Influence of the phosphine arrangement on the reactivity of palladium(II) and platinum(II) polyphosphine complexes with copper(I) chloride

Article abstract of DOI:10.1016/j.ica.2005.03.018

The distorted square-planar complexes [Pd(PNHP)Cl]Cl (1) (PNHP = bis[2-(diphenylphosphino)ethyl]amine), [M(P₃)Cl]Cl [P₃ = bis[2-(diphenylphosphino)ethyl]phenylphosphine; M = Pd (2), Pt (3)] and [Pt(NP₃)Cl]Cl (5) (NP₃ = tris[2-(diphenylphosphino)ethyl] amine), coexisting in the later case with a square-pyramidal arrangement, react with one equivalent of CuCl to give the mononuclear heteroionic systems [M(L)Cl](CuCl₂) [L = PNHP, M = Pd (1a); L = P₃, M = Pd (2a), Pt (3a); L = NP₃, M = Pt (5a)]. The crystal structure of 3a confirms that Pt(II) retains the distorted square-planar geometry of 3 in the cation with P₃ acting as tridentate chelating ligand, the central P atom being trans to one chloride. The counter anion is a nearly linear dichlorocuprate(I) ion. However, the five-coordinate complexes [Pd(NP ₃)Cl]Cl (4), [M(PP₃)Cl]Cl (M = Pd (6), Pt (7); PP ₃ = tris[2-(diphenylphosphino)ethyl] phosphine) containing three fused five-membered chelate rings undergo a ring-opening by interaction with one (4, 6, 7) and two (6, 7) equivalents of CuCl with formation of neutral MCu(L)Cl₃ [L = NP₃, M = Pd (4a); L = PP₃, M = Pd (6a), Pt (7a)] and ionic [MCu(PP₃)Cl₂](CuCl ₂) [M = Pd (6b), Pt (7b)] compounds, respectively. The heteronuclear systems were shown by ³¹P NMR to have structures where the phosphines are acting as tridentate chelating ligands to M(II) and monodentate bridging to Cu(I). Further additions of CuCl to the neutral species 6a and 7a in a 1:1 ratio resulted in the achievement of the ionic complexes 6b and 7b with CuCl2- ions as counter anions. It was demonstrated that the formation of heterobimetallic or just mononuclear mixed salt complexes was clearly influenced by the polyphosphine arrangement with the tripodal ligands giving the former compounds. However, complexes [M(NP₃)Cl]Cl constitute one exception and the type of reaction undergone versus CuCl is a function of the d ⁸ metal centre.

Full text of DOI:10.1016/j.ica.2005.03.018

Inorganica Chimica Acta 358 (2005) 2575–2584
www.elsevier.com/locate/ica
Influence of the phosphine arrangement on the reactivity
of palladium(II) and platinum(II) polyphosphine complexes
with copper(I) chloride
´ ´
Damian Fernandez, M. Ines Garcıa-Seijo, Paloma Sevillano, Alfonso Castin˜eiras,
*
´
M. Esther Garcıa-Fernandez
´
´
´
Department of Inorganic Chemistry, University of Santiago de Compostela, Avda. de las Ciencias s/n, E-15782 Santiago de Compostela, Spain
Received 5 February 2004; accepted 6 March 2005
Available online 6 April 2005
Abstract
The distorted square-planar complexes [Pd(PNHP)Cl]Cl (1) (PNHP = bis[2-(diphenylphosphino)ethyl]amine), [M(P3)Cl]Cl
[P3 = bis[2-(diphenylphosphino)ethyl]phenylphosphine; M = Pd (2), Pt (3)] and [Pt(NP3)Cl]Cl (5) (NP3 = tris[2-(diphenylphosph-
ino)ethyl]amine), coexisting in the later case with a square-pyramidal arrangement, react with one equivalent of CuCl to give the
mononuclear heteroionic systems [M(L)Cl](CuCl2) [L = PNHP, M = Pd (1a); L = P3, M = Pd (2a), Pt (3a); L = NP3, M = Pt
(5a)]. The crystal structure of 3a confirms that Pt(II) retains the distorted square-planar geometry of 3 in the cation with P3 acting
as tridentate chelating ligand, the central P atom being trans to one chloride. The counter anion is a nearly linear dichlorocuprate(I)
ion. However, the five-coordinate complexes [Pd(NP3)Cl]Cl (4), [M(PP3)Cl]Cl (M = Pd (6), Pt (7); PP3 = tris[2-(diphenylphosph-
ino)ethyl] phosphine) containing three fused five-membered chelate rings undergo a ring-opening by interaction with one (4, 6,
7) and two (6, 7) equivalents of CuCl with formation of neutral MCu(L)Cl3 [L = NP3, M = Pd (4a); L = PP3, M = Pd (6a), Pt
(7a)] and ionic [MCu(PP3)Cl2](CuCl2) [M = Pd (6b), Pt (7b)] compounds, respectively. The heteronuclear systems were shown by
31P NMR to have structures where the phosphines are acting as tridentate chelating ligands to M(II) and monodentate bridging
to Cu(I). Further additions of CuCl to the neutral species 6a and 7a in a 1:1 ratio resulted in the achievement of the ionic complexes
ꢀ
6b and 7b with CuCl2 ions as counter anions. It was demonstrated that the formation of heterobimetallic or just mononuclear
mixed salt complexes was clearly influenced by the polyphosphine arrangement with the tripodal ligands giving the former com-
pounds. However, complexes [M(NP3)Cl]Cl constitute one exception and the type of reaction undergone versus CuCl is a function
of the d8 metal centre.
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: Pd(II) and Pt(II) complexes; Linear and tripodal polyphosphines; Reactions with CuCl; Heteronuclear systems; 31PNMR spectroscopy;
Crystallography of a dichlorocuprate(I)
1. Introduction
Homo- and heterobinuclear complexes containing
bridged and heterobridged halide, sulfide, dithiolato,
alkynyl, diphosphine, aminophosphine and other hybrid
*
Corresponding author. Tel.: +34 981 563100/14241; fax: +34 981
ligands were shown to play a prominent role as starting
materials in organometallic chemistry providing the
597525.
´ ´
E-mail address: qiegfq@usc.es (M.E. Garcıa-Fernandez).
0020-1693/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2005.03.018

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D. Fernandez et al. / Inorganica Chimica Acta 358 (2005) 2575–2584
2576
means for the study of cooperative bimetallic reactivity
and the achievement of materials with novel structures
and desirable properties [1–8]. Thus, the heterobimetal-
lic chloride-bridged d6–8 complexes [(PEt3)(g5-
C5Me5)M0(l-Cl)2Pt(C6F5)2] (M0 = Rh, Ir) react with
the alkynylating agents [M00(C„CR)]n (M00 = Cu, Ag)
with formation of novel heterotetrametallic d6–d10–d8
polyalkynyl compounds [(PEt3)Cp*M0(l-1kCa:g2-
metal–polyphosphine complexes [14]. This prompted
us to be interested in using precursors containing linear
or tripodal polyphosphines such as [M(L)Cl]Cl
(M = Pd,
Pt;
L = PNHP = bis[2-(diphenylphosph-
ino)ethyl]amine, P3, NP3, PP3), for reactions with CuCl.
The polyphosphine arrangement resulted to be decisive
in the formation of either mononuclear heteroionic or
heterodinuclear systems, the linear ligands affording
only the former ones.
C„CPh)2M00 (l-4kCa:g2-C„CPh)2Pt(C6F5)2], in which
2
two widely divergent bis(alkynyl)metal fragments (d6
and d8) are connected through d10 (Cu or Ag) metal ions
[4b]. However, similar reactions between [cis-
M(C6F5)2(thf)2] (M = Pd, Pt) and [{M0Cp*Cl(l-Cl)}2]
(M0 = Rh, Ir) involve a chloride transfer to yield the
2. Experimental
2.1. General procedures and instrumentation
mixed
salt
complexes
{Cp*M0(l-Cl)3M0Cp*}2
[{(C6F5)2M(l-Cl)}2]. On the other hand, the heterome-
tallic sulfide clusters [Cu4(dcpm)4(M#S4)](ClO4)2
containing a bulky phosphine ligand (dcpm = bis(dic-
yclohexylphosphino)methane) and obtained by reaction
Palladium chloride and potassium tetrachloroplati-
nate were purchased from Strem Chemicals, copper
chloride, tris[2-(diphenylphosphino)ethyl]phosphine
and bis[2-(diphenylphosphinoethyl)]phenylphosphine
of
[Cu2(dcpm)2(MeCN)2](ClO4)2
with
M#S4
2ꢀ
from Aldrich, sodium chloride from Panreac. Microa-
nalyses were performed on a Fisons Instrument EA
1108 CHNS-O. Fast atom bombardment (FAB) or li-
quid secondary-ion (L-SIMS) mass spectra were ob-
tained in a Micromass Autospec spectrometer using
nitrobenzylic alcohol as the matrix. Infrared spectra
were recorded at ambient temperature as KBr pellets
(4000–500 cmꢀ1) and Nujol mulls (500–100 cmꢀ1) on
a Mattson Cygnus 100 spectrophotometer. The bands
are reported as vs = very strong, s = strong, m = med-
ium, w = weak, sh = shoulder, br = broad. 31P {1H}
and 195Pt {1H} NMR spectra were recorded on a Bru-
ker AMX500 spectrometer at 202.46 and 107.52 MHz,
respectively. Chemical shifts (d) are reported in ppm
relative to external 85% H3PO4 (31P) and 1 M
(M# = Mo, W) are luminescent systems with a saddle
shaped {Cu4M#S4} core and unusual {Cu4P8Cu4}
metallomacrocycles [9]. Although bimetallic combina-
tions with diphosphine assembling ligands are relatively
common [5,8d,10], little work has been directed towards
the study of heteronuclear compounds containing
triphosphine or tetraphosphine ligands. One of these
reports describes the reaction of syn-[Pt2(l-
dpmp)2(xylNC)2](PF6)2 (dpmp = bis(diphenylphosphi-
nomethyl)phenylphosphine) with CuX (X = Cl, Br, I)
to give the heterotrinuclear complex [Pt2CuX(l-
dppm)2(xylNC)2](PF6)2 with a rhombic Pt2CuX struc-
ture. In contrast, the same reaction with CuI in the
presence of NH4PF6 or with [Cu(CH3CN)4](PF6) gives
a diplatinum (II) compound, [Pt2(l-dpmp)2-(xylNC)]
(PF6)2, that could be regarded as a product derived from
removal of one isocyanide molecule from the precursor
with the subsequent ring-closure process since the pre-
existent dangling phosphorus atom coordinates now to
Pt(II) [11].
Na2PtCl6
(
195Pt); s = singlet, d = doublet, t = triplet,
dt = doublet of triplets, dq = doublet of quartets,
br = broad signal, J = coupling constant in Hz. Con-
ductivities were measured at 25 ꢁC using 10ꢀ3 M solu-
tions in DMF or CH3CN on a WTW model LF-3
instrument.
In previous works, we demonstrated that the square-
planar complexes [M(P3)X]X (M = Pd, Pt; P3 = bis[2-
(diphenylphosphino)ethyl]phenylphosphine; X = Cl, Br,
I) undergo a ring-opening reaction upon addition of
Au(I) to give the heterobimetallic compounds
MAu(P3)X3 [M = Pd, X = Cl, Br, I; M = Pt, X = Cl,
Br] containing distorted square-planar M(II) and linear
Au(I) centres [12,13]. However, the reaction with AgCl
does not take place and with AgNO3 affords the nitrate
derivatives [M(P3)(ONO2)](NO3) [13]. The study of sim-
ilar reactions with Au(I) or Ag(I) for complexes contain-
ing tripodal polyphosphines such as [Pd(NP3)X]X (NP3
= tris[2-(diphenylphosphino)ethyl]amine) or [M(PP3)X]X
(PP3 = tris[2-(diphenylphosphino)ethyl] phosphine) (X =
Cl, Br, I) is very scarce [14,15] and less work has been
done to investigate reactions between Cu(I) and
2.2. Syntheses
2.2.1. Aminophosphines
NP3 and PNHP were prepared following the proce-
dures previously described [16,17].
2.2.2. Syntheses of 1–7
A solution of PNHP (1.0471 mmol), P3 (1.1220–
1.8700 mmol), NP3 (0.4594–0.6125 mmol) in CH2Cl2
(8–50 ml) or PP3 (0.2922–0.4160 mmol) in CHCl3 (25–
35 ml) was added dropwise to a solution of Na2PdCl4
[17] in MeOH (12 ml, 4) or H2O (15–25 ml, 1, 2, 6) or
to a solution of K2PtCl4 in H2O (15–35 ml, 3, 5, 7) in
1:1 stoichiometric ratio. The resultant mixtures were

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2577
stirred for l–24 h at room temperature and after that sol-
vents were partially removed in vacuo to leave a solution
(4) that was filtered or a suspension (1–3, 5–7). Et2O was
added to complete the precipitation and solids were
filtered off, washed with H2O and dried in vacuo. Com-
plexes 1–3 and 5 were recrystallised from CH2Cl2/n-hex-
ane (1–3) or MeOH/n-hexane (5) and then dried in
vacuo. 1 Æ H2O: Yield: 90%, white solid, m.p. 172 ꢁC.
