Synthesis, reactivity and comparative structural studies on copper(I) and gold(I) halo complexes with tripodal polyphosphines in 1:1 metal to ligand ratio. The X-ray crystal structures of three mononuclear neutral compounds

Article abstract of DOI:10.1016/S0020-1693(03)00253-6

Cu(I) and Au(I) halides interact with equimolecular amounts of tripodal polyphosphines as CH₃C(CH₂PPh₂) ₃(CP₃) in CHCl₃, N(CH₂CH ₂PPh₂)₃(NP₃) in CH ₂Cl₂ or CH₂Cl₂-S (S=MeOH, Et ₂O) and P(CH₂CH₂PPh₂)₃ (PP₃) in CH₂Cl₂ to form Cu(CP₃)X [X=Br (1), I (2)], [Au₃(CP₃)₂Cl₂]Cl (3), [Au₃(CP₃)₃X]X₂ [X=Br (4), I (5)], Cu(NP₃)X [X=Cl (6), Br (7), I (8)], [Au₂(NP ₃)₂]X₂ [X=Cl (9), Br (10)], Au(NP ₃)I (11), [Cu₂(PP₃)₂X]X [X=Cl (12), Br (13)] and [Au₂(PP₃)₂]X₂ [X=Br (14), I (15)]. Complexes 1, 7 and 11 were shown by X-ray diffraction to consist of neutral monomers with distorted tetrahedral geometry around the metal and the phosphine acting as tridentate chelating ligand. The mass spectra, conductivity measurements and ³¹P{¹H} NMR studies for 9 and 10 are indicative of a coexistence with mononuclear forms. Complexes 3, 9 and 14 were also achieved in solution by addition of the appropriate polyphosphine to the compounds Au₃(CP₃)Cl₃ (3a), Au₃(NP₃)Cl₃ (9a) and Au ₄(PP₃)Br₄ (14a), respectively, involving ring-closure reactions. Likewise, crystals of 1 were obtained both from solutions of this compound in CH₂Cl₂-EtOH and from solutions in CHCl₃ of (1a)·2.5Et₂O (1a=Cu ₃(CP₃)Br₃). Further additions of the appropriate polyphosphine to 9 and 14 give complexes with new "MP ₄" environments and dangling phosphorus that for 14 involve ring-opening processes. By reaction of 3 with CP₃ the complex [Au₃(CP₃)₃Cl]Cl₂, isostructural with 4 and 5, is afforded in solution. The reaction of Cu(CP₃)Cl (I) with CP₃ followed by ³¹P{¹H} NMR seems to occur with retention in part of the starting CuP₃ core and formation of other species containing linear arrangements for Cu(I). No reaction was observed between 6 or 13 and NP₃ or PP₃, respectively.

Full text of DOI:10.1016/S0020-1693(03)00253-6

Inorganica Chimica Acta 353 (2003) 206ꢀ216
/
www.elsevier.com/locate/ica
Synthesis, reactivity and comparative structural studies on copper(I)
and gold(I) halo complexes with tripodal polyphosphines in 1:1 metal
to ligand ratio. The X-ray crystal structures of three mononuclear
neutral compounds
M. Ine´s Garc´ıa-Seijo a, Paloma Sevillano a, Robert O. Gould b, Damia´n Ferna´ndez-
Anca a, M. Esther Garc´ıa-Ferna´ndez a,*
a Department of Inorganic Chemistry, University of Santiago de Compostela, Avda. de las Ciencias, s/n. E-15782 Santiago de Compostela, Spain
b Department of Chemistry, The University of Edinburgh, King’s Buildings, West Mains Road, Edinburgh EH9 3JJ, UK
Received 9 December 2002; accepted 5 April 2003
Abstract
Cu(I) and Au(I) halides interact with equimolecular amounts of tripodal polyphosphines as CH3C(CH2PPh2)3(CP3) in CHCl3,
N(CH2CH2PPh2)3(NP3) in CH2Cl2 or CH2Cl2ꢀ
[XꢁBr (1), I (2)], [Au3(CP3)2Cl2]Cl (3), [Au3(CP3)3X]X2 [Xꢁ
Cl (9), Br (10)], Au(NP3)I (11), [Cu2(PP3)2X]X [XꢁCl (12), Br (13)] and [Au2(PP3)2]X2 [Xꢁ
/
S (Sꢁ
/
MeOH, Et2O) and P(CH2CH2PPh2)3 (PP3) in CH2Cl2 to form Cu(CP3)X
Br (4), I (5)], Cu(NP3)X [XꢁCl (6), Br (7), I (8)], [Au2(NP3)2]X2 [Xꢁ
Br (14), I (15)]. Complexes 1, 7 and 11
/
/
/
/
/
/
were shown by X-ray diffraction to consist of neutral monomers with distorted tetrahedral geometry around the metal and the
phosphine acting as tridentate chelating ligand. The mass spectra, conductivity measurements and 31P{1H} NMR studies for 9 and
10 are indicative of a coexistence with mononuclear forms. Complexes 3, 9 and 14 were also achieved in solution by addition of the
appropriate polyphosphine to the compounds Au3(CP3)Cl3 (3a), Au3(NP3)Cl3 (9a) and Au4(PP3)Br4 (14a), respectively, involving
ring-closure reactions. Likewise, crystals of 1 were obtained both from solutions of this compound in CH2Cl2ꢀ
/EtOH and from
solutions in CHCl3 of (1a)×2.5Et2O (1aꢁCu3(CP3)Br3). Further additions of the appropriate polyphosphine to 9 and 14 give
/
/
complexes with new ‘‘MP4’’ environments and dangling phosphorus that for 14 involve ring-opening processes. By reaction of 3 with
CP3 the complex [Au3(CP3)3Cl]Cl2, isostructural with 4 and 5, is afforded in solution. The reaction of Cu(CP3)Cl (I) with CP3
followed by 31P{1H} NMR seems to occur with retention in part of the starting CuP3 core and formation of other species containing
linear arrangements for Cu(I). No reaction was observed between 6 or 13 and NP3 or PP3, respectively.
# 2003 Elsevier B.V. All rights reserved.
Keywords: Copper(I) and gold(I); Tripodal polyphosphines; X-ray diffraction; 31P NMR spectroscopy; Ring-closure and opening reactions
1. Introduction
arrangement and the other ligands surrounding the
metal centre [3]. In recent years, manipulation of the
Polynuclear P- or N-donor ligands have been usually
employed in the synthesis of a broad diversity of mono-
and polynuclear species that in the case of latter
transition metals may present interesting applications
metalꢀhalide functionality has revealed that this can be
/
used as a highly valuable method of tuning the reactivity
of a given complex that can provide a way for the
development of new catalytic systems [5]. The starting
point for these findings was a work dealing with the
study of the chemistry salt effects in inorganic and
organometallic chemistry [6]. On the other hand,
changes in the nature of the ‘‘non-coordinating’’ ligands
of cationic complexes also influence the outcome of
catalytic processes [7]. In a previous work we found that
while the tripodal tetraphosphine tris[2-(diphenylpho-
[1ꢀ4]. The way in which a given polyphosphine or
/
aminophosphine coordinates to Group 11 metal centres
depends on the metal, the counter ions, the ligand
* Corresponding author. Tel.: ꢂ
597525.
E-mail address: qiegfq@usc.es (M.E. Garc´ıa-Ferna´ndez).
/
34-9-81 591076; fax: ꢂ34-9-81
/
0020-1693/03/$ - see front matter # 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0020-1693(03)00253-6

M.I. Garc´ıa-Seijo et al. / Inorganica Chimica Acta 353 (2003) 206ꢀ
/216
207
sphino)ethyl]phosphine (PP3) reacted with AgNO3 in 1:1
stoichiometric ratio to form the ionic dinuclear system
[Ag2(PP3)2](NO3)2 the triphosphines 1,1,1-tris(diphenyl-
phosphinomethyl)ethane (CP3) and tris[2-(diphenylpho-
sphino)ethyl]amine (NP3) afforded mononuclear
photometer. The bands are reported as vs, very strong;
s, strong; m, medium; w, weak; sh, shoulder; br, broad.
31P{1H} NMR spectra were recorded on a Bruker
AMX500 NMR spectrometer at 202.46 MHz. Chemical
shifts (d) are reported in ppm relative to external 85%
H3PO4; s, singlet; d, doublet; q, quartet; m, multiplet; bs,
broad signal; J, coupling constant in Hz. Conductivities
were measured at 25 8C using 10ꢄ3 M solutions in DMF
or CH3CN on a WTW model LF-3 instrument.
complexes with AgX salts (Xꢁnitrate or halide) there
/
being not influence of the halogen in the nuclearity of
the resultant compounds [8].
Balch and Fung reported in 1990 the crystal structure
of the ionic dinuclear complex [Au2(PP3)2]Cl2 prepared
in 1:1 metal to ligand ratio where the tripodal tetrapho-
sphine is coordinating in a tridentate chelating and a
monodentate bridging fashion [9]. Likewise, the crystal
structure of Cu(CP3)Cl was reported in 1993 by Fife et
al. consisting of monomers with a distorted tetrahedral
environment around the metal [10]. However, little work
has been directed toward the analysis of how the effect
of changing the nature of the metal, the halide or the
tripodal polyphosphine influences the structure of the
compounds and their reactivity. For that reason, this
work is focussed on a comparative structural study of
copper(I) and gold(I) halo complexes containing tripo-
dal ligands as CP3, NP3 and PP3 in 1:1 metal to ligand
ratio. For gold(I) we also report the preparation in
solution of 1:1 ionic compounds starting from neutral
2.2. Syntheses
2.2.1. Au(tdg)X
Au(tdg)X (Xꢁ
thiodiglycol) were prepared following literature proce-
dures [11ꢀ14].
/
Cl, Br; tdgꢁ
/
2,2?-thiodiethanolꢁ
/
/
2.2.2. Tris(2-diphenylphosphinoethyl)amine (NP3)
Tris(2-diphenylphosphinoethyl)amine (NP3) was pre-
pared as previously described [15].
2.2.3. Synthesis of 1ꢀ15 and 1a, 3a, 9a and 14a
In the syntheses with copper halides and gold iodide
dry CHCl3 or CH2Cl2 were used to dissolve the
/
phosphine. To a solution of L [Lꢁ
mmol; PP3: 0.347ꢀ0.523 mmol; NP3: 0.230 mmol) in a
minimum volume of CHCl3 or CH2Cl2, solutions of
Au(tdg)X in MeOH (XꢁCl) or in Et2O (XꢁBr) or
CuX (XꢁCl, Br, I) and AuI as solids were added in the
/
CP3: 0.127ꢀ/0.320
polynuclear systems, containing linear Pꢀ
/
Auꢀ/X frag-
/
ments, upon reaction with the appropriate polypho-
sphine via ring-closure reactions. The formation of
mononuclear complexes for copper(I) starting from
polynuclear systems and the reactivity of 1:1 compounds
with tripodal polyphosphines are also described.
/
/
/
appropriate stoichiometric ratio. For copper halide and
gold iodide complexes the mixture reaction was stirred
under nitrogen until the metallic salt was completely
dissolved (with AuI in an ice bath). Solvents were
partially removed in vacuo and n-hexane (1, 5) or
2. Experimental
Et2O (2, 6ꢀ
/
8, 11ꢀ13, 15) was added to complete the
/
2.1. General procedures and instrumentation
precipitation of the complexes. For gold chloride or
bromide complexes the resultant mixtures were stirred
Dichloromethane and chloroform were redistilled
under nitrogen over CaCl2 and P4O10, respectively.
1,1,1-Tris(diphenylphosphinomethyl)ethane, copper(I)
bromide and iodide and gold(I) iodide were purchased
from Strem Chemicals, 2,2?-thiodiethanol and tris[2-
(diphenylphosphino)ethyl]phosphine from Aldrich and
gold metal from SEMPSA. Microanalyses were per-
formed on a Fisons Instrument EA 1108 CHNS-O. Fast
Atom Bombardment (FAB) or Liquid Secondary-Ion
(LSI MS) mass spectra were obtained in a Micromass
Autospec spectrometer using nitrobenzylic alcohol as
the matrix. Positive electrospray ion mass spectra (ESI
MS) were recorded on a Micromass VG-QUATTRO
for 14ꢀ24 h at room temperature and after that solvents
were removed in vacuo to leave precipitates which were
filtered off and treated with H2O. Some of the solids
/
were recrystallised from CH2Cl2ꢀEt2O and in all cases
/
the final solids were filtered off and dried in vacuo.
Crystals of 1 and 7, used for X-ray diffraction studies,
were obtained by recrystallisation from CH2Cl2ꢀ
(2:1) and MeOHꢀCH3CN (1:2), respectively, and of 11
by slow evaporation of a saturated solution in CD2Cl2ꢀ
CD3OD (1:1). 1: Yield: 87%. Colour: white, melting
point (m.p.)ꢀ250 8C. Found: C, 63.7; H, 4.9. Calc. for
C41H39P3CuBr: C, 64.1; H, 5.1%. IR nmax (cmꢄ1) (Cuꢀ
Br) 212s. MS (FAB): m/z 767 (Mꢂ, 10%); 687 (Mꢂꢄ
Br, 100%). 31P{1H} NMR (CDCl3): see Table 1.
L(DMF)ꢁ 2.5Et2O: Yield:
2.1 Ohmꢄ1 cm2 molꢄ1. (1a)×
97%. Colour: white, m.p.ꢀ250 8C. Found: C, 50.4; H,
5.0. Calc. for C51H64P3Cu3Br3O2.5: C, 49.4; H, 5.2%. IR
nmax (cmꢄ1) (CuꢀBr) 227w. MS (FAB): m/z 975 (Mꢂꢄ
Br, 6%); 830 (Mꢂꢄ Cu, 51%); 767 (Mꢂꢄ
2Brꢄ 2Brꢄ
/EtOH
/
/
/
/
/
spectrometer from 0.5ꢃ
plexes using CH3CNꢀH2Oꢀ
phase. Infrared spectra were recorded at ambient
temperature as KBr pellets (4000ꢀ
500 cmꢄ1) or Nujol
mulls (500ꢀ
100 cmꢄ1) on a Nicolet IMPACT 400 with a
DTGS detector and a Mattson Cygnus 100 spectro-
/
10ꢄ4 M solutions of the com-
formic acid 1% as mobile
/
/
/
/
/
/
/
/
/
/
/
/
/

208
M.I. Garc´ıa-Seijo et al. / Inorganica Chimica Acta 353 (2003) 206ꢀ216
/
Table 1
31P{1H} NMR data for complexes I, Ia, 1ꢀ
3a, 9a and 14a with the appropriate polyphosphine
L(DMF)ꢁ
/
19.7 Ohmꢄ1 cm2 molꢄ1. (4)×
/
3H2O: Yield:
/
15 and for titrations of I,
74%. Colour: white, m.p. 187 8C. Found: C, 53.0; H, 4.0.
Calc. for C123H123P9Au3Br3O3: C, 53.5; H, 4.5%. IR
nmax (cmꢄ1) (Auꢀ
/
Br) 233sh. ESI MS (ꢂ
([Au3(CP3)3Br]2ꢂ, 32%). MS (FAB): m/z 1098 (Mꢂꢄ
2BrꢄAuꢄ 2Brꢄ2AuꢄCP3,
2CP3, 15%); 821 (Mꢂꢄ
53%). 31P{1H} NMR (CDCl3): see Table 1.
19.0 Ohmꢄ1 cm2 molꢄ1. 5: Yield: 43%.
/): m/z 1273
Compound
dP (ppm) a
Solvent
/
I a
ꢄ
ꢄ/
/
33.6s
28.0bs (I), 27.4s, 26.8s, 24.4s, ꢄ
15.1bs, ꢄ21.5bs (Ia?, Iaƒ)
33.5bs (I), ꢄ11.5bs, ꢄ18.2bs, ꢄ
27.6s, ꢄ29.8s (Ia1, Ia2, CP3)
35.4bs
CDCl3
CDCl3
/
/
/
/
/
Ia a
/
/
L(DMF)ꢁ
/
Iꢂ
CP3
/0.5 equiv.
ꢄ/
/
/
/
CDCl3
Colour: white, m.p. 182 8C. Found: C, 51.3; H, 4.3.
Calc. for C123H117P9Au3I3: C, 51.9; H, 4.1%. ESI MS
/
1
ꢄ/
CDCl3
CDCl3
(ꢂ
821 (Mꢂꢄ
(CDCl3): see Table 1. L(DMF)ꢁ
molꢄ1. 6: Yield: 84%. Colour: white, m.p.ꢀ
/
): m/z 1296 ([Au3(CP3)3I]2ꢂ, 35%). MS (FAB): m/z
1a×
1a
(2)×
5H2O
Et2O
/
2.5Et2O
ꢄ
/
25.3bs (1), 32.7s, 31.2s
22.6bs (1), 31.0s, 28.0s
15.2bs
ꢄ
/
CDCl3
DMSO-d6
/
2Iꢄ
/
2Auꢄ
/
CP3, 53%). 31P{1H} NMR
19.5 Ohmꢄ1 cm2
250 8C.
/
CHCl3×
/
ꢄ/
/
/
2a×
/
ꢄ
/
24.9s (2), 30.1s, 28.6s
DMSO-d6
CDCl3
3
3a
24.7s, 16.4bs, ꢄ
15.2s
1.0 equiv. 15.6s, 15.0s, ꢄ
/
5.4bs, ꢄ
4.8bs, ꢄ12.6bs (3)
12.8bs
/
12.0bs
Found: C, 66.5; H, 6.0; N, 2.0. Calc. for
C42H42NP3CuCl: C, 67.0; H, 5.6; N, 1.9%. IR nmax
CDCl3
3aꢂ
/
/
/
CDCl3
(cmꢄ1) (Cuꢀ
/
Cl) 244sh. MS (FAB): m/z 716 (Mꢂꢄ
/
Cl,
100%). 31P{1H} NMR (CDCl3): see Table 1.
L(CH3CN)ꢁ
10.4 Ohmꢄ1 cm2 molꢄ1. 7: Yield: 77%.
Colour: white, m.p.ꢀ250 8C. Found: C, 63.0; H, 5.7; N,
1.8. Calc. for C42H42NP3CuBr: C, 63.3; H, 5.3; N, 1.8%.
IR nmax (cmꢄ1) (Cuꢀ
Br) 223vs,br. MS (FAB): m/z 716
(MꢂꢄBr, 100%). 31P{1H} NMR (CD2Cl2ꢀ
CD3OD):
see Table 1. L(CH3CN)ꢁ
11.1 Ohmꢄ1 cm2 molꢄ1. 8:
Yield: 84%. Colour: beige, m.p.ꢀ250 8C. Found: C,
59.1; H, 5.3; N, 1.7. Calc. for C42H42NP3CuI: C, 59.8;
H, 5.0; N, 1.7%. IR nmax (cmꢄ1) (Cuꢀ
I) 158vs,br. MS
(FAB): m/z 716 (MꢂꢄI, 100%). 31P{1H} NMR
(CDCl3): see Table 1. L(CH3CN)ꢁ
12.7 Ohmꢄ1 cm2
8H2O: Yield: 80%. Colour: white, m.p.
CP3
3aꢂ
CP3
(4)×3H2O
/2.0 equiv. 24.7s, ꢄ
/
5.3bs, ꢄ
/
CDCl3
/
/
24.9s, ꢄ
25.0s, ꢄ5.2bs, ꢄ
26.1bs
8.4s
/
5.4bs, ꢄ
/
12.5bs
CDCl3
CDCl3
CDCl3
/
5
6
7
/
/11.8bs
ꢄ
/
/
ꢄ/
CD2Cl2 ꢀ
/
/
/
CD3OD
/
8
ꢄ/29.4bs
CDCl3
CDCl3
(9)×
/8H2O
29.0s, 26.5s, 23.8s
28.6s
/
9a
DMSO-d6
9aꢂ
/
2.0 equiv. 35.9bs, 30.9s, 28.4s (9)
DMSO-d6 ꢀ
/
/
NP3
CDCl3
/
9aꢂ
/
3.0 equiv. 30.9s, 22.4s, ꢄ12.2bs
/
DMSO-d6 ꢀ
/
/
NP3
CDCl3
molꢄ1. (9)×
/
(10)×
/8H2O
33.5s, 27.0bs, 22.8s
24.4s
CDCl3
11
CD2Cl2 ꢀ
/
171 8C. Found: C, 52.6; H, 5.1; N, 1.6. Calc. for
C84H100N2P6Au2Cl2O8: C, 52.6; H, 5.3; N, 1.5%. MS
CD3OD
12×
/
CH2Cl2
CH2Cl2
8.6bs, 3.2bs, ꢄ
/
11.1bs
9.4bs
CDCl3
(FAB): m/z 1082 (Mꢂꢄ
/
Clꢄ
/
NP3, 2%); 850 (Mꢂꢄ
/
13×
/
8.8bs, 3.3bs, ꢄ
/
CD2Cl2
CD2Cl2
DMSO-d6
2Clꢄ
/
NP3ꢄ
/
Au, 100%). 31P{1H} NMR (CDCl3): see
14 b
34.0m, 26.6m, 15.0m
36.8q, 35.7d
14a b
Table 1. L(CH3CN)ꢁ
/
136.7 Ohmꢄ1 cm2 molꢄ1. (10)×
/
14aꢂ
/
2.0 equiv. 37.9m, 28.4m, 18.6m (14)
DMSO-d6 ꢀ
/
8H2O: Yield: 79%. Colour: white, m.p. 181 8C. Found:
C, 50.5; H, 4.8; N, 1.5. Calc. for C84H100N2P6Au2Br2O8:
PP3
CDCl3
14aꢂ
/
3.0 equiv. 37.7m, 28.4m, 18.5m (14), 23.9m,
DMSO-d6 ꢀ
/
C, 50.3; H, 5.0; N, 1.4%. MS (FAB): m/z 1047 (Mꢂꢄ
/
PP3
15 b
0.0bs, ꢄ
33.9m, 25.7m, 15.2m
/
10.4m
CDCl3
CD2Cl2
2Brꢄ
/
NP3, 1%); 850 (Mꢂꢄ
/
2Brꢄ
/
NP3ꢄAu, 100%).
/
31P{1H} NMR (CDCl3): see Table 1. L(CH3CN)ꢁ
/
a
dP (CDCl3): CP3 (ꢄ
/
27.6s), PP3 (ꢄ
/
14.7q, ꢄ
/
18.9d), NP3 (ꢄ22.7s);
/
114.3 Ohmꢄ1 cm2 molꢄ1. 11: Yield: 67%. Colour:
white, m.p. 278 8C (dec.). Found: C, 50.9; H, 4.5; N,
1.4. Calc. for C42H42NP3AuI: C, 51.6; H, 4.3; N, 1.4%.
I, Cu(CP3)Cl; Ia, Cu3(CP3)Cl3.
b
J(31P,31P) (Hz): 14 (132, 72, 60), 14a: (48), 15 (132, 71, 62).
MS (FAB): m/z 850 (Mꢂꢄ
(CD2Cl2ꢀCD3OD): see Table 1. L(DMF)ꢁ
Ohmꢄ1 cm2 molꢄ1. 12×
CH2Cl2: Yield: 59%. Colour:
white, m.p. 162 8C. Found: C, 62.6; H, 5.5. Calc. for
C85H86P8Cu2Cl4: C, 62.8; H, 5.3%. IR nmax (cmꢄ1
(Cuꢀ ClꢄPP3,
Cl) 240m,br. LSI MS: m/z 833 (Mꢂꢄ
58%); 735 (Mꢂꢄ Cu, 57%). 31P{1H} NMR
2ClꢄPP3ꢄ
(CDCl3): (see Table 1). L(DMF)ꢁ
63.9 Ohmꢄ1 cm2
molꢄ1. 13×
CH2Cl2: Yield: 53%. Colour: white, m.p.
179 8C. Found: C, 60.0; H, 5.3. Calc. for
C85H86P8Cu2Br2Cl2: C, 59.6; H, 5.1%. IR nmax (cmꢄ1
(Cuꢀ BrꢄPP3,
Br) 200m,br. LSI MS: m/z 877 (Mꢂꢄ
16%); 735 (Mꢂꢄ Cu, 29%). 31P{1H} NMR
2BrꢄPP3ꢄ
/
I, 100%). 31P{1H} NMR
2Cu, 22%); 687 (Mꢂꢄ
NMR (CDCl3): see Table 1. L(DMF)ꢁ
cm2 molꢄ1. (2)×
CHCl3×5H2O: Yield: 93%. Colour:
white, m.p.ꢀ250 8C. Found: C, 50.0; H, 5.0. Calc. for
C42H50P3CuICl3O5: C, 49.2; H, 4.9%. IR nmax (cmꢄ1
I) 149sh. 31P{1H} NMR (DMSO-d6): see Table 1.
/
3Brꢄ
/
2Cu, 100%). 31P{1H}
/
/74.6
/
67.1 Ohmꢄ1
/
/
/
/
)
)
/
/
/
(Cuꢀ
/
/
/
/
3: Yield: 53%. Colour: white, m.p. 201 8C. Found: C,
/
51.7; H, 4.0. Calc. for C82H78P6Au3Cl3: C, 50.6; H,
/
4.0%. IR nmax (cmꢄ1) (Auꢀ
/
Cl) 316sh, 308sh. ESI MS
): m/z 937 ([Au3(CP3)2Cl]2ꢂ, 14%). MS (FAB): m/z
1054 (Mꢂꢄ CP3, 16%); 821 (Mꢂꢄ
2ClꢄAuꢄ 2Clꢄ
2Auꢄ
CP3, 20%). 31P{1H} NMR (CDCl3): see Table 1.
(ꢂ
/
)
/
/
/
/
/
/
/
/
/
/
/
/

M.I. Garc´ıa-Seijo et al. / Inorganica Chimica Acta 353 (2003) 206ꢀ
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209
(CD2Cl2): (see Table 1). L(DMF)ꢁ
/
72.1 Ohmꢄ1 cm2
3. Results and discussion
3.1. Syntheses
molꢄ1. 14: Yield: 60%. Colour: white, m.p. 160 8C.
Found: C, 52.8; H, 4.5. Calc. for C84H84P8Au2Br2: C,
53.2; H, 4.5%. LSI MS: m/z 1522 (Mꢂꢄ
/
2Brꢄ
PP3, 6%); 867
31P{1H}
NMR
132.6 Ohmꢄ1 cm2
/
C2H4PPh2, 12%); 1064 (Mꢂꢄ
(Mꢂꢄ
2BrꢄPP3ꢄAu, 100%).
/
2Brꢄ
/
Scheme 1 shows the complexes prepared in this work.
The tripodal ligand tris[2-(diphenylphosphino)ethyl]a-
mine (NP3) was synthesised following a variation of the
method described in the literature [25].
Complexes 4, 9 and 10 gave satisfactory microana-
lyses for hydrates, while 12 and 13 were isolated as
dichloromethane solvates. Analytical data for complex 2
were in agreement with the presence of water and
chloroform molecules.
/
/
/
(CD2Cl2): (see Table 1). L(DMF)ꢁ
/
molꢄ1. 14a: Yield: 30%. Colour: white, m.p. 257 8C
(dec). Found: C, 28.8; H, 2.7. Calc. for C42H42P4Au4Br4:
C, 28.4; H, 2.4%. IR nmax (cmꢄ1) (Auꢀ
/Br) 232vs, 220s.
31P{1H} NMR (DMSO-d6): (see Table 1). L(DMF)ꢁ
/
4.2 Ohmꢄ1 cm2 molꢄ1. 15: Yield: 45%. Colour: white,
m.p. 271 8C. Found: C, 50.3; H, 4.3. Calc. for
C84H84P8Au2I2: C, 50.7; H, 4.3%. LSI MS: m/z 1522
Compounds 1ꢀ15 were obtained as solids using a 1:1
/
(Mꢂꢄ
/
2Iꢄ
/
C2H4PPh2, 12%); 867 (Mꢂꢄ
/
2Iꢄ
/
PP3ꢄAu,
/
metal to ligand ratio that for 3 resulted in a trinuclear
ionic compound with a 3:2 stoichiometric ratio. To
avoid the oxidation from Cu(I) to Cu(II), reactions with
the copper salts were carried out under nitrogen.
100%). 31P{1H} NMR (CD2Cl2): (see Table 1). Char-
acterisation of complexes 3a and 9a was previously
reported [16,17].
Crystals suitable for X-ray diffraction of 1, 7 and 11
were obtained from solutions of the complexes in the
appropriate solvent system. Crystals of 1 were also
2.3. Titrations of I, 3a, 9a and 14a
To a solution of complexes I (Cu3(CP3)Cl3) and 3a in
CDCl3 and of 9a and 14a in DMSO-d6 solutions of the
corresponding polyphosphine in CDCl3 were added
reaching the 1:1, 1:2 or 2:1 (I, Ia1, Ia2), 3:2 (3) and 1:1
(9 and 14) metal to ligand stoichiometric ratios. The
31P{1H} NMR spectra were recorded and the most
significant signals are given in Table 1.
achieved from solutions of (1a)×
/
2.5Et2O (1aꢁ
/
Cu3(CP3)Br3) in CHCl3.
3.2. Characterisation
Complexes 1ꢀ
spectra copperꢀ
frequencies assigned to terminal Mꢀ
/
4, 6ꢀ
halogen or goldꢀ
/
8, 12 and 13 showed in the far IR
halogen vibrational
X stretches [26,27].
/
/
/
2.4. Crystal structure determination of 1, 7 and 11
Colourless plates of 1, colourless needles of 7 and
yellow needles of 11 were mounted on glass fibres and
used for data collection. Crystal data for 1 were
collected at 220(2) K, using a Stoe Stadi-4 diffract-
ometer equipped with an Oxford Cryosystem variable-
temperature device [18]. Graphite monochromated Cu
Ka radiation was used throughout and a semi-empirical
absorption correction was made. Crystal data for 7 and
11 were collected at 293(2) K, using a BRUKER
SMART CCD 1000 diffractometer. Graphite mono-
chromated Mo Ka radiation was used throughout. The
data were processed with SAINT [19] and empirical
absorption correction was made using SADABS [20].
The structures were solved by direct methods, 1 using
the program SHELXS-97 [21] and 7 and 11 using the
program SIR-92 [22]. The structures were refined by full-
matrix least-squares techniques against F2 using
SHELXL-97 [21]. Positional and anisotropic atomic
displacement parameters were refined for all non-
hydrogen atoms. Hydrogen atoms were placed geome-
trically and positional parameters were refined using a
riding model. Atomic scattering factors were obtained
with the use of International Tables for X-ray Crystal-
lography [23]. Molecular graphics were obtained from
ORTEP-3 for WINDOWS [24].
3.2.1. Complexes with CP3
Conductivity measurements for complexes 1ꢀ
consistent with a non electrolyte behaviour in 10ꢄ3
DMF solutions [28]. The FAB mass spectrum for 1
exhibits a peak at m/z 767 due to the molecular ion Mꢂ.
The positive electrospray mass spectrum of 3 displays a
peak at m/z 937 corresponding to [Au3(CP3)2Cl]2ꢂ, the
/
5 are
M
spectra of
[Au3(CP3)3X]2ꢂ (m/zꢁ
In accordance with these results, trinuclear ionic species
seem to exist in solution for 3ꢀ5 and the non electrolyte
4
and
5
showing
a peak due to
/
1273 and 1296, respectively).
/
behaviour observed in DMF is probably due to the
formation of ion pairs or trios. The only broad signal at
d ꢄ
/
35.4 and ꢄ
15.2 present in the 31P{1H} NMR
/
spectrum of 1 and 2, respectively, is consistent with
the formation of neutral tetrahedral complexes with the
three phosphorus of the ligand and the halide coordi-
nated to the copper. The broadening of the signal is
indicative of a fluxional behaviour.
The 31P{1H} NMR spectra for 3ꢀ
5, recorded at room
/
(Table 1) and low temperature [16], confirm in all three
cases the coexistence of mixtures of species containing
linear and tetrahedral environments for Au(I) and some
phosphine oxide forms (d ꢁ
proposal for one of these structures of compounds 3ꢀ
/
25.0). Scheme 2 shows the
5.
/

210
M.I. Garc´ıa-Seijo et al. / Inorganica Chimica Acta 353 (2003) 206ꢀ216
/
Scheme 1. Copper(I) and gold(I) complexes prepared with CP3 (1ꢀ
/
5), NP3 (6ꢀ
/
11) and PP3 (12ꢀ15) in 1:1 metal to ligand ratio. Reactions of 3a, 9a
/
and 14a with CP3, NP3 and PP3, respectively, and formation of 1 from 1a.
In case of 3 this proposal coincides with the structure
found in solid state by X-ray diffraction [16].
the other hand, in the spectrum of complexes 9 and 10
peaks assigned to the dinuclear Au2(NP3)Cl (m/z 1082)
and Au2(NP3) (m/z 1047) fragments, respectively, were
observed. The presence of these peaks, absent in the
iodo derivative, seems to be consistent with a dimeric
structure for both compounds. The 31P{1H} NMR
3.2.2. Complexes with NP3
Conductivity measurements for solutions in CH3CN
of Cu(NP3)X complexes (6ꢀ
behaviour. However, solutions of 9 and 10 in CH3CN
and 11 in DMF resulted to be conductors (ꢁ1:1
electrolytes) [28]. The FAB mass spectra of complexes
6ꢀ8 showed a peak due to the Cu(NP3) fragment. On
/
8) reflected a non electrolyte
spectra for complexes 6ꢀ
/
8 exhibit only one resonance
29.4, respectively. This is in
at d ꢄ26.1, ꢄ8.4 and ꢄ
/
/
/
/
accordance with the formation of tetrahedral complexes,
with the three phosphorus atoms of the ligand coordi-
/
Scheme 2. Structures proposed in solution for complexes 1ꢀ
/
8 and 12ꢀ15.
/

M.I. Garc´ıa-Seijo et al. / Inorganica Chimica Acta 353 (2003) 206ꢀ
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211
nated to the copper in an equivalent arrangement
(Scheme 2). However, due to the broadening of the
signal observed for 6 and 8 a fluxional behaviour in
solution involving the N of the aminophosphine in the
coordination to Cu(I) should not be excluded.
The 31P{1H} NMR spectrum of the complexes 9 and
10 exhibits three signals [d 29.0, 26.5, 23.8 (9); 33.5, 27.0,
22.8 (10)] (Fig. 1(a, b)). The set of signals formed by the
two resonances at down field can be assigned to the
dinuclear compounds [Au2(NP3)2]X2 where each ami-
nophosphine of the cation acts as bidentate chelating
and bridging ligand, each metal centre being three-
coordinate. The signal at higher field can be attributed
to the monomers Au(NP3)X containing equivalent
phosphorus atoms with gold(I) in
a tetrahedral
(AuP3Cl) environment. The coexistence of both struc-
tures allows to justify the low value of conductivities for
2:1 electrolytes.
The signal at d 24.4 found in the 31P{1H} NMR
spectrum for 11 (Fig. 1(c)) points to the presence of only
monomers. The high value of conductivity can be due to
the replacement of iodide by DMF [8,16] or to the
presence of Au(I) in a trigonal pyramidal geometry with
a iodide as counter anion.
3.2.3. Complexes with PP3
Complexes 12ꢀ15 are conductors in DMF solutions
/
and behave as 1:1 (12, 13) and 1:2 (14, 15) electrolytes
[28]. The FAB mass spectra of complexes 12 and 13
showed a peak at m/z 833 and 877, respectively,
assigned to the dinuclear fragment Cu2(PP3)X. The
31P{1H} NMR spectra exhibit three broad signals
around 8, 3 and ꢄ10 ppm (Table 1) with integration
/
2:4:2, the downfield resonance, assigned to the apical
phosphorus, being splitted into two signals. The reso-
nance at higher field is characteristic for uncoordinated
phosphorus of the ligand, the width of the signal
indicating the existence of exchange processes that could
involve the dangling phosphorus and the halogen.
According to these data, the conductivity values and
the presence of dinuclear species in the mass spectra, a
dinuclear ionic structure as that one shown in Scheme 2
was proposed. In the cation one phosphine acts as a
tridentate chelating ligand with an uncoordinated dan-
gling phosphorus and the other coordinates to the metal
centres in both tridentate chelating and bridging fash-
ions giving rise to CuP4 and CuP3X environments, there
being one halide as counter ion.
The 31P{1H} NMR spectra of complexes 14 and 15
showed three multiplets at d 34.0, 26.6 and 15.0 (14) and
d 33.9, 25.7 and 15.2 (15). On the basis of the
multiplicity and the integration ratio (1:1:2) these signals
suggest the formation of the dinuclear species
Fig. 1. 31P{1H} NMR spectra for 9 (a) and 10 (b) in CDCl3 and 11 (c)
in CD2Cl2 ꢀCD3OD: (*) is attributed to [Au2(NP3)2]X2 and (m) to
Au(NP3)X.
/
[Au2(PP3)2]X2 (XꢁBr (14), I (15)] as was previously
/
observed for the chloro derivative [9]. The spectra can be
analysed as AMX2 systems and the resonances can be
assigned, from lower to higher field, to two apical, two
terminal bridging and four terminal chelating phospho-

212
M.I. Garc´ıa-Seijo et al. / Inorganica Chimica Acta 353 (2003) 206ꢀ216
/
rus in accordance with each PP3 acting as tridentate
chelating and monodentate bridging ligand (Scheme 2).
The ꢁ130, 70 and 60 Hz coupling constants found are
/
due to P involved in the five-membered rings, the unlike
terminal P and internal and terminal P of the bridging
arm, respectively. Furthermore, the digold fragments
detected in the LSI MS mass spectra also support the
existence of dinuclear species.
3.3. X-ray diffraction studies: crystal structures of 1, 7
and 11
The molecular structures with the numbering schemes
of complexes 1, 7 and 11 are shown in Figs. 2 and 3. A
summary of crystal parameters, data collection and
refinement for the crystal structures is given in Table 2
and selected bond lengths and angles are listed in Table
3.
The X-ray crystal structures of 1, 7 and 11 consist of
monomeric neutral CuLBr [LꢁCP3(1), NP3 (7)] and
/
Au(NP3)I (11) units with the metal bound to the three P
atoms of the ligand and the halogen in a distorted
tetrahedral geometry, confirming an identical behaviour
for these complexes in solid state and solution.
The average for Cuꢀ
/
P bond lengths in 1 (2.2867(17)
˚
A) is very close to the value found (2.2953(4) A) in the
˚
chloro complex [10] and in both cases are in the expected
˚
range for four-coordinate Cu(I) systems (2.304 A) [29a].
˚
Br distance of 7 (2.4965(13) A) is
˚
longer than expected (literature values of 2.393 A) and
However, the Cuꢀ
/
˚
compared with that one found for 1 (2.3983(15) A). This
is indicative of a weaker coordination of the halide to
Cu(I) compared with 1 as was also observed for NO3ꢄ
Fig. 3. Molecular structure of 7 (a) and 11 (b).
in the complex Ag(NP3)NO3 [30] with Ag(I) achieving
an AgP3O arrangement. The averages for Pꢀ
PꢀCuꢀBr angles are very close to the ideal tetrahedral
/
Cuꢀ
/
P and
/
/
values in 7 (109.47(3) and 109.46(7)8, respectively)
supporting the coordination of the bromide to the
copper centre and show deviations in 1 (94.49(5) and
121.99(5)8, respectively) attributable to the strain im-
posed by the six-membered chelate rings formed [31]. It
should be noted that in 7 the apical nitrogen of the
˚
N: 3.070 A)
ligand does not coordinate to copper (Cuꢀ
/
Fig. 2. Molecular structure of 1.
in contrast with the trigonal pyramidal structure found

M.I. Garc´ıa-Seijo et al. / Inorganica Chimica Acta 353 (2003) 206ꢀ
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213
Table 2
Summary of crystal parameters, data collection and refinement for 1, 7 and 11
1
7
11
Empirical formula
Formula weight
Temperature (K)
C
41H39CuBrP3
C42H42P3NCuBr
797.13
293(2)
C42H42P3NAuI
977.54
293(2)
768.08
220(2)
1.54178
˚
Wavelength (A)
0.71073
0.71073
Crystal size (mm)
Colour/habit
0.50ꢃ
/
0.50ꢃ
/
0.15
1.13ꢃ
/
0.04ꢃ
/
0.04
0.94ꢃ
/
0.10ꢃ0.06
/
colourless/plates
orthorhombic
P21
colourless/needles
monoclinic
P21
yellow/needles
monoclinic
Cc
Crystal system
Space group
˚
a (A)
20.435(9)
10.272(5)
17.010(10)
90
10.224(2)
8.9741(18)
20.646(4)
90
16.763(3)
12.853(2)
17.745(3)
90
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
Volume (A )
Z
Calculated density (mg mꢄ3
Absorption coefficient (mmꢄ1
F(000)
90
90
90.551(4)
90
93.180(3)
90
3
˚
3576(3)
4
1.427
1894.2(6)
2
1.398
3817.2(11)
4
1.737
)
)
3.649
1576
1.788
820
1.701
1912
u Range for data collection (8)
Index ranges
4.82ꢀ
95
l 519
6829
2904 [Rint
/
70.18
1.97ꢀ
115
l 522
8845
5236 [Rint
/
23.36
2.00ꢀ
205
l 522
11 472
6420 [Rint
/
26.39
ꢄ/
/
h 524, ꢄ
/
/
65
/
k 5
/
12, ꢄ
/
205
/
ꢄ/
/k 5
/
11, ꢄ
/
95
/
l 5
/
9, 05
/
ꢄ/
/
h 5
/
20, 05
/
k 5
/
16, ꢄ
/
205
/
/
/
/
Reflections collected
Independent reflections
Max/min transmission
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices
ꢁ
/
0.0193]
ꢁ
/
0.0512]
ꢁ0.0467]
/
0.338/0.688
2904/1/418
1.065
0.9319/0.2371
5229/1/433
0.949
0.8650/0.5056
6170/2/436
0.929
R1ꢁ
/
0.0340, wR2ꢁ
/
0.0969
R1ꢁ/0.0482, wR2ꢁ
/0.0900
R1ꢁ
/
0.0305, wR2ꢁ
/0.0602
Largest difference peak and hole (e 0.351 and ꢄ
/
0.420
0.637 and ꢄ
/
0.619
1.385 and ꢄ
/
0.745
ꢄ3
˚
A
)
molecule of P3 being coordinated to copper(I) in a
bidentate chelating and a bridging fashion with two
CuP2PX environments. Both situations of complexes
with tripodal and linear polyphosphines constitute an
example of how the ligand arrangement influences its
coordination mode and the nuclearity of the complexes
formed.
Table 3
Selected distances (A) and angles (8) for complexes 1, 7 and 11
˚
1
7
11
Bond lengths
M(1)ꢀ
M(1)ꢀ
M(1)ꢀ
M(1)ꢀ
/
P(1)
P(2)
P(3)
X(1)
2.2934(16)
2.2787(18)
2.2880(18)
2.3983(15)
2.306(2)
2.304(2)
2.3903(16)
2.4473(18)
2.3911(18)
3.0440(6)
/
/
2.3025(18)
2.4965(13)
The
crystal structure
of
the
cation
in
/
[Au2(NP3)2](BPh4)2 [34] is identical to that one proposed
for solutions of the dinuclear complexes [Au2(NP3)2]X2,
Bond angles
P(1)ꢀM(1)ꢀ
P(1)ꢀM(1)ꢀ
P(2)ꢀM(1)ꢀ
P(1)ꢀM(1)ꢀ
P(2)ꢀM(1)ꢀ
P(3)ꢀM(1)ꢀ
/
/
P(2)
P(3)
P(3)
X(1)
X(1)
X(1)
92.49(5)
94.55(5)
96.43(6)
121.30(6)
126.11(5)
118.56(5)
108.60(9)
109.67(9)
110.15(7)
108.40(6)
112.60(7)
107.38(8)
108.04(6)
112.57(6)
112.25(6)
109.24(4)
103.52(4)
110.78(4)
Xꢁ
/
Cl (9) and XꢁBr (10), which seem to coexist with
/
/
/
the mononuclear species Au(NP3)X. Although complex
11 was prepared using the same metal:ligand ratio and
following the same procedure that for the chloro and
bromo derivatives, the structural studies in solution
showed a monomeric behaviour, the single-crystal
analysis also confirming the existence of tetrahedral
/
/
/
/
/
/
/
/
˚
N: 2.288 A) [32]. Thus, the
for [Cu(NP3)](BPh4) (Cuꢀ
/
mononuclear units.
The average for Auꢀ
is close to that one found for the AuP4 environment
˚
P bond distances (2.4095(17) A)
change of bromide by the non-coordinating anion,
BPh4ꢄ is responsible of the different resultant structure.
On the other hand, for comparison purposes it is
important to note that White et al. [33] reported the
/
˚
(2.4102 A) in the complex [Au3(CP3)2Cl2]Cl (3) [16] and
in the range expected for four-coordinate gold(I)
˚
I distance (3.0440(6) A) is
crystal structure of compounds [Cu(P3)X]2 (P3ꢁ
(diphenylphosphino)ethyl]phenylphosphine; XꢁCl, Br,
I) confirming the presence of neutral dimers, each
/bis[2-
compounds [29a]. The Auꢀ
/
˚
2.6 A range usually
/
significantly longer than the 2.5ꢀ
/
observed for AuꢀI bond lengths [29b] and very close to
/

214
M.I. Garc´ıa-Seijo et al. / Inorganica Chimica Acta 353 (2003) 206ꢀ216
/
the value found in [Au(EtTPA)3]I4×
/
3H2O (EtTPAꢁ
C8H17N3P) (2.9129(2) A) showing an AuP3 trigonal-
planar arrangement with tetrahedral distortion (PꢀAuꢀ
P angles of 117.97(3)8) induced by one iodide [35].
However, the averages for PꢀAuꢀP (110.95(6)8) and Pꢀ
AuꢀI (107.84(4)8) angles are very close to those
/
being around 10 ppm lower field shifted due to the
coexistence with other species. On the other hand,
˚
/
/
solutions of 1a and (1a)×/2.5Et2O in DMF show con-
ductivity values in the lower range for 1:1 electrolytes in
consistence with the coordinating behaviour of this
solvent that could give rise to a process similar to that
one described in eq. 1. Solutions of Ia in DMF exhibit a
molar conductivity of 25 Ohmꢄ1 cm2 molꢄ1 in accor-
dance now with the process shown in eq. 2. The
reactivity of Cu(CP3)Cl (I) with CP3 was studied by
31P{1H} NMR and the results (Fig. 4(A)) showed that
by addition of 0.5 equiv. of CP3 the starting compound
/
/
/
/
corresponding to the ideal tetrahedral geometry, indi-
cating as for complex 7 and for Ag(NP3)Cl [8] that the
halide is coordinated to the metal centre. Thus, the
crystal structures of 7 and 11 constitute the first example
of neutral mononuclear compounds for NP3 with Cu(I)
and Au(I), respectively.
(resonance at d ꢄ
and other species (d ꢄ
phosphorus (d 29.8) and probably linear Cu(I)
arrangements (eq. 3).
/
33.5) coexists with free CP3 (d ꢄ
/
27.6)
/
18.2, ꢄ11.5) containing dangling
/
3.4. Conversion to the 1:1 stoichiometry of complexes
ꢄ
/
with n:1 (nꢁ3, 4) metal to ligand ratios
/
CDCl3
4Cu(CP3)Clꢂ2CP3 0 Cu(CP3)ClꢂPC(PCuCl)2
From solutions of (1a)×
(1)×2Et2O were obtained, the process being reproduced
several times (eq. 1).
/
2.5Et2O in CHCl3, crystals of
I
I
/
Ia ꢂ[P2CPCuPCP2]Clꢂ2CP3
(3)
1
Ia2
CHCl3
2Cu3(CP3)Br3 ×2:5Et2O 0
Further additions of CP3 result in an increase of the
intensity of the resonance due to free phosphine.
The titrations of 3a, 9a and 14a with CP3, NP3 and
PP3, respectively, were also followed by 31P{1H} NMR
(Table 1). Complex 3 was afforded when 3a reacted with
1 molecular equiv. of CP3, in consistence with a 3:2
metal to ligand ratio previously found for 3 (eq. 4). As
expected, the formation of 9 as a mixture of a mono-
nuclear and a dinuclear form (Scheme 3) required the
addition of 2 molecular equiv. of NP3 to 9a (eq. 5).
However, complex 14 was only species observed in
solution by reaction of 14a with 2 equiv. of PP3 (eq. 6,
Fig. 4(B)).
(1a)×2:5Et2O
 Cu(CP3)Br×2Et2Oꢂ[Cu3(CP3)(OEt2)3Br][CuBr2]2
(1)×2Et2O
1a?
(1)
The 31P{1H} NMR spectrum of (1a)×
/
2.5Et2O in
CDCl3 (Table 1) shows a broad signal at d ꢄ
/
25.3
attributable to (1)×2Et2O and two signals at d 31.2 and
/
32.7 with integration ratio 2:1 assignable to the ionic
compound 1a?. Assuming linear geometries for copper
in 1a? the signal with double integration could be
attributed to two PCuOEt2 fragments while the reso-
nance at lower field to one POCuBr moiety. Although
crystals of complex 2 were not achieved from solutions
Et2O (2aꢁ
Cu3(CP3)I3) the 31P{1H} NMR in
/
Au3(CP3)Cl3ꢂCP3 0 [Au3(CP3)2Cl2]Cl
(4)
of 2a×
/
3a
3
DMSO-d6 of this etherate also reveals the presence of
the mononuclear system, 2, besides the iodo derivative
2a? analogous to 1a?. When complex 1a is prepared in
absence of ether its 31P{1H} NMR spectrum in CDCl3
Au3(NP3)Cl3ꢂ2NP3
9a
0 [Au2(NP3)2]Cl2 ꢂAu(NP3)Cl
(5)
(6)
9
shows a broad signal at d ꢄ
/
22.6 (Dd ꢁ
/
12) assignable to
ꢄ2Au(I)Br
1 together with two clearly weaker resonances at d 28.0
and 31.0 probably due to species containing totally and
partially oxidised CP3. Similar results leading to
Cu(CP3)Cl (I) and other compounds (Table 1) seeming
to contain PO, POCuCl, PCuCl and PCuP fragments
(eq. 2) were observed when the 31P{1H} NMR spectrum
of Cu3(CP3)Cl3 (Ia) was recorded in CDCl3.
2Au4(PP3)Br4ꢂ4PP3
0
3[Au2(PP3)2]Br2
14
14a
In all cases starting from neutral polynuclear com-
pounds, with linear PꢀAuꢀX units, the addition of
/
/
polyphosphine produces ring-closure reactions with
formation of ionic complexes containing tetrahedral-
linear (3), trigonal (9) or tetrahedral (14) environments
for Au(I).
When 1 equiv. of CP3 is added to 3 a dicationic
complex [Au3(CP3)3Cl]Cl2 isostructural with 4 and 5
(Scheme 2) seems to be formed via a ring-closure
process. Further additions of the appropriate polypho-
sphine to 9 and 14 result in the formation of complexes
with new ‘‘AuP4’’ arrangements and uncoordinated
dangling phosphorus (Table 1) involving for 14 ring-
opening reactions.
air
4Cu3(CP3)Cl3 0 Cu(CP3)Clꢂ(ClCuOP)C(PCuCl)2
CDCl3
Ia
I
Ia?
ꢂ[(ClCuOP)(OP)CPCuPC(PO)(POCuCl)]Clꢂ5CuCl
Iaƒ
(2)
Thus, solutions in CDCl3 or DMSO-d6 of the systems
0, 1, 2.5) seem to generate the
Cu3(CP3)X3×
/
nE2O (nꢁ
/
mononuclear compounds Cu(CP3)X, its 31P resonance

M.I. Garc´ıa-Seijo et al. / Inorganica Chimica Acta 353 (2003) 206ꢀ
/216
215
Fig. 4. Titrations of Cu(CP3)Cl(I) in CDCl3 and Au4(PP3)Br4 (14a) in CDCl3 ꢀDMSO-d6 with CP3 (A) and PP3 (B), respectively.
/
Scheme 3. Formation of 9 and 10 by reaction of Au3(NP3)X3 [XꢁCl (9a), Br(10a)] with NP3.
/
4. Conclusions
5. Supplementary material
The nature of the tripodal ligand modifies not only
the structures of the resultant complexes, but also their
reactivity. On the other hand, changes in the halogen
lead to different structures in gold complexes with CP3
(3 vs. 4 and 5) and NP3 (9 and 10 vs. 11). Finally,
substitution of copper(I) by gold(I) in complexes with
CP3 or NP3 produce changes in their nuclearