Synthesis, spectroscopic and structural characterization of adducts of stoichiometry CuX:dppe (1:2) (X = I, ClO4, BH4, O 3SCF3, SCN, dppe = Ph2P(CH2) 2PPh2)

Article abstract of DOI:10.1016/j.ica.2005.06.046

Syntheses and spectroscopic features (IR, NMR and ESI MS) are reported for five 1:2 adducts of CuX with dppe (X = I, ClO₄, NCS, O ₃SCF₃ (tfs) BH₄; dppe = Ph₂P(CH ₂)₂PPh₂). ESI MS and ³¹P NMR spectroscopy indicate that these species dissociate in solution yielding free diphosphine and 3:2 species. A single crystal X-ray structure determination has been carried out on Cu(dppe)₂NCS defining a four-coordinate complex of the form [(P,P′-dpex)M(P-dpex)X] for M = Cu, the thiocyanate being N-bound; the ionic [Cu(P,P′-dppe)₂]tfs has also been structurally characterized.

Full text of DOI:10.1016/j.ica.2005.06.046

Inorganica Chimica Acta 358 (2005) 4003–4008
www.elsevier.com/locate/ica
Synthesis, spectroscopic and structural characterization of adducts
of stoichiometry CuX:dppe (1:2) (X = I, ClO4, BH4, O3SCF3, SCN,
dppe = Ph2P(CH2)2PPh2)
a
a,
a
b
Corrado di Nicola , Claudio Pettinari *, Massimo Ricciutelli , Brian W. Skelton ,
b
b
Neil Somers , Allan H. White
a
`
Dipartimento di Scienze Chimiche, Universita degli Studi di Camerino, via S. Agostino 1, 62032 Camerino MC, Italy
Chemistry M313, School of Biomolecular, Biomedical and Chemical Sciences, University of Western Australia, Crawley, W.A. 6009, Australia
b
Received 6 June 2005; accepted 22 June 2005
Available online 10 August 2005
Abstract
Syntheses and spectroscopic features (IR, NMR and ESI MS) are reported for five 1:2 adducts of CuX with dppe (X = I, ClO4,
NCS, O3SCF3 („tfs) BH4; dppe = Ph2P(CH2)2PPh2). ESI MS and 31P NMR spectroscopy indicate that these species dissociate in
solution yielding free diphosphine and 3:2 species. A single crystal X-ray structure determination has been carried out on Cu(dp-
pe)2NCS defining a four-coordinate complex of the form [(P,P0-dpex)M(P-dpex)X] for M = Cu, the thiocyanate being N-bound;
the ionic [Cu(P,P0-dppe)2]tfs has also been structurally characterized.
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: Silver; 31P NMR; X-ray crystal structure; Diphosphine; ESI MS
1. Introduction
nate: for ꢀdppeꢁ (=bis(diphenylphosphine)ethane = Ph2P-
(CH2)2PPh2) [Cu(dppe)2](ClO4) [8], [Cu(dppe)2](NO3)
[9], ð‘tfa’ ð¼ CF3ꢀÞÞ [10], (PF6) [11], [Ag(dppe)2](NO3)
[12], for ꢀdpppꢁ (=bis(diphenylphosphino)propane =
Ph2P(CH2)3PPh2), [Cu(dppp)2](ClO4) [13,14], (BF4)
[8], [Ag(dppp)2](SCN) [15], for ꢀdppfꢁ (=bis-(diph-
Previous contributions [1–7] in the present sequence
have described the structural characterization of ad-
ducts of stoichiometry MX:dpex (1:1) [1–5] or (2:3)(n)
[6] or (2:1) [7], M = univalent coinage metal (cop-
per(I), silver(I)), X = simple anion, usually (pseudo)-
halide or, where possible, oxyanions ClO4, NO3,
carboxylate (spanning a range of basicities), dpex =
Ph2E(CH2)xEPh2, bis(diphenylpnicogeno)alkane (or,
on occasion, bis(diphenylphosphino)-ferrocene, ꢀdppfꢁ)
[5]. Structurally defined adducts of the form MX:L
(1:2) are few in number, all defined as E = P. The
majority are ionic, with mononuclear cations of the
form [M(P-dppx-P0)2]X, the metal being four-coordi-
enylphosphino)ferrocene)
[Ag(dppf)2](ClO4)
[16],
(BF4) [17]; an ionic binuclear form is defined for
[(P,P0-dppe)Ag(P-dppe-P0)2Ag(P,P0-dppe)](NO3)2 [18].
A neutral mononuclear four-coordinate form (errone-
ously described by us as three-coordinate on p. 721
of [1]) is found in [(P,P0-dppp)Ag(P-dppp)X], X =
Cl, Br, I, CN [15]. Thus far, there have been no re-
ports of structurally characterized adducts of the form
CuX:ppx (1:2) for any X = halide or pseudo-halide,
although a hint as to the possible accessibility of a
[(P,P0-dppx)Cu(P-dppx)X] array is provided by the
isolation and structural characterization of the adduct
CuCl:dppe (2:3) as [{(P,P0-dppe)CuCl}2(P-dppe-P0)]
*
Corresponding author. Tel.: +390 737 402234; fax: +390 737
637345.
E-mail address: claudio.pettinari@unicam.it (C. Pettinari).
0020-1693/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2005.06.046

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C. di Nicola et al. / Inorganica Chimica Acta 358 (2005) 4003–4008
[19], where the four-coordinate environment is filled
by a combination of uni-and bi-dentate dppe.
F3)Æ1/2C6H6 (0.25 g, 1.0 mmol). The suspension was
stirred until a clear solution was obtained. After 48 h,
the solution was slowly evaporated until a microcrystal-
line precipitate formed, which was washed with a mix-
ture of ethanol/diethyl ether at a ratio of 1:1 to give
complex 2 as a colourless solid in 80% yield; m.p. 198–
Adducts of the form CuX:dppe (1:2) have been of
interest in respect of their biological activity against
P388 leukaemia, M5076 reticulum cell sarcoma and
B16 melanoma [20]. In particular, for X = halide, much
of their chemistry is ill-defined, with a poverty of struc-
tural data. We have synthesized a number of CuX:dppe
(1:2) adducts and characterized them as described here-
in. In undertaking single crystal X-ray characterization,
we were intrigued by the dichotomy described above be-
tween the forms obtained for AgX:dppp (1:2) for
X = SCN (ionic) and X = Cl, Br, I, CN (neutral mono-
nuclear molecules). With the CuX:dppe (1:2) array, the
thiocyanate, obtained adventitiously crystalline, being
shown to be of the form [(P,P0-dppe)Cu(NCS)(P-dppe)],
provides a platform for the understanding of the
remainder of its less tractable halide counterparts.
1
201 ꢁC dec. H NMR (CDCl3, 293 K): d 2.44 (m br,
8H, PCH2), 7.2–7.7 (m br, 40H, C6H5). 31P {1H}
NMR (CDCl3, 293 K): d 5.6br, 32.97s. IR(nujol,
cmꢀ1): 3058w, 1587w, 1571, 1236s, 1145s, 571w, 553w,
522m, 510m, 482m, 471sh, 421w, 415w, 370w. ESI MS
(+): 502 [18] [Cu(MeCN)(dppe)]+; 859 [100] [Cu-
(dppe)2]+. Anal. Calc. for C53H48CuF3O3SP4: C, 63.06;
H; 4.79; S, 3.18. Found: C, 63.39; H, 4.93; S, 2.98%.
Km(CH2Cl2, 10ꢀ3 M): 48 Xꢀ1 mol2 cmꢀ1. Recrystalliza-
tion from chloroform–ethanol yields 95% of 2ÆH2O.
