reaction was investigated by the method of solvent-assisted
mechanochemical synthesis, which has recently been shown to
be applicable to the synthesis of a range of different types
of coordination compound.2,5 The IR spectrum of the initially
formed product showed the presence of both a carbonate and
a bicarbonate complex, with the proportion of bicarbonate
increasing at the expense of carbonate with successive treatments
(see Experimental and IR Spectroscopy sections). This implies
that the reaction proceeds in two stages:
CuCO3·Cu(OH)2 + 5Ph3P + CO2 → 2[(Ph3P)2Cu(HCO3)] +
(6)
Ph3PO
A previously reported synthesis of [(Ph3P)2Cu(HCO3)] used an
indirect route, involving decarboxylation of the precursor complex
bis(triphenylphosphine)copper(I) phenylmalonate benzyl ester.1
In the present study we have prepared a compound of the same
composition by a metathesis route analogous to that in eqn (4) for
the corresponding silver(I) complex (see Experimental, Infrared,
and 31P CP MAS NMR sections).
Ag2CO3 + 4PPh3 → [{(Ph3P)2Ag}2(CO3)]
(2)
[{(Ph3P)2Ag}2(CO3)] + H2O + CO2 → 2[(Ph3P)2Ag(HCO3)] (3)
Subsequent experiments resulted in the synthesis of
both of these compounds by conventional solution meth-
ods. [{(Ph3P)2Ag}2(CO3)] was prepared as the dihydrate
[{(Ph3P)2Ag}2(CO3)]·2H2O by reaction of Ag2CO3 and PPh3 in
a 1 : 6 mole ratio in acetonitrile. Carrying out the reaction in
dry acetonitrile with exclusion of air resulted in no dissolution
of the Ag2CO3 and no product formation, but the product formed
rapidly in contact with ambient air, with incorporation of H2O
from the air. Removal of [{(Ph3P)2Ag}2(CO3)]·2H2O as a solid
product prevented further reaction with CO2 from the air to
form a bicarbonate complex. Use of ethanol as a solvent, as
Structure determinations
The results of the single crystal X-ray studies define the sto-
ichiometries and forms of the above silver(I) (bi-)carbonate:
triphenylphosphine complexes. The maximal stoichiometry of
four triphenylphosphine ligands per silver atom is achieved
in the salt formulated as [Ag(PPh3)4](HCO3)·2EtOH·3H2O, the
anionic and solvent components being ill-defined in the context
of very extensive data, despite expectations consequent on their
appreciable charges and/or dipolar characteristics. One half of
the formula unit comprises the asymmetric unit of the structure,
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the cation being disposed with the metal atom lying on a
crystallographic 2-axis in space group C2/c (Fig. 1; cf. a number
6
of the other examples of [M(EPh3)4]+ recorded in ref. in salts
¯
which crystallize in space group R3, with the cation disposed on
(and, usually somewhat disordered about) the crystallographic
3-axis)). Here we find Ag–P precisely established to be almost
˚
identical (2.6037(4), 2.6168(4) A) with P–Ag–P about the axis
108.97(2), and 110.69(2)◦, and between the distinct phosphorus
atoms 108.42(2) and 110.16(1)◦, a closely regular tetrahedral array
˚
with Ag–P 2.61 A, more in keeping with the trend expected for the
+
˚
sequence Ag–As 2.67, Ag–Sb 2.73 A in [Ag(EPh3)4] arrays than
previously estimated.6
Fig. 2 Projection of a single molecule of [{(Ph3P)2Ag}2(CO3)], normal to
the carbonate plane.
residues assigned as probable water molecule components all
lie at sensibly interacting distances with the carbonate oxygen
atoms, thus O(4) (full component) ◊ ◊ ◊ O(2,5) 2.702(6), 2.92(1);
˚
O(5)(fragment) ◊ ◊ ◊ O(3) 2.88(1); O(6)(fragment) ◊ ◊ ◊ O(3) 2.54(3) A.
With the bicarbonate two forms have been obtained, both
crystallized from acetonitrile and both unsolvated, with neu-
tral molecules of quite different nuclearities. The asymmetric
unit of the mononuclear, triclinic ‘a’ phase contains a single
molecule of the form [(Ph3P)2Ag(O2COH)], devoid of crys-
tallographic symmetry; it is depicted in Fig. 3. Ag–P;O are
˚
2.4323(3), 2.4345(3); 2.4128(7), 2.5951(9) A, with P–Ag–P, O–
Ag–O 132.882(9), 52.47(3), and P–Ag–O 100.47(2)–116.33(2)◦.
˚
C–O;OH are 1.274(1), 1.241(1);◦1.347(1) A, with O–C–O; O–C–
˚
OH 123.9(1); 118.2(1), 117.9(1) ; the silver atom lies 0.071(2) A
out of the CO3 plane. The molecule lies close to its inversion
image, as shown in Fig. 3, by virtue of hydrogen bonding between
their bicarbonate OH components (O,H(3) ◊ ◊ ◊ O(1¢) 2.624(1),
Fig.
1
Projection of the [Ag(PPh3)4]+ cation in [Ag(PPh3)4]-
(HCO3)·2EtOH·3H2O down the/its (crystallographic) two-fold axis.
˚
1.75(2) A).
The remaining structurally characterized adducts all have two
triphenylphosphine ligands per silver atom, all silver atoms being
three- or four-coordinate with P2AgO1,2 environments. One of
these incorporates the carbonate ion as a complex of disilver(I)
carbonate, thus Ag2CO3:PPh3 (1 : 4) ·2H2O. The complex is shown
to be binuclear [{(Ph3P)2Ag}2(CO3)], in a triclinic cell rather
1
similar to that of the copper(I) analogue recorded in ref. ; a full
neutral molecule devoid of crystallographic symmetry (together
with solvent), comprises the asymmetric unit of the structure.
The molecule is shown projected normal to the plane of the
carbonate group which bridges the two silver atoms (Fig. 2). The
structure, however, is subtly different from that of the copper
atom, the linkage between the metal atoms being M(O·C(m-
O)·O)M in the case of the copper complex, the bridging array
having quasi-C2v symmetry, and the metal atoms both four-
coordinate, P2CuO,(m-O), while in the silver complex, the array
becomes unsymmetrical M(O·CO(m-O))M (m-symmetry), Ag(1)
being four-coordinate P2AgO,(m-O) and Ag(2) three-coordinate
P2Ag(m-O), the distance Ag(2) ◊ ◊ ◊ O(3) having now become long.
Core geometries for both species are presented in Table 1, wherein
we see that the geometry about Ag(2) may be considered trigonal
planar. Although hydrogen atoms have not been defined, the
Fig. 3 Projection of mononuclear [(Ph3P)2Ag(O2COH)], through the
(bi)carbonate plane, together with its hydrogen-bonded inversion image.
The second form was obtained adventitiously on only one
occasion, and there was no obvious difference in the experimental
conditions that led to this product. It takes a binuclear form
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Table 1 Comparative core geometries of [{(Ph3P)2M}2(CO3)], M = Cu, Ag
Atoms
Parameter
Atoms
Parameter
˚
Distances (A)
M(1)–O(1)
M(1)–O(2)
M(1)–P(1)
M(1)–P(2)
C(1)–O(1)
C(1)–O(2)
2.20(1), 2.438(4)
2.12(1), 2.376(4)
2.23(1), 2.438(1)
2.21(1), 2.426(2)
1.32(5), 1.314(7)
1.29(1), 1.277(7)
M(2)–O(1)
M(2)–O(3)
M(2)–P(3)
M(2)–P(4)
C(1)–O(3)
2.11(1), 2.232(4)
2.18(1), 2.914(6)
2.24(1), 2.434(1)
2.27(1), 2.455(1)
1.24(5), 1.231(8)
Angles (degrees)
P(1)–M(1)–P(2)
P(1)–M(1)–O(1)
P(2)–M(1)–O(1)
P(1)–M(1)–O(2)
P(2)–M(1)–O(2)
O(1)–M(1)–O(2)
M(1)–O(1)–C(1)
M(2)–O(1)–C(1)
M(1)–O(1)–M(2)
M(1)–O(2)–C(1)
127.0(6), 125.15(5)
109.3(8), 121.2(1)
114.4(8), 106.8(1)
115.3(8), 103.7(1)
110.5(8), 126.3(1)
63(1), 54.3(1)
P(3)–M(2)–P(4)
P(3)–M(2)–O(1)
P(4)–M(2)–O(1)
P(3)–M(2)–O(3)
P(4)–M(2)–O(3)
O(1)–M(2)–O(3)
M(2)–O(3)–C(1)
O(1)–C(1)–O(2)
O(1)–C(1)–O(3)
O(2)–C(1)–O(3)
119.1(6), 124.09(5)
112.7(8), 129.0(1)
125.8(8), 106.4(1)
118.6(7), —
104.4(7), —
60(1), —
87(1), 92.0(3)
91(1), —
92(1), 105.8(3)
174(1), 151.9(2)
91(1), 95.8(4)
119(1), 116.1(6)
115(1), 120.4(6)
126(1), 123.5(6)
1
˚
˚
In the copper complex, Cu(1,2) lie 0.16(4), -0.35(4) A out of the carbonate plane; counterpart values in the silver complex are 0.56(1), -1.24(1) A. In the
◦
silver complex, the angle sum about Ag(2) is 359.5
.
Table 2 Comparative [(Ph3P)2M(m-OX)2M(PPh3)2] core geometries
M/OX Cu/m-OCOOH Ag/m-OCOOH Ag/m-ONO2
[(Ph3P)2Ag(m-O·COOH)2Ag(PPh3)2], also unsolvated, one half of
the dimer comprising the asymmetric unit of the structure. It is
isomorphous with its copper(I) counterpart of ref. 1, and also
4
the nitrate of ref. ; the dimer is depicted in Fig. 4(a). The silver
˚
Distances (A)
M–P(1)
M–P(2)
M–O(11)
M–O(21)
N,C(1)–O(11)
N,C(2)–O(21)
N,C(1)–O(12)
N,C(2)–O(22)
atoms have P2Ag(m-O)2 coordination environments and are linked
by a four-membered Ag(m-O)2Ag ring; comparative geometries
which, apart from differing metal radii, are remarkably similar, but
very different from those of the mononuclear form, are presented
in Table 2. The generator of the dimer is the two-fold axis of
the rather unusual space group P21212 which passes through the
(m-O)-C bonds of each of the two bicarbonate components. The
molecules are linked into columns along the 2-axis by hydrogen-
2.272(3)
2.283(3)
2.150(7)
2.154(7)
1.22(2)
1.27(2)
1.29(1)
1.27(2)
2.457(2)
2.441(2)
2.353(3)
2.351(3)
1.251(9)
1.269(9)
1.295(5)
1.277(5)
2.448(1)
2.425(1)
2.341(3)
2.340(3)
1.248(8)
1.288(7)
1.295(5)
1.290(4)
Angles (degrees)
P(1)–M–P(2)
˚
116.9(1)
104.5(2)
119.6(1)
121.9(1)
110.1(2)
78.6(3)
120.55(5)
101.63(6)
117.87(4)
121.37(5)
111.24(6)
76.19(14)
128.13(10)
128.06(10)
120.3(4)
119.7(4)
119.5(7)
120.6(7)
103.7(2)
120.6(1)
101.2(1)
117.0(1)
122.1(1)
111.9(1)
75.7(1)
127.9(1)
127.8(1)
120.8(3)
119.4(3)
118.3(6)
121.2(5)
104.3(2)
104.4(2)
bonds (O(12) ◊ ◊ ◊ O(22) 2.591(5) A; Fig. 4(b)), a feature not possible
P(1)–M–O(11)
P(1)–M–O(21)
P(2)–M–O(11)
P(2)–M–O(21)
O(11)–M–O(21)
M–O(11)–C(1)
M–O(21)–C(2)
O(11)–C(1)–O(12) 122.1(7)
O(21)–C(2)–O(22) 119.4(8)
O(12)–C(1)–O(12¢) 116(1)
O(22)–C(2)–O(22¢) 121(2)
M–O(11)–M¢
M–O(21)–M¢
in the isomorphous nitrate.
Infrared spectroscopy
129.2(1)
129.4(2)
The IR spectra of the air-stable complexes in the range 800–
1800 cm-1 are shown in Fig. 5. The bands of coordinated
2-
2-
CO3 arising from the E¢ n(CO) (n3) mode of CO3 normally
occur in the range 1260–1580 cm-1;7 in the IR spectrum of
[{(Ph3P)2Ag}2(CO3)]·2H2O the bands at 1308, 1460 cm-1 are thus
assigned, with possible additional absorption around 1400 cm-1
partially obscured by a strong Ph3P band at 1433 cm-1 (Fig. 5(a)).
The corresponding n3 absorption in pure solid Ag2CO3 occurs at
1410 cm-1.8 The splitting Dn of this band in [{(Ph3P)2Ag}2(CO3)]
(ca. 150 cm-1) is at the lower end of the range 0–440 cm-1 that
has been reported for a wide range of carbonato complexes.9 It is
also small compared with the range 200–300 cm-1 calculated on
the basis of a linear correlation that has been proposed between
Dn and Da (the difference between the largest and the smallest
O–C–O angle in the coordinated carbonate ion;9 in the present
101.5(4)
101.3(2)
103.9(2)
˚
Metal atom deviations (dA) from the m-O(C/N)O2 plane
dM/plane 1
dM/plane 2
0.18(2)
0.10(2)
0.05(1)
0.22(1)
0.19(1)
0.05(1)
A2¢¢ out-of plane bending (n2) mode of CO32- in Ag2CO3 occurs at
880 cm-1,8 and the band at 854 cm-1 in [{(Ph3P)2Ag}2(CO3)]·2H2O
(Fig. 5(a)) is assigned to this mode. The n2 band has been reported
to occur in the range 820–890 cm-1 in a wide range of carbonato
complexes.7,10
case Da = 11 2◦; Table 1). The A1 n(CO) (n1) mode of CO3 in
2-
Ag2CO3 occurs at 1020 cm-1,8 but unfortunately this is close to a
strong Ph3P band at 1069 cm-1, so that unambiguous assignment
of this mode in [{(Ph3P)2Ag}2(CO3)]·2H2O cannot be made. The
The uncomplexed bicarbonate ion HCO3 shows asymmetric
-
and symmetric CO stretching vibrations nas(CO) = 1697, ns(CO) =
1338 cm-1, as well as a stretching vibration of the C–OH
7214 | Dalton Trans., 2011, 40, 7210–7218
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Fig.
5
Mid-IR spectra of (a) [{(Ph3P)2Ag}2(CO3)]·2H2O; (b)
[(Ph3P)2Ag(O2COH)]; (c) [(Ph3P)2Ag(m-O.CO.OH)2Ag(PPh3)2]; (d)
[(Ph3P)2Cu(HCO3)].
of bands in its IR spectrum can be made.12 However, the
stoichiometric mixed valence silver(I, II, III) oxide bicarbonate
Ag7O8HCO3 has been reported and its IR spectrum assigned.13
Assignments of nas(CO) = 1632, ns(CO) = 1314 cm-1 are in good
-
agreement with those discussed above for uncomplexed HCO3
and [(Ph3P)2Ag(O2COH)]. In addition, a band at 1448 cm-1 is
assigned as d(OHO) associated with the O–H ◊ ◊ ◊ O hydrogen
bonding between the bicarbonate ions in the compound, which
agrees exactly with the value 1448 cm-1 calculated for the isolated
[HCO3 ]2 dimer.13 In the present [(Ph3P)2Ag(O2COH)] complex,
-
the band at 1405 cm-1 is therefore assigned as d(OHO) for the
-
2¥(Ph3P)2Ag+ complexed [HCO3 ]2 dimer present in this complex
Fig. 4 (a) Projection of binuclear [(Ph3P)2Ag(m-O.CO.OH)2Ag(PPh3)2],
through the central bis(bicarbonate) plane; (b) Projection normal to the
central bis(bicarbonate) plane, showing the hydrogen-bonded columnar
formation.
(Fig. 3). Rather surprisingly, the IR spectrum of the O-bridged
dimer polymorph [(Ph3P)2Ag(m-O.CO.OH)2Ag(PPh3)2] is almost
identical with that of the “monomer” form [(Ph3P)2Ag(O2COH)]
(Fig. 5(c)), so the same assignments can be made. In the case
of the O-bridged dimer, the presence of a d(OHO) band at 1404
cm-1 is due to association of the dimers in a hydrogen-bonded
columnar formation Fig. 4(b). While the IR spectra of the two
polymorphs of [(Ph3P)2Ag(HCO3)] are almost identical, the 31P
CPMAS NMR spectra are more distinctly different (see NMR
Spectroscopy section below). The uncomplexed bicarbonate ion
bond n(COH) = 960 cm-1.11 The corresponding absorptions
in [(Ph3P)2Ag(O2COH)] are assigned at 1600, 1334, 936 cm-1
(Fig. 5(b)). An additional strong band is present at 1405 cm-1,
which does not appear to correspond to any of the n(CO) modes
-
in uncomplexed HCO3 . Although there are some reports of
the existence of uncomplexed AgHCO3 in the literature, with
IR spectra reported in some cases, the material concerned has
not been characterized to the extent that confident assignments
-
HCO3 shows an out-of-plane bending mode (corresponding to
the A2¢¢ out-of plane bending (n2) mode of CO32-) at 835 cm-1,11 and
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the band at 827 cm-1 in both polymorphs of [(Ph3P)2Ag(HCO3)]
(Fig. 5(b,c)) is assigned to this mode.
The IR spectrum of [(Ph3P)2Cu(HCO3)] (Fig. 5(d)) is similar
to those of the two corresponding [(Ph3P)2Ag(HCO3)] poly-
morphs (Fig. 5(b,c)) so that similar assignments can be made:
nas(CO) = 1598, ns(CO) = 1300, d(OHO) = 1392 cm-1 (the
expected n(COH) band is not obvious in this case). There is
some evidence of splitting of the nas(CO) band at ca. 1600 cm-1 in
the two [(Ph3P)2Ag(HCO3)] polymorphs (Fig. 5(b,c)), and this is
more pronounced in the spectrum of [(Ph3P)2Cu(HCO3)], with
partially resolved bands at 1665, 1634, 1598, 1584, 1571 cm-1
(Fig. 5(d)). The crystal structure of a complex of this composition
has been reported previously, and shows the O-bridged dimer
structure [(Ph3P)2Cu(m-O.CO.OH)2Cu(PPh3)2], with association
of the dimers in a hydrogen-bonded columnar formation.1 It is
likely that the complex prepared in the present study has the
same structure, although the fact that both “monomer” and
O-bridged dimer forms have been found for the corresponding
silver(I) complex leaves room for some ambiguity on this point.
The band due to the out-of-plane bending mode of the bicarbonate
-
ion HCO3 that corresponds to the A2¢¢ out-of plane bending
2-
(n2) mode of CO3 occurs at 817 cm-1 in [(Ph3P)2Cu(HCO3)]
(Fig. 5(d)), shifted to lower wavenumber relative to the correspond-
ing band at 827 cm-1 in both polymorphs of [(Ph3P)2Ag(HCO3)]
(Fig. 5(b,c)).
The IR spectra of the dry products from the solvent (ethanol)
assisted mechanochemical reaction of Ag2CO3 + 2Ph3P after 1–
6 mechanochemical treatments (see Experimental section) are
2-
shown in Fig. 6. Initially the E¢ n(CO) (n3) mode of CO3
gives a single broad band centred at 1378 cm-1, and there
is no evidence of the bicarbonate nas(CO) band at 1600 cm-1
(Fig. 6(a)). Upon further mechanochemical treatments, the band
at 1378 cm-1 splits, and a band at ca. 1600 cm-1 begins to
appear (Fig. 6(b,c)). Finally, after six successive treatments, the
spectrum (Fig. 6(d)) is essentially identical with those of the two
[(Ph3P)2Ag(HCO3)] polymorphs (Fig. 5(b,c)). This is consistent
with the reaction (3) above, although the band at 1308 cm-1
corresponding to [{(Ph3P)2Ag}2(CO3)]·2H2O does not gain much
intensity before the bicarbonate band begins to build, suggesting
that the formation of the bicarbonate complex occurs almost as
rapidly as the reaction between Ag2CO3 and Ph3P. The A2¢¢ out-
Fig. 6 Mid-IR spectra (800–1800 cm-1) of the dry products from the
solvent (ethanol) assisted mechanochemical reaction of Ag2CO3 + 2Ph3P
after (a) one; (b) two; (c) four; (d) six mechanochemical treatments.
the two polymorphs of [(Ph3P)2Ag(HCO3)]; in [(Ph3P)2Cu(HCO3)]
n(OH) is observed as a single band at 2615 cm-1.
Solid State 31P MAS NMR Spectroscopy
The 31P CPMAS NMR spectra of the air-stable complexes are
shown in Fig. 8, and the derived NMR parameters are listed
in Table 3. In general, the spectra of the silver complexes are
expected to consist of partially resolved multiplets due to the
individual 31P chemical shifts emanating from the chemically
inequivalent P nuclei bound to each Ag centre. Each resonance
displays 1J(107,109Ag,31P) scalar coupling between the 31P (I = 1/2)
and 107,109Ag nuclei (I = 1/2), and further splitting of these doublets
can occur via 2J(31P,31P) coupling.14,15 For the present compounds,
this is well illustrated by the case of [(Ph3P)2Ag(O2COH)], which
contains two inequivalent P atoms bound to the same Ag atom,
resulting in an ABX spin system (A, B = 31P; X = 107,109Ag)
for each Ag isotope. The 31P spectrum shows the AB part of
the ABX spectra, which in general consists of two overlapping
sets of AB quartets,16 the separate patterns for coupling to
the 107,109Ag isotopes normally remaining unresolved. In the
case of [(Ph3P)2Ag(O2COH)] the spectrum consists of two non-
overlapping, nearly identical AB quartets (Fig. 8(b)). This occurs
in the special case for which the JAX, JBX coupling constants are
2-
of plane bending (n2) mode of CO3 in the initial product of
the mechanochemical synthesis occurs at 845 cm-1 (Fig. 6(a)),
significantly lower than the values for Ag2CO3 (880 cm-1)8 and
[{(Ph3P)2Ag}2(CO3)]·2H2O (854 cm-1; Fig. 5(a)). This band shifts
to lower wavenumber upon further mechanochemical treatment
(Fig. 6(b–d)), approaching the value 827 cm-1 found for both
polymorphs of [(Ph3P)2Ag(HCO3)] (Fig. 5(b,c)), and in accordance
with the reaction (3) above.
Further IR spectroscopic evidence for this reaction can be seen
in changes in the spectra in the n(OH) region, shown in Fig. 7.
Broad bands due to H2O in the 3200–3400 cm-1 region in the
early stages of the mechanochemical process (Fig. 7(a,b)) decrease
in intensity upon further mechanochemical treatment (Fig. 7(c,d)
and are replaced by bands at 2670, 2615 cm-1 (Fig. 7(c,d)). These
latter bands are assigned to n(OH) of the H-bonded bicarbonate
dimer groups in [(Ph3P)2Ag(HCO3)], and may be compared with
the values 2935, 2615 cm-1 in the H-bonded bicarbonate dimers in
KHCO3.11 There is essentially no difference in the n(OH) bands in
7216 | Dalton Trans., 2011, 40, 7210–7218
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Table 3 31P CPMAS NMR parameters
Compound
d(31P)/ppm
1J(107,109Ag,31P) or 1J(63,65Cu,31P)/Hz
[{(Ph3P)2Ag}2(CO3)]·2H2O
[(Ph3P)2Ag(O2COH)]
[(Ph3P)2Ag(m-O.CO.OH)2Ag(PPh3)2]
[(Ph3P)2Cu(HCO3)]
6.8
6.1, 7.2
5.4
421
475, 469 (2J(PP) = 147 Hz)
432
1340
-7.7
Fig. 7 Mid-IR spectra (2200–3600 cm-1) of the dry products from the
solvent (ethanol) assisted mechanochemical reaction of Ag2CO3 + 2Ph3P
after (a) one; (b) two; (c) four; (d) six mechanochemical treatments.
nearly equal and the difference between the two 31P chemical
shifts dA, dB is small, as is evident from the values of the NMR
parameters for [(Ph3P)2Ag(O2COH)] in Table 3. Expansion of this
spectrum reveals that each line is an incompletely resolved doublet
and this is attributed to resolution of the 1J(107,109Ag,31P) coupling
for the two silver isotopes, as evidenced by the good fit of the
1
observed spectrum to that simulated with distinct J(109Ag,31P),
1J(107Ag,31P) values in the ratio 1.1496 corresponding to the ratio
of the 109Ag, 107Ag magnetic moments (Fig. 9).
The spectrum of the sample from which crystals of the
O-bridged dimer [(Ph3P)2Ag(m-O.CO.OH)2Ag(PPh3)2] were ob-
tained shows a dominant intense doublet and a set of weaker
signals (Fig. 8(c)), the latter being identical to those of the
“monomer” polymorph [(Ph3P)2Ag(O2COH)] (Fig. 8(b)). This
implies that the sample is a mixture consisting predominantly
of the O-bridged dimer, but containing a smaller amount of the
“monomer” form as well. The dominant doublet assigned to the
dimer implies that the two P atoms are effectively equivalent
in this case, although this is not required crystallographically
(see Structure determination section and Fig. 3), resulting in a
Fig. 8 31P CP MAS NMR spectra of (a) [{(Ph3P)2Ag}2(CO3)]·2H2O;
(b) [(Ph3P)2Ag(O2COH)]; (c) [(Ph3P)2Ag(m-O.CO.OH)2Ag(PPh3)2]; (d)
[(Ph3P)2Cu(HCO3)].
1
single 31P chemical shift and J(107,109Ag,31P) coupling constant
The spectrum of [(Ph3P)2Cu(HCO3)] is shown in Fig. 8(d). The
31P CP MAS NMR spectra of copper(I) phosphine complexes
consist of quartets due to the 2I + 1 = 4 splitting arising from
1J(63,65Cu,31P) coupling (63Cu, 65Cu, I = 3/2). Multiplet peaks
arising from 31P coupling to 65Cu are seen just outside of those
(Table 3). A similar situation is found for the carbonate complex
[{(Ph3P)2Ag}2(CO3)]·2H2O, which shows essentially a simple
doublet, despite the presence of four inequivalent P atoms in the
molecule (see Structure determination section and Fig. 2).
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Advanced Materials Project 2), with support from Advantage West
Midlands (AWM) and partial funding by the European Regional
Development Fund (ERDF). CP thanks the Universita` degli Studi
di Camerino, Italy, for funding.
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107
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JAX = 508 Hz, JBX = 437 Hz, JBX = 502 Hz, JAB = 147 Hz.
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˚
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1
3
˚
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the (I = 1/2) 31P and the quadrupolar (I = 3/2) 63,65Cu nuclei.14,17–21
These features are evident in the spectrum of [(Ph3P)2Cu(HCO3)]
(see Fig. 8(d)). If the structure of this complex is the same as
that of the previously published O-bridged dimer [(Ph3P)2Cu(m-
O.CO.OH)2Cu(PPh3)2]1 then the two P atoms bound to each Cu
atom should be inequivalent. However, no evidence of 2J(31P,
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Conclusion
Solution and mechanochemical methods involving incorporation
of gaseous reactants have been used in the study of triphenylphos-
phine complexes of silver(I) carbonate and bicarbonate. In the
case of the mechanochemical syntheses, this demonstrates an
additional aspect of this type of synthesis, which potentially
increases its versatility. The study further demonstrates the value
of ATR IR and CPMAS NMR spectroscopy for monitoring the
progress of mechanochemical syntheses.
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Acknowledgements
JVH thanks EPSRC and the University of Warwick for partial
funding of the solid state NMR infrastructure at Warwick, and
acknowledges additional support for this infrastructure obtained
through Birmingham Science City: Innovative Uses for Advanced
Materials in the Modern World (West Midlands Centre for
7218 | Dalton Trans., 2011, 40, 7210–7218
This journal is
The Royal Society of Chemistry 2011
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