C28H31NP2PdCl2O requires: C, 52.7; H, 4.9; N, 2.3.
Found: C, 52.4; H, 4.8; N, 2.2%. IR mmax/cmꢀ1 3436s
(N–H); 312s (Pd–Cl). MS (FAB): m/z 582 (M+ ꢀ Cl,
100%); 547 (M+ ꢀ 2Cl, 8%). K(DMF) = 22.8
ohmꢀ1 cm2 molꢀ1. (2): Yield: 68%, white solid, m.p.
210 ꢁC. C34H33P3PdCl2 requires: C, 57.3; H, 4.7. Found:
(Pd–Cl); 396m ma(Cu–Cl); 296w ms(Cu–Cl).IR d/cmꢀ1
109sh (CuCl2). MS (FAB): m/z 582 (M+ ꢀ Cu ꢀ 2Cl,
34%). K(CH3CN) = 67.1 ohmꢀ1 cm2 molꢀ1. 2a: Yield:
90%, yellow solid, m.p. 233 ꢁC. C34H33P3PdCuCl3 re-
quires: C, 50.3; H, 4.1. Found: C, 49.1; H, 3.9%. IR
m
max/cmꢀ1 317vs (Pd–Cl); 404s ma(Cu–Cl); 282m
ms(Cu–Cl). IR d/cmꢀ1 115s (CuCl2). MS (FAB): m/z
675 (M+ ꢀ Cu ꢀ 2Cl, 98%). K(DMF) = 80.8 ohmꢀ1
cm2 molꢀ1. 3a: Yield: 79%, yellow solid, m.p. > 250 ꢁC.
C34H33P3PtCuCl3 requires: C, 45.4; H, 3.7. Found: C,
44.9; H, 3.6%. IR mmax/cmꢀ1 320vs (Pt–Cl); 400s ma(Cu–
Cl); 282m ms(Cu–Cl). IR d/cmꢀ1 117s (CuCl2). MS
(FAB): m/z 765 (M+ ꢀ CuCl2, 100%). K(DMF) =
82.9 ohmꢀ1 cm2 molꢀ1. (4a) Æ 2H2O: Yield: 70%, yellow
solid, m.p. 250 ꢁC (dec.). C42H46NP3PdCuCl3O2 requires:
C, 52.2; H, 4.8; N, 1.4. Found: C, 52.1; H, 4.8; N, 1.1%. IR
C, 57.0; H, 4.9%. IR
m
max/cmꢀ1 318vs (Pd–Cl).
MS (FAB): m/z 675 (M+ ꢀ Cl, 100%). K(DMF) =
91.5 ohmꢀ1 cm2 molꢀ1. (3): Yield: >70%, white solid,
m.p. > 250 ꢁC. C34H33P3PtCl2 requires: C, 51.0; H, 4.1.
Found: C, 51.2; H, 4.3%. IR mmax/cmꢀ1 320vs (Pt–Cl).
MS (FAB): m/z 764 (M+ ꢀ Cl, 100%). K(DMF) =
82.9 ohmꢀ1 cm2 molꢀ1. (4) Æ 2H2O: Yield: 70%, orange
solid, m.p. 161 ꢁC (dec.). C42H46NP3PdCl2O2 requires:
C, 58.1; H, 5.4; N, 1.6. Found: C, 58.1; H, 5.8; N,
1.6%. IR mmax/cmꢀ1 300w (Pd–Cl). MS (FAB): m/z 794
m
max/cmꢀ1 337m (Pd–Cl); 255w (Cu–Cl). MS (FAB):
m/z 892 (M+ ꢀ Cl, 3%); 794 (M+ ꢀ Cu ꢀ 2Cl, 7%);
759 (M+ ꢀ Cu ꢀ 3Cl, 1%). K(CH3CN) = 35.6 ohmꢀ1
cm2 molꢀ1. (5a) Æ 4H2O: Yield: 73%, green solid, m.p.
205 ꢁC. C42H50NP3PtCuCl3O4 requires: C, 46.3; H, 4.6;
N, 1.3. Found: C, 46.4; H, 5.2; N, 1.3%. IR mmax/cmꢀ1
290s (Pt–Cl); 390vs ma(Cu–Cl); 290vs ms(Cu–Cl). IR
d/cmꢀ1 115sh (CuCl2). MS (FAB): m/z 884
(M+ ꢀ Cu ꢀ 2Cl, 55%); 848 (M+ ꢀ Cu ꢀ 3Cl, 11%).
K(DMF) = 54.7 ohmꢀ1 cm2 molꢀ1. (6a) Æ 2H2O: Yield:
90%, brown solid, m.p. 180 ꢁC. C42H46P4PdCuCl3O2
requires: C, 51.3; H, 4.7. Found: C, 51.8; H, 4.8%. IR
(M+ ꢀ Cl, 17%). K(CH3CN) = 139.2 ohmꢀ1 cm2 molꢀ1
.
(5) Æ 4H2O: Yield: 63%, orange solid, mp > 250 ꢁC.
C42H50NP3PtCl2O4 requires: C, 50.8; H, 5.1; N, 1.4.
Found: C, 50.1; H, 5.4; N, 1.4%. IR mmax/cmꢀ1 305sh
(Pt-Cl). MS (FAB): m/z 883 (M+ ꢀ Cl, 4%); 848
m
max/cmꢀ1 300vs, br (Pd–Cl); 285vs (Cu–Cl). MS
(M+ ꢀ 2Cl, 3%). K(DMF) = 39.8 ohmꢀ1 cm2 molꢀ1
.
(L-SIMS): m/z 909 (M+ ꢀ 2Cl, 5%); 874 (M+ ꢀ 3Cl, 1%)
811 (M+ ꢀ Cu ꢀ 2Cl, 56%). K(DMF) = 23.2 ohmꢀ1
cm2 molꢀ1. (7a) Æ 4H2O Æ Et2O: Yield: 85%, yellow solid,
m.p. 182 ꢁC. C46H60P4PtCuCl3O5 requires: C, 46.7; H,
5.1. Found: C, 46.3; H, 5.1%. IR mmax/cmꢀ1 310s, br
(Pt–Cl); 284vs, (Cu–Cl). MS (L-SIMS): m/z 998
(M+ ꢀ 2Cl, 6%); 900 (M+ ꢀ Cu ꢀ 2Cl, 75%).
K(DMF) = 26.7 ohmꢀ1 cm2 molꢀ1. (6b) Æ 4H2O: Yield:
94%, green solid, m.p. 148 ꢁC. C42H50P4PdCu2Cl4O2 re-
quires: C, 45.1; H, 4.5. Found: C, 44.8; H, 4.4%. IR
(6) Æ 4H2O: Yield: 92%, red solid, m.p. 260 ꢁC.
C42H50P4PdCl2O4 requires: C, 55.6; H, 5.6. Found: C,
55.0; H, 5.4%. IR mmax/cmꢀ1 284s (Pd–Cl). MS (L-
SIMS): m/z 811 (M+ ꢀ Cl, 56%); 776 (M+ ꢀ 2Cl, 2%).
K(DMF) = 77.1 ohmꢀ1 cm2 molꢀ1
. (7) Æ 2H2O: Yield:
85%, yellow solid, m.p. 281 ꢁC. C42H46P4PtCl2O2 re-
quires: C, 51.8; H, 4.7. Found: C, 51.4; H, 4.7%. IR
m
max/cmꢀ1 275s (Pt–Cl). MS (L-SIMS): m/z 900 (M+ ꢀ
Cl, 45%); 865 (M+ ꢀ 2Cl, 1%). K(DMF) = 72.1 ohmꢀ1
cm2 molꢀ1
.
m
max/cmꢀ1 310vs, br (Pd–Cl); 410m ma(Cu–Cl); 296s
ms(Cu–Cl). K(DMF) = 82.5 ohmꢀ1 cm2 molꢀ1
(7b) Æ
4H2O Æ 0.5CHCl3: Yield: 94%, green solid, m.p. 148 ꢁC.
.
2.2.3. Syntheses of 1a–7a and 6b–7b
To a solution of 1 Æ H2O (0.1886 mmol) in CH2Cl2
(20 ml), 2, 3, (6) Æ 4H2O and (7) Æ 2H2O (0.1250–
0.2273 mmol) in CHCl3 (15–40 ml), 4 Æ H2O and
(5) Æ 4H2O (0.1512–0.1731 mmol) in MeOH (15–20 ml),
CuCl was added, as a solid, in the appropriate stoichiom-
etric ratio. The resultant mixtures were stirred for 0.5–
24 h at room temperature and after that Et2O (1, 4–7) or
n-hexane (2, 3) was added to precipitate the solids. The
complexes were filtered off and dried in vacuo. Crystals
of 3a, suitable for X-ray diffraction, were obtained by
recrystallisation from acetone/Et2O. (1a) Æ H2O: Yield:
45%, green solid, m.p. 150 ꢁC (dec.). C28H31NP2PdCu-
Cl3O requires: C, 45.6; H, 4.3; N, 1.9. Found: C, 45.1;
H, 4.3; N, 1.8%. IR mmax/cmꢀ1 3446m, br (N–H); 314s
C42.5H50.5P4PdCu2Cl5.5O2 requires: C, 45.1; H, 4.5.
Found: C, 44.8; H, 4.4%. IR mmax/cmꢀ1 310m, br (Pt–
Cl); 296s ms(Cu–Cl). IR d/cmꢀ1 110vs (CuCl2).
K(DMF) = 75.8 ohmꢀ1 cm2 molꢀ1
.
2.3. Titrations of 4 and 6a with CuCl
To a solution of complex 4 in CD3OD or 6a in
CDCl3, CuCl was added as a solid, reaching different
stoichiometric ratios. The mixtures were stirred for
12 h, then DMSO-d6 was added to solve the new com-
plex formed and the 31P{1H} NMR spectra were re-
corded. The most significant signals are given in Table 1.

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D. Fernandez et al. / Inorganica Chimica Acta 358 (2005) 2575–2584
2578
Table 1
31P{1H} NMR data (r.t.) for complexes 1–7, 1a–7a, 6b and 7b and for reaction of 4 and 6a with CuCl
Compound
dPa
1J(31P,195Pt)
Solvent
1
34.6 s
109.4 t [1P], 44.3 d [2P]
83.3 s [1P], 39.8 [2P]
CDCl3
CDCl3
CDCl3
2b
3
3010, 2490
2738, 3317
2505, 2590
4
37.7 br [1P], 34.1 br [1P], 23.6 s [1P]
33.9 br [2P], ꢀ2.5 br [1P]
134.1 s [1P], 29.5 s [3P]
118.3 s [1P], 25.0 s [3P]
37.0 br
CD3OD
CD3OD
CDCl3
5
6
7c
1a
CDCl3
CDCl3
2ab
108.5 t [1P], 44.5 d [2P]
83.4 s [1P], 39.7 s [2P]
CDCl3
CDCl3
3ac
4 + 1 eq. CuCl
3046, 2472
35.7 br, ꢀ6.1br, ꢀ13.2 br
36.9 br [2P], ꢀ11.1 br [1P]
34.9 br [2P], ꢀ0.9 s [1P]
113.5 s [1P], 43.0 br [3P]
88.3 br [1P], 39.6 s [2P]*, 31.0 br [1P]
113.9 d [1P], 44.0 s [2P], 29.0 br [1P]
121.5 s [1P], 49.9 s [2P], 33.7 br [1P]
95.3 d [1P], 46.4 s [2P], 33.5 br [1P]
CD3OD/DMSO-d6
DMSO-d6
CD3OD
CDCl3
4a
5a
2718, 3289
2496*
6a
7a
CDCl3
6a + 1 eq. CuClb
CDCl3/DMSO-d6
DMSO-d6
DMSO-d6
6b
7bb,c
2957, 2507
a
Relative intensities: [nP].
2J(31P,31P): 9.4 Hz (2) (d,t); 9.5 Hz (2a) (d,t); 38.0 Hz (6a + 1 eq. CuCl) (d); 42.0 Hz (7b) (d).
b
c
Compound (solvent), d195Pt/1J(31P,195Pt): 7 (CDCl3), ꢀ4373dq/2590 Hz. 3a (CDCl3), ꢀ4875dt/3046, 2472 Hz. 7b (DMSO-d6), ꢀ4830dt/2947,
2520 Hz.
2.4. X-ray structure determination
respectively) that are lower than those expected in this
solvent for 1:1 electrolytes (65–90 ohmꢀ1 cm2 molꢀ1
)
A yellow crystal of 3a was mounted on a glass fibre
and used for data collection. Cell constants and an ori-
entation matrix for data collection were obtained by
least-squares refinement of the diffraction data from 25
reflections in the range of 10.497ꢁ < h < 18.002ꢁ in a EN-
RAF-NONIUS MACH 3 automatic diffractometer [18].
Data were collected at 293 K using Mo Ka radiation
[25], suggesting the presence of mixtures of species [16]
or ionic pairs formation [17].
The FAB (1–5) and L-SIMS (6–7) mass spectra show
in all cases peaks due to MLCl (L = polyphosphine li-
gand) fragments by loss of the Clꢀ counter anion. For
the NP3 derivatives 4 and 5, peaks assigned to oxida-
tions of dangling P atoms of the ligand, M(N(PO)P2)Cl
and M(N(PO)2P)Cl, were also observed.
˚
(k = 0.71073 A) and the x scan technique and corrected
for Lorentz and polarisation effects [19] and semi-
empirical absorption correction (w scan) was made [20].
The structure was solved by direct methods [21],
which revealed the position of all non-hydrogen atoms,
and refined on F2 by a full-matrix least-squares proce-
dure using anisotropic displacement parameters [22].
The hydrogen atoms were located in their calculated
The 31P{1H} NMR spectrum of 1 (Table 1) shows
one single resonance in consistence with PNHP acting
as tridentate chelating ligand in a distorted square-
planar arrangement to Pd(II) with the two equivalent
P atoms mutually trans and the N atom trans to Cl.
Likewise, the spectra for complexes 2 and 3 exhibit
two resonances in a 1:2 integration ratio and support
the formation of square-planar compounds where P3
coordinates to M(II) through the three P atoms giving
rise to two fused five-membered chelate rings. This is
˚
positions (C–H 0.93–0.97 A) and refined using a riding
model. Atomic scattering factors from International Ta-
bles for X-ray Crystallography [23]. Molecular graphics
from ORTEP-3 for Windows [24].
1
in agreement with J(31P, 195Pt) couplings of 3010 and
2490 Hz for 3 typical of P trans to Cl and P trans to
P, respectively [26,27].
3. Results and discussion
The 31P{1H} NMR spectra for complexes 4 and 5,
containing the tripodal ligand NP3, consist of three
and two signals, respectively. The two signals at lower
field for 4 exhibit a double integration ratio compared
to the resonance at d 23.6 and can be assigned to P
atoms mutually trans. The broadening of these signals,
corresponding to a 1:1 electrolyte, suggests the existence
of an equilibrium between two five-coordinate species
[15,28] with distorted square-pyramidal geometry at
3.1. Characterisation of complexes 1–7
The conductivity measurements for 10ꢀ3 M DMF
solutions of complexes 2–3, 6 and 7 and a CH3CN
solution of 4 reveal that these systems behave as 1:1 elec-
trolytes. However, complexes 1 and 5 exhibit molar con-
ductivities in DMF (22.8 and 39.8 ohmꢀ1 cm2 molꢀ1
,

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D. Fernandez et al. / Inorganica Chimica Acta 358 (2005) 2575–2584
2579
Pd(II). The N and the P atom with the resonance at
higher field can be alternating the trans to Cl and apical
positions with all four donor atoms forming three fused
and the three P atoms of the ligand forming three fused
eight-membered chelate rings, and a five-coordinate spe-
cies where the nitrogen is also coordinated to platinum
(Scheme 1).
1
five-membered rings (Scheme 1). The J(31P,195Pt) cou-
pling constants of 2738 and 3317 Hz obtained from
the two broad peaks (in a 2:1 integration ratio) for 5
are in accordance with the presence of P trans to P
and P trans to Cl, respectively [16]. The broadening de-
creased as the spectrum was recorded in CD3OD above
40 ꢁC, leading to a doublet and a triplet with 2J(31P,31P)
coupling constants of 20 Hz. The broadening of the sig-
nals below and at ambient temperature points to the
existence of an equilibrium between a four-coordinate
species whereby the metal is coordinated to one chloride
Complexes 6 and 7 containing the tripodal ligand
PP3 show a 31P{1H} NMR spectrum with two reso-
nances in a 1:3 integration ratio (Table 1) supporting
the formation of five-coordinate trigonal-bipyramidal
systems [29,30] where the central P atom is in apical po-
sition trans to Cl and the three terminal P atoms are in
the equatorial plane of the bipyramid (Scheme 1). This
1
arrangement was confirmed for 7 from the J(31P,195Pt)
coupling values of 2505 and 2590 Hz characteristic of P
trans to Cl and P in the equatorial plane, respectively.
Likewise, the 195Pt{1H} NMR spectrum of 7 showed,
as expected, an overlapped doublet of quartets at d
ꢀ4373 from which the 1J(31P,195Pt) coupling of
2590 Hz was obtained.
P
M
P
P
M
P
CuCl
A
Cl Cl
A
Cl
(CuCl2)
The near far infrared spectrum of 1 showed a band at
3436 cmꢀ1 assignable to the N–H vibration and shifted
to higher energy compared to the band observed at
3300 cmꢀ1 for the free amine, as a result of the complex-
ation [17,31].
A = NH : M = Pd (1)
A = PPh : M = Pd (2), Pt (3) A = PPh : M = Pd (2a), Pt (3a)
A = NH : M = Pd (1a)
N
[Pt(NP3)Cl](CuCl2) (5a)
P
P
Cl
Pt
The far infrared spectra for 1–7 exhibit in all cases
one band assigned to one terminal M–Cl bond in agree-
ment with the other characterisation data.
CuCl
Cl
P
M = Pt (5)
P
N
3.2. Formation of mononuclear monocationic complexes
ꢀ
P
Cl
P
P
Cl
with CuCl2 as counter anion
Pd
P
N
Cu
Cl
M
Cl
Cl
P
The reaction of complexes 1–3 (containing linear li-
gands) and 5 (containing the tripodal ligand NP3) with
CuCl occurs without any chelate ringꢀ-opening giving
compounds 1a–3a and 5a where CuCl2 is the counter
anion.
Complexes 2a and 3a were also obtained in lower
yields (47% and 41% versus 90% and 79%) by interac-
tion between the dinuclear complex, Cu2(l-P3)2Cl2 [32]
and MCl2 (M = Pd, Pt) in CHCl3 using the same
Cu:M ratio (Eq. (1)).
CuCl
M = Pd (4)
A = N: M = Pd (4a)
P
P
P
P
N
P
Cl
Cl
M
P
A
Cu
Pd
Cl
Cl
Cl
A = P: M = Pd (6a), Pt (7a)
CuCl
P
CuCl
P
P
Cl
M
Cl
P
P
P
Cu2ðl-P3Þ Cl2 þ 2MCl2 ! 2½MðP3ÞClꢁðCuCl2Þ
ð1Þ
2 CuCl
2
Cl
M
P
P
(CuCl2)
Cu
Cl
2a; 3a
M = Pd (6), Pt (7)
The P3 derivatives 2a and 3a behave as 1:1 electrolytes in
10ꢀ3 M DMF solutions. However, 10ꢀ3 M CH3CN
solutions of the PNHP derivative 1a are not conductors
in consistence with ion pairs formation [17].
The FAB mass spectra for 1a–3a and 5a show peaks
assignable in all cases to MLCl (M = Pd, Pt, L = PNHP,
P3, NP3) fragments.
The 31P{1H} NMR spectrum of 1a in CDCl3 shows
one resonance at d 37.0 slightly shifted to lower field
compared to 1. This resonance is assigned to the two
equivalent phosphorus of the tridentate ligand mutually
trans. For 2a and 3a, the spectra show two signals
with integration ratio 1:2 from lower to higher field
M = Pd (6b), Pt (7b)
: A = NH (PNHP), PPh (P3)
P
A
P
PNHP = (Ph2PCH2CH2)2NH, P3 = (Ph2PCH2CH2)2PPh
P
P
: A = N (NP3), P (PP3)
P
A
NP3 = N(Ph2PCH2CH2)3, PP3 = P(Ph2PCH2CH2)3
Scheme 1. Reactions with CuCl of the ionic complexes 1–3, 5 to give
the dichlorocuprate(I) derivatives 1a–3a, 5a and of the ionic precursors
4, 6–7 to afford the neutral and ionic systems 4a, 6a–7a and 6b–7b,
respectively.

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D. Fernandez et al. / Inorganica Chimica Acta 358 (2005) 2575–2584
2580
attributed to P trans to Cl and P mutually trans, respec-
1
tively. The J(31P, 195Pt) couplings for 3a of 3046 and
2472 Hz confirm a retention of the distorted square-pla-
nar arrangement of the precursor and are coincident
with the couplings obtained from the 195Pt{1H} NMR
spectrum that consists of a doublet of triplets centred
at d ꢀ4875.
The 31P{1H} NMR spectrum of 5a shows two signals
at d 34.9 and ꢀ0.9 in a 2:1 integration ratio, respectively,
the 1J(31P,195Pt) coupling constants of 2718 and
3289 Hz being characteristic of P trans to P and P trans
to Cl, respectively, as also found for the precursor.
Asoccurredfor1,complex1ashowsaN–Hvibrationin
the near infrared spectrum at higher energy (3446 cmꢀ1
)
than the stretching mode found for the free amine
(3300 cmꢀ1) as a consequence of complexation [16].
The far infrared spectra of 1a–3a and 5a are consis-
tent with the presence of terminal M–Cl bonds and
ꢀ
CuCl2 anions. The bands at 396, 404, 400 and
Fig. 1. Crystal structure of 3a.
390 cmꢀ1 correspond to the asymmetric m(Cu–X)
stretching mode of the bent ClCuCl units and the bands
at 296 and 282 cmꢀ1 for (1a, 5a) and (2a, 3a), respec-
tively, were due to the symmetric m(Cu–X) mode. In
addition, the bands at 109, 115 and 117 cmꢀ1 for 1a,
(2a, 5a) and 3a, respectively, were attributed to the
d(CuCl2) bending vibration [33].
It should be noted that the reactivity of complexes 1–3
and 5 with monovalent group 11 cations is influenced by
the polyphosphine ligand and both the d8 and d10 metal
ions. Thus, while the reaction with CuCl, here reported,
gives in all four cases the dichlorocuprate(I) derivatives
and the reaction of AgNO3 with 1–3 leads to the forma-
tion of the nitrate compounds, [M(L)(ONO2)](NO3)
(L = PNHP, M = Pd; L = P3, M = Pd, Pt) [13,17], the
addition of AgNO3 to complex 5 does not allow the isola-
tion of any complex [15b]. On the other hand, Au(tdg)Cl
(tdg = thiodiglycol) produces abstraction of PNHP from
1 giving the dinuclear compound Au2(PNHP)Cl2 [17] and
reacts with 2–3 via a ring-opening process with formation
of the heterobimetallic systems MAu(P3)Cl3 [12]. No
heterobimetallic compound was isolated by interaction
of 5 with Au(tdg)Cl [15a].
Table 2
Summary of crystal parameters, data collection and refinement for 3a
Complex
3a
Empirical formula
Formula weight
Temperature (K)
C
899.49
34H33Cl3CuP3Pt
293(2)
0.71073
˚
Wavelength (A)
Crystal size (mm)
Colour/habit
Crystal system
0.20 · 0.20 · 0.20
yellow/prisms
monoclinic
P21/n
Space group
˚
a (A)
˚
10.1244(9)
20.1633(15)
16.6257(11)
90
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
93.782(6)
90
3
˚
Volume (A )
3386.6(5)
4
1.764
Z
Calculated density (Mg/m3)
Absorption coefficient (mmꢀ1
F(000)
)
5.156
1760
h range for data collection (ꢁ)
Index ranges
2.25–26.29
ꢀ12 6 h 6 12,
0 6 k 6 25,
0 6 l 6 20
7112
3.3. Crystallography of 3a
Reflections collected
Independent reflections
Maximum and minimum transmission
Data/restraints/parameters
Goodness of fit on F2
6875 [Rint = 0.0335]
0.985 and 0.876
6875/0/ 379
0.984
Recrystallisation of 3a in acetone/ether solutions
afforded single crystals of the entitled compound.
A perspective view of the molecular structure and
numbering scheme is shown in Fig. 1. A summary of
crystal parameters, data collection and refinement for
this crystal structure is given in Table 2 and selected
bond lengths and angles are listed in Table 3.
Final R indices
R1 = 0.0316,
w2R = 0.0606
0.928 and ꢀ0.840
ꢀ3
˚
Largest differential peak and hole (e A
)
The complex consists of a monocation with a dis-
torted square-planar geometry for platinum and a
dichlorocuprate(I) anion with a slightly distorted linear
ClCuCl arrangement.
The Pt–P bond lengths in the monocation of 2.320
˚
(P1), 2.207 (P2) and 2.310 (P3) A are in the expected
range and almost coincident with the same distances
for the precursor complex 3 [12], with the Pt–P(2) bond

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D. Fernandez et al. / Inorganica Chimica Acta 358 (2005) 2575–2584
2581
Table 3
Fig. 2 shows the titration of 4 with CuCl followed by
31P{1H} NMR. The addition of one equivalent of CuCl
produces a slight shift to higher field of the resonance at
d 37.7 and the disappearance of the signals at d 34.1 and
23.6 of the precursor (Fig. 2(a)). The resultant spectrum
(Fig. 2(b)) exhibits three resonances at d 35.7, ꢀ6.1 and
ꢀ13.2 pointing to the formation of two isomers for 4a.
The most intense resonance at lower field can be as-
signed to P atoms mutually trans bound to Pd(II) in
two environments with the ligand adopting the same
coordination mode, and the two broad signals at higher
field can be attributed to P atoms bound to Cu(I) that
achieves two different coordination numbers. The
31P{1H} NMR spectrum for solutions of 4a in
DMSO-d6 shows two broad resonances at d 36.9 and
ꢀ11.1 with the signal at higher field, due to P bound
to Cu(I), including the two signals found in the titra-
tion. Addition of a second equivalent of CuCl to 4 does
not produce any modification (Fig. 2(c)). Since solu-
tions of 4a in CH3CN behave as non-conductors, two
neutral structures are proposed. One contains trigonal-
bipyramidal (Cl2PdNP2) and linear (PCuCl) arrange-
ments and the other distorted square-planar (ClPdNP2)
and trigonal planar (PCuCl2) geometries for Pd(II) and
Cu(I), respectively (Scheme 1). Thus, one of the three
fused five-membered rings of 4 is opened by interaction
with CuCl, the phosphine acting as tridentate chelating
for Pd(II) and monodentate bridging ligand for Cu(I).
On the basis of the broadening of the peaks, another
neutral form with NP3 acting as bidentate ligand to pal-
ladium (Cl2PdNP) and copper (P2CuCl) should not be
excluded.
The presence of a peak in the FAB mass spectrum of
4a due to PdCu(NP3)Cl2 confirms the formation of het-
eronuclear species. Furthermore, another peak with
0.5% abundance was observed at m/e = 1819 attribut-
able to a Pd2Cu2(NP3)2Cl5 fragment. This coexistence
in some extent of heterodinuclear and heterotetranu-
clear structures was also observed for the analogous sys-
tem PdAg(NP3)Cl3 [15b].
The two bands at 337 and 255 cmꢀ1 found in the far
infrared spectrum of 4a are consistent with the existence
of terminal Pd–Cl and Cu–Cl bonds, respectively.
The trigonal-bipyramidal arrangements for M(II) in 6
and 7 change to distorted square-planar in complexes 6a
and 7a upon reaction with one equivalent of CuCl. The
resultant compounds behave as non-conductors in
10ꢀ3 M DMF solutions showing peaks in their L-SIMS
mass spectra due to MCu(PP3)Cl and M2Cu2(PP3)2Cl5
[m/e = 1853 (M = Pd, 1%), 2031 (M = Pt, 1%)] frag-
ments. The 31P{1H} NMR spectra show two and three
resonances for 6a (Fig. 3(a)) and 7a, respectively, with
the broad signal at higher field for 6a (d 43.0) including
the two signals (d 39.6, 31.0) found for 7a. The peak of
7a at lower field was assigned to the central P atom
trans to Cl, the resonance in the middle to two P atoms
˚
Selected distances (A) and angles (ꢁ) for 3a
Complex
3a
Pt(1)–P(1)
Pt(1)–P(2)
2.320(2)
2.207(2)
2.310(2)
2.349(2)
2.103(2)
2.091(2)
Pt(1)–P(3)
Pt(1)–Cl(1)
Cu(1)–Cl(11)
Cu(1)–Cl(12)
P(1)–Pt(1)–P(2)
P(1)–Pt(1)–P(3)
P(2)–Pt(1)–P(3)
P(1)–Pt(1)–Cl(1)
P(2)–Pt(1)–Cl(1)
P(3)–Pt(1)–Cl(1)
Cl(11)–Cu(1)–Cl(12)
84.33(5)
169.39(5)
85.07(5)
97.64(5)
176.81(5)
92.93(5)
170.43(9)
being shorter than the Pt–Pterminal due to the double che-
˚
late effect. The Pt–Cl distance of 2.349 A is within the
expected values for a terminal bond. The PPtP angles,
85.07ꢁ, 84.3ꢁ, and PPtCl, 176.81ꢁ, 169.39ꢁ, 97.64ꢁ, and
92.93ꢁ, confirm the distorted square-planar geometry
at Pt(II). The coordination sphere for Pt(1) is tetrahe-
drally distorted from planar arrangement, with the two
mutually trans P atoms [P(1) and P(3)] on one side
(0.017 and 0.018 A) of the least-squares plane defined
by [P(1)P(2)P(3)Cl(1)] and with the central phosphorus
˚
and the chlorine (0.019 and 0.015 A) atoms on the oppo-
˚
˚
site side. The platinum atom was deviated 0.032 A from
the least-squares plane and to the same side as the phos-
phorus P(1) and P(3).
There were not found unusual inter or intracationic
ꢀ
˚
contacts. The CuCl2 anions show CuCl bond lengths
of 2.091 and 2.103 A shorter than the same distances
for other chlorocuprates(I) suꢀch as [CuCl3]2ꢀ (av.
˚
2.22 A) [34] and [Cu(PPh3)Cl2] (av. 2.24 A) [33] or
˚
˚
for the neutral compound [Cu(PPh3)2Cl] (2.21 A) [35].
The ClCuCl angle of 170.4ꢁ indicates a distortion (about
10ꢁ) from the ideal linear geometry. Concerning interan-
ionic interactions, there is a Cu–Cl distance of 3.317 A
˚
that inꢀvolves Cu(1) and the chlorine atom of an adjacent
CuCl2 anion. This produces an intermetallic separation
˚
˚
of 3.853 A which is 0.425 A longer than the Cuꢂ ꢂ ꢂCu dis-
tance of 3.428 A found in [Cu2(PPh3)2I4]2ꢀ, where two
˚
three-coordinate metal centres are bridged by two iodide
anions [33]. There are not unusual cation–anion interac-
tions with a separation between Pt(1) and Cu(1) of
˚
6.136 A.
3.4. Neutral heterobimetallic complexes obtained by
ring-opening reaction
The precursors containing tripodal polyphosphine li-
gands [Pd(NP3)Cl]Cl (4) and [M(PP3)Cl]Cl [M = Pd (6),
Pt (7)] react with one equivalent of CuCl to give the
heterobimetallic systems PdCu(NP3)Cl3 (4a) and
MCu(PP3)Cl3 [M = Pd (6a), Pt (7a)].

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D. Fernandez et al. / Inorganica Chimica Acta 358 (2005) 2575–2584
2582
Fig. 2. 31P{1H} NMR spectra in CD3OD/DMSO-d6 of (a) complex 4, (b) 4 + 1 mol eq. of CuCl affording complex 4a and (c) 4a + 1 mol eq. of CuCl.
mutually trans and the signal at higher field to one P
atom bound to one CuCl2 moiety. The 1J(31P,195Pt)
coupling constant of 2496 Hz obtained from the reso-
nance at d 39.6 confirms the presence of P trans to P.
These data point to the formation of complexes contain-
ing distorted square-planar M(II) and trigonal planar
Cu(I) centres as it was proposed for one of the isomers
of 4a (Scheme 1).
Fig. 3. 31P{1H} NMR spectra for: (a) PdCu(PP3)Cl3 (6a in CDCl3), (b) [PdCu(PP3)Cl2](CuCl2) (6b in DMSO-d6), (c) [PtCu(PP3)Cl2](CuCl2) (7b in
DMSO-d6). (d) 195Pt{1H} NMR spectrum for 7b in DMSO-d6.

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D. Fernandez et al. / Inorganica Chimica Acta 358 (2005) 2575–2584
2583
The bands in the far infrared spectrum at 300, 285
and 310, 284 cmꢀ1 for 6a and 7a were attributed to ter-
minal M–Cl and Cu–Cl bonds, respectively, with the
broadening of the vibration at higher energy suggesting
the inclusion of m(M–Cl) and m(Cu–Cl).
It should be noted that the precursors 4, 6 and 7, con-
taining tripodal ligands, form heterobimetallic com-
pounds not only by reaction with CuCl but also with
Au(tdg)Cl (MAu(NP3)Cl3, [MAu(PP3)Cl2]Cl), AgCl or
AgNO3 [15].
It should be noted that while excess CuCl and AgCl
[15b] only produce a ring-opening from the precursors
4, 6 and 7 to give compounds MM0(L)Cl3 [L = NP3,
M = Pd, M0 = Cu, Ag; L = PP3, M = Pd, Pt, M0 = Cu,
Ag] and [MCu(PP3)Cl2](CuCl2) (M = Pd, Pt), the addi-
tion of Au(tdg)Cl to the heterobimetallic systems
[MAu(PP3)Cl2]Cl (M = Pd, Pt) results in a second
ring-opening with formation of MAu2(PP3)Cl4 [15a].
4. Conclusions
3.5. Formation of monocationic heterobimetallic
ꢀ
complexes with CuCl2 as counter anion
CuCl reacts with distorted square-planar complexes
containing linear polyphosphines of the type [M(L)Cl]Cl
(L = PNHP, M = Pd; L = P3, M = Pd, Pt) to give the
corresponding dichlorocuprates(I). The crystal structure
of [Pt(P3)Cl](CuCl2) consists of monocations, where
Pt(II) retaiꢀns the distorted square-planar arrangement,
and CuCl2 anions with a certain distortion from the
linear geometry. However, the reaction of [M(NP3)Cl]Cl
with CuCl affords a heterobimetallic complex when
M = Pd and the dichlorocuprate(I) derivative when
M = Pt. On the other hand, the trigonal-bipyramidal
complexes [M(PP3)Cl]Cl (M = Pd, Pt) containing a tri-
podal tetraphosphine react with one and two equiva-
lents of CuCl to give heterobimetallic neutral
MCu(PP3)Cl3 and ionic [MCu(PP3)Cl2](CuCl2) com-
pounds, respectively, via a ring-opening process.
When complexes 6 and 7 react with two equivalents
of CuCl, the heterobimetallic monocationic compounds
6b and 7b, respectively, containing one CuCl2 counter
ꢀ
anion were formed. These compounds were also affor-
ded by interaction of 6a and 7a with one equivalent of
CuCl, demonstrating that only the first equivalent of
CuCl added to 6 and 7 is involved in a ring-opening pro-
cess with the second one changing the ionicity of the
resultant heterobimetallic systems. Indeed, the molar
conductivities for 10ꢀ3 M DMF solutions of 6b and 7b
reveal an ionogenic behaviour corresponding to 1:1 elec-
trolytes, while compounds 6a and 7a were shown to be
non-conductors in the same solvent (vide supra).
The L-SIMS mass spectra for both complexes show a
peak with 100% abundance attributed to M(P(PO)P2)Cl
fragments, which is consistent with the loss of the CuCl
moiety from the cations [MCu(PP3)Cl2]+ and oxidation
of the dangling phosphorus. No peak assigned to het-
erotetrametallic species (as observed for 6a and 7a)
was detected now.
5. Supplementary material
A complete set of X-ray crystallographic structural
studies for complex 3a (CCDC No. 230211) is available
at the Cambridge Crystallographic Data Centre, 12 Un-
ion Road, Cambridge CB2 1EZ, UK (fax: +44 1223 336
033; e-mail: deposit@ccdc.cam.ac.uk) on request, quot-
ing the deposition number.
The 31P{1H} NMR spectra show three signals [Fig.
3(b) (6b), Fig. 3(c) (7b)] with a 1:2:1 integration ratio
supporting the presence of two types of P atoms bound
to M(II) and one third bound to Cu(I) (Scheme 1). The
1
signals at lower field for 7b allow the J(31P,195Pt) cou-
plings of 2957 and 2507 Hz in accordance with P trans to
Cl and P trans to P, respectively. Similar coupling con-
stants were obtained from the 195Pt{1H} NMR spec-
trum in DMSO-d6, which consisted of an overlapped
doublet of triplets at ꢀ4830 (Fig. 2d) corresponding to
a distorted square-planar arrangement to Pt(II), ClPtP3
[12]. As also observed for [PtAu(PP3)Cl2]Cl [15a], this
resonance appears higher field shifted compared to the
overlapped doublet of quartets at d ꢀ4373 (CDCl3)
found for the trigonal-bipyramidal precursor 7 [30].
The broad bands in the far infrared spectra at
310 cmꢀ1 for 6b and 7b are consistent with the presence
of terminal M–Cl and Cu–Cl bonds in the cationic com-
plexes. On the other hand, the appearance of vibrations
assigned to copper-chloride stretching (6b, 7b) and
bending (7b) modes evidences the existence of dichloro
cuprate(I) anions [36].
Acknowledgements
We thank Xunta de Galicia for financial support.
Crystallographic data for complex 3a were measured
at the Unidade de Raios X, RIAIDT, University of San-
tiago de Compostela, Spain.
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