2.2.3. CuSCN:dppe (1:2) (3)
dppe (1.60 g, 4.0 mmol) was added at room tempera-
ture to an ethanol suspension (20 ml) of CuSCN (0.12 g,
1.0 mmol). The suspension was stirred for 48 h. The
colourless precipitate was filtered and washed with a
mixture of ethanol/diethyl ether 1:1 to give complex 3
2. Experimental
2.1. Materials and methods
1
as a colourless solid in 80% yield; m.p. 226 ꢁC dec. H
All syntheses, handling and measurements were car-
ried out as described in the preceding paper [1]. For
the ESI-MS data, masses and intensities were compared
to those calculated by using the IsoPro Isotopic Abun-
dance Simulator Version 2.1 [21]; peaks containing cop-
per ions are identified as the centres of isotopic clusters.
NMR (CDCl3, 293 K): d 2.1, 2.3 (br, 4H, PCH2),
7.0–7.7 (m br, 20H, C6H5). 31P {1H} NMR (CDCl3,
293 K): d ꢀ5.7 br. IR(nujol, cmꢀ1): 3042w, 2067s
(CN), 1583w, 1570w, 1482sh, 518s, 509s, 491m, 481m,
443w, 420w, 363w, 340w, 236w. ESI MS (+): 502 [15]
[Cu(MeCN)(dppe)]+; 859 [100] [Cu(dppe)2]+. Anal.
Calc. for C53H48CuNP4S: C, 69.31; H; 5.27; N, 1.53;
S, 3.49%. Found: C, 68.89; H, 5.23; N, 1.89; S, 3.76%.
2.2. Syntheses of the copper complexes
Km(CH2Cl2, 10ꢀ3 M): 40.0 Xꢀ1 mol2 cmꢀ1
.
2.2.1. CuI:dppe (1:2) (1)
dppe (0.79 g, 2.0 mmol) was added at room tempera-
ture to a chloroform suspension (20 ml) of CuI (0.19 g,
1.0 mmol). The suspension was stirred until a clear solu-
tion was obtained. After 48 h, the solution was evapo-
rated under vacuum and the residue washed with a
mixture of ethanol/diethyl ether at a ratio of 1:1. A clear
precipitate has been obtained which was filtered off and
washed with diethyl ether to give complex 1 as a colour-
less solid in 60% yield; m.p. 277 ꢁC dec. 1H NMR
(CDCl3, 293 K): d 2.4 (br, 4H, PCH2), 7.2–7.7 (m br,
20H, C6H5). 31P {1H} NMR (CDCl3, 293 K): d ꢀ11.9,
ꢀ5.7, +6.6. IR(nujol, cmꢀ1): 3042w, 1584w, 1570w,
1480m, 511s, 489m, 478m, 462m, 453w, 420w, 412w,
362w, 342w, 264w, 244w 203w, 174w. ESI MS (+):
502 [65] [Cu(MeCN)(dppe)]+; 859 [100] [Cu(dppe)2]+.
Anal. Calc. for C52H48CuIP4: C, 63.26; H; 4.90. Found:
C, 62.91.45; H, 5.15%. Km(CH2Cl2, 10ꢀ3 M):
2.2.4. CuClO4:dppe (1:2) (4)
dppe (1.60 g, 4.0 mmol) was added at room tempera-
ture to an ethanol suspension (20 ml) of (PPh3)4Cu-
(ClO4) (1.21 g, 1.0 mmol). A colourless precipitate
formed which was filtered off and washed with ethanol
to give complex 4 as a colourless solid in 40% yield;
1
m.p. 140–143 ꢁC dec. H NMR (CDCl3, 293 K): d 2.42
(t, 4H, PCH2), 7.2–7.5 (m br, 20H, C6H5). 31P {1H}
NMR (CDCl3, 293 K): d ꢀ12.1, 5.8 br. IR(nujol,
cmꢀ1): 3065w, 3046w, 1684w, 1569w, 1480sh, 1082s br,
622s (ClO4), 514s, 506m, 489m, 475m, 443w, 369w,
337w, 203br. ESI MS (+): 502 [15] [Cu(MeCN)(dppe)]+;
859 [100] [Cu(dppe)2]+. Anal. Calc. for C52H48ClCu-
O4P4: C, 65.07; H; 5.04%. Found: C, 65.27; H, 5.23%.
Km(CH2Cl2, 10ꢀ3 M): 40.0 Xꢀ1 mol2 cmꢀ1
.
2.2.5. CuBH4:dppe (1:2) (5)
39.5 Xꢀ1 mol2 cmꢀ1
.
dppe (1.60 g, 4.0 mmol) was added at room tempera-
ture to an ethanol suspension (20 ml) of Cu(PPh3)2-
(BH4) (0.60 g, 2.0 mmol). A colourless precipitate
formed which was filtered off and washed with ethanol
to give complex 5 as a colourless solid in 80% yield;
2.2.2. CuO3SCF3:dppe (1:2) (2)
dppe (0.79 g, 2.0 mmol) was added at room tempera-
ture to a chloroform suspension (20 ml) of Cu(O3SC-

C. di Nicola et al. / Inorganica Chimica Acta 358 (2005) 4003–4008
4005
1
m.p. 263 ꢁC dec. H NMR (CDCl3, 293 K): d 2.51 (t,
Variata. The tfs anion was modelled as disordered
over two sets of sites, occupancies refining to
0.661(9) and complement. A difference map residue
was assigned as a water molecule oxygen, site occu-
pancy set at unity after trial refinement, associated
H not located.
4H, PCH2), 7.5, 7.7 (m br, 20H, C6H5). 31P {1H}
NMR (CDCl3, 293 K): d ꢀ12.1, 5.8 br. IR(nujol,
cmꢀ1): 3073w, 3051w, 1589, 1482m, 532s, 511m, 500m,
455m, 409m, 392m, 310w, 301w, 288w, 269w, 251w,
198m, 188m, 171w. ESI MS (+): 431 [48] [(dppe-
O2) + H]+; 859 [100] [(dppe-O)2Na]+. Anal. Calc. for
C52H52BCuP4: C, 71.36; H; 5.99%. Found: C, 71.59;
2.3.1.2. CuSCN:dppe (1:2) (3). C53H48CuNP4SÆ3/2
C6H13N, M = 1067.3. Monoclinic, space group C2/c
H, 5.98%. Km(CH2Cl2, 10ꢀ3 M): 1.0 Xꢀ1 mol2 cmꢀ1
.
ðC62h; No: 15Þ, a = 46.355(5), b = 10.783(1), c = 22.306
3
˚
˚
2.3. Structure determination
(2) A, b = 91.871(2)ꢁ, V = 11144 A . Dc(Z = 8) =
1.272 g cmꢀ3. lMo = 5.9 cmꢀ1; specimen: 0.25 · 0.20 ·
0.10 mm; ꢀTꢁmin/max = 0.85. 2hmax = 58ꢁ; Nt = 54937,
N = 14270 (Rint = 0.039), No = 10226; R = 0.045, Rw =
0.052. T ca. 153 K.
Full spheres of CCD area-detector diffractometer
data (Bruker AXS instrument, x-scans, monochromatic
Mo Ka radiation, k = 0.71073 A) were measured yield-
˚
ing Ntotal reflections, these merging to N unique (Rint
cited) after ꢀempiricalꢁ/multiscan absorption correction
(proprietary software), No with F > 4r(F) being consid-
ered ꢀobservedꢁ and used in the full matrix least squares
refinement, refining anisotropic displacement parameter
Variata. Difference map residues were modelled in
terms of cyclohexylamine molecules, one comprising a
pair of overlapping half-weighted components, the other
disordered about one of the crystallographic 2-axes (iso-
tropic displacement parameter forms).
forms for the non-hydrogen atoms, (x,y,z,Uiso)H being
constrained at estimates. Conventional residuals R,
Rw are cited at convergence (weights: (r2(F) +
0.0004F2)ꢀ1), neutral atom complex scattering factors
being employed within the XTAL 3.7 program system
[22]. Pertinent results are given below and in the text,
tables and figures, the latter showing 50% probability
amplitude displacement ellipsoids for the non-hydrogen
3. Results and discussion
3.1. Syntheses
The reaction in solution at room temperature of one
equivalent of CuX (X = I, O3SCF3, SCN) with at least
two equivalents of 1,2-bis(diphenylphosphino)ethane
(dppe) at room temperature has given rise to the 1:2 ad-
ducts CuX:dppe 1–3 (Chart 1). Derivatives 4 and 5
formed when the triorganophosphine copper(I) com-
plexes [(PPh3)4Cu]ClO4 and [(PPh3)2CuBH4] were re-
acted with excess of the dppe donor. The P-donor
ligand to metal ratio employed is an important determi-
nant for the syntheses of the compounds, different spe-
cies being generally formed when equimolar quantities,
or donor excesses were employed. For example, when
the reaction between dppe and CuX (X = Cl or Br)
was carried out in a 1:2 equimolar ratio, the previously
reported trinuclear species CuX:dppe (2:3) formed [6].
The choice of the solvent is also important: the adducts
˚
atoms, hydrogen atoms having arbitrary radii of 0.1 A.
Full .cif depositions (excluding structure factor ampli-
tudes) reside with the Cambridge Crystallographic Data
Centre (CCDC 271376, 273448).
2.3.1. Crystal/refinement data
2.3.1.1. Cutfs:dppe (1:2) ꢀH2Oꢁ (2ÆH2O). C53H50Cu-
F3O4P4S, M = 1027.5. Monoclinic, space group P21/n
5
˚
(C2h, No. 14; variant), a = 15.068(2) A, b = 18.778(3)
3
˚
˚
˚
A, c = 18.584(3) A, b = 91.283(3)ꢁ, V = 5257 A .
Dc(Z = 4) = 1.296 g cmꢀ3
. l ; specimen:
Mo = 6.3 cmꢀ1
0.62 · 0.48 · 0.28 mm; ꢀTꢁmin/max = 0.90. 2hmax = 55ꢁ;
Nt = 45565, N = 11992 (Rint = 0.030), No = 8161; R =
0.058, Rw = 0.099. T ca. 300 K.
+
P
P
P
P
P
NCS
P
P
Cu
Cu
P
X-
a
b
Chart 1.

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C. di Nicola et al. / Inorganica Chimica Acta 358 (2005) 4003–4008
1–5 have been obtained when the reaction was carried
out in ethanol, whereas in MeCN adducts of stoichiom-
etries 1:1 were generally obtained. The materials are dif-
ficult to obtain suitably crystalline from the usual
solvents, the specimen of the thiocyanate used for the
X-ray work being obtained from cyclohexylamine.
Compounds 1–5 are generally air-stable, colourless
materials, moderately soluble not only in strongly ion-
izing solvents such as DMSO, dimethylformamide and
acetone, but also in chlorinated solvents such as
CH2Cl2 or CHCl3. Conductivity measurements, as ex-
pected, indicated that 1, 2 and 4 are 1:1 electrolytes in
dichloromethane, Km being always in the range 39–
48 Xꢀ1 cm2 molꢀ1. This suggests the absence of any
strong interaction between Cu and the counterions
in solution. The BH4 complex 5 is a non-electrolyte
in solution, presumably in consequence of rapid oxi-
dation of the dppe and partial dissociation of the
complex in solution according to the following equi-
librium (Eq. (1)).
downfield shifted with respect to those found in the free
donors.
The 31P NMR room temperature spectra of com-
pounds 1–5 (CDCl3 solution) exhibit broad singlets
shifted downfield with respect to the signal of the free
donor. This suggests that dissociation occurs in solution,
yielding species having a smaller ligand to metal ratio
(1:1 or 3:2) and the free dppe. In order to investigate dis-
sociative processes, we have added dppe to the NMR
tube containing solutions of compound 1. Three differ-
ent resonances were immediately distinguishable at ca.
ꢀ12, ꢀ6 and +6 ppm. The sharp signal at ca ꢀ12 ppm
is attributable to free dppe, whereas those at ca +6
and ꢀ6 ppm are most likely due to species having
CuP3 and CuP2 cores. On the addition of further dppe,
the signal at +6 ppm increases in intensity and shifts
downfield to 10.0 ppm in accordance with the formation
of a [Cu(dppe)2]+ cation. Oxidation of the dppe occurs
mainly in the solutions containing ClO4, BH4 and
MeSO3 counterions.
The positive electrospray mass spectra of 1–4 (the
most relevant data are reported in Section 2) clearly sup-
port the existence of the ionic 1:2 form in acetonitrile
solution, indicating, also, considerable dissociation in
that solvent. It is noteworthy that the major peaks in
the positive ion spectra of all species always arise from
the cationic species [Cu(dppe)2]+, consequent upon the
breaking of bridging bonds, and the loss of X counteri-
ons. However, peaks due to [Cu(MeCN)(dppe)]+ species
have always been detected; compound 5 is completely
dissociated in solution, peaks due to oxidized dppe only
being found.
ðdppeÞ2CuBH4 þ O2 $ dppe-O2 þ dppeCuBH4
ð1Þ
The conductivity value found for compound 3 sug-
gests ionic dissociation Eq. (2) in solution as confirmed
also by ESI-MS and NMR spectroscopy (see below).
½ðdppeÞ2Cuꢁþ þ SCN $ ½ðdppeÞ2CuꢁþSCNꢀ
ð2Þ
3.2. Spectroscopy
The infrared spectra of 1–5 (see Section 2) are consis-
tent with the formulations proposed, showing all of the
bands required by the presence of the counterion and of
the phosphorus or arsenic donor [23], the bands due to
the phosphine ligands being only slightly shifted with re-
spect to those of the free donors. In the far-IR spectra of
derivatives 1–5, the broad absorptions near 500 cmꢀ1
and those at 450–400 cmꢀ1 are due to Whiffenꢁs y and
t vibrations, respectively. In the case of 3 the absorption
at 2067 cmꢀ1 due to SCN is in accordance with those re-
ported in the literature for monodentate N-bound
pseudohalide groups [24,25] (Chart 1a). The trifluorom-
ethanesulfonate and perchlorate complexes 2 and 4 exhi-
bit absorptions which are not useful in distinguishing
between monodentate or ionic counterions. However,
on the basis of a previous report [8] and, in the case of
2, on the basis of the diffraction studies, a four-coordi-
nate ionic structure (Chart 1b) can be assigned to both
complexes.
3.3. X-ray diffraction study
The single crystal X-ray structure determination of
the thiocyanate 3 was carried out on a specimen ob-
tained from cyclohexylamine solution, a fortuitous
product from a crystallization directed towards the
acquisition of a mixed ligand CuSCN/dppe/N-base
complex. One molecule, devoid of crystallographic
symmetry, comprises the asymmetric unit of the struc-
ture. The results of the study are of considerable inter-
est, the first structural definition of a complex of the
form [(P,P0-dpex)M(P-dpex)X] (four-coordinate metal)
for M = Cu (Fig. 1; Table 1), previously only known
for the AgX/dppp (X = halide, CN) adducts. It is fur-
ther of interest in that the thiocyanate is now bound
to the metal atom (=Cu), whereas in AgSCN:dppp
(1:2) it remains ionic. The role of the solvent and
the denticity and bite of the ligand remain imponde-
rables in accessing the present complex – the P3MX
system has been defined for silver(I) with thiocyanate,
N-bound, [26]; the present, N-bound, is compatible
with the only example showing a similar environment
for copper(I) [27]. In the present, four-coordinate array,
In the 1H NMR spectra of 1–5 in CDCl3 (see Section
2), the signals due to the diphosphine ligands show dif-
ferent patterns with respect to those found for the free
donors, confirming the existence of complexes in solu-
tion. The bridging methylene resonances in 1–5 appear
as broad signals generally between 2.50 and 2.70 ppm

C. di Nicola et al. / Inorganica Chimica Acta 358 (2005) 4003–4008
4007
Table 2
Selected cation geometries, Cutfs: dppe (1:2)(:ꢀH2Oꢁ) (2ÆH2O)
Atoms
Parameter
˚
Distances (A)
Cu–P(1)
Cu–P(2)
Cu–P(3)
Cu–P(3)
2.295(1)
2.298(1)
2.294(1)
2.297(1)
Angles (ꢁ)
P(1)–Cu–P(2)
P(1)–Cu–P(4)
P(1)–Cu–P(3)
P(3)–Cu–P(4)
P(2)–Cu–P(3)
P(2)–Cu–P(4)
89.03(4)
128.19(4)
122.42(4)
88.36(4)
115.40(4)
116.02(4)
Torsion angles (ꢁ) (carbon atoms denoted by number only)
Cu–P(1)–10–20
P(1)–10–20–P(2)
10–20–P(2)–Cu
Cu–P(3)–30–40
P(3)–30–40–P(4)
30–40–P(4)–Cu
ꢀ39.0(3)
59.1(3)
ꢀ49.1(3)
ꢀ50.0(3)
50.6(4)
ꢀ25.3(3)
Fig. 1. Projection of CuSCN:dppe (1:2) (3).
Table 1
Selected molecular geometries of 3
Atoms
Parameter
2.2844(7)
˚
Distances (A)
Cu–P(1)
Cu–P(2)
Cu–P(3)
Cu–N
N–C
2.2952(7)
2.2686(7)
1.996(2)
1.151(3)
1.638(3)
C–S
Angles (ꢁ)
N–Cu–P(1)
N–Cu–P(2)
N–Cu–P(3)
Cu–N–C
P(1)–Cu–P(2)
P(1)–Cu–P(3)
P(2)–Cu–P(3)
N–C–S
115.90(7)
114.43(7)
98.09(6)
154.9(2)
90.14(2)
120.65(3)
119.11(3)
178.8(2)
Torsion angles (ꢁ) (carbon atoms denoted by number only)
P(2)–Cu–P(1)–1
Cu–P(1)–1–2
1–2–P(2)–Cu
2–P(2)–Cu–P(1)
Cu–P(3)–3–4
P(3)–3–4–P(4)
P(1)–1–2–P(2)
ꢀ18.58(8)
Fig. 2. The cation of [Cu(dppe)2](F3CSO3)(ꢀH2Oꢁ) (2ÆH2O).
45.4(2)
34.9(2)
ꢀ5.17(8)
ꢀ63.4(2)
ꢀ174.2(1)
ꢀ54.4(2)
The structure of the triflate adduct 2, modelled as a
monohydrate, Cutfs:dppe (1:2) (:ꢀH2Oꢁ), with the possi-
bility of the anion or solvent behaving as donors, is, in
the event, unꢀsurprising, being simply ionic [Cu(P-
dppe-P0)2]+(tfs )ÆꢀH2Oꢁ. The cation geometry is similar
to those previously established in the perchlorate, ni-
trate, trifluoroacetate, and hexafluorophosphate salts
[8–12], Cu–P spanning a very narrow range (Table 2),
Cu–P(1,2) are somewhat longer than Cu–P(3), in keep-
ing with their incorporation in the chelate, the difference
being less marked than in the AgX:dppp (1:2) arrays
(X = Cl, Br, I, CN) of [15].

4008
C. di Nicola et al. / Inorganica Chimica Acta 358 (2005) 4003–4008
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109897; CDB ꢀDAFLAXꢁ).
although the non-ꢀbiteꢁ P–Cu–P angles are diverse and
only poorly approximate 222-symmetry, despite the sim-
ilarity in torsion strings in the chelate rings, the confor-
mation of the latter differing appreciably from that of
the chelate in the thiocyanate (see Fig. 2).
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1411.
Acknowledgement
Support from the Australian Research Council, the
University of Camerino and Fondazione CARIMA is
gratefully acknowledged.
[16] M. Gimeno, P.G.. Jones, A. Laguna, C. Sarroca, J. Chem. Soc.,
Dalton Trans. (1995) 1473.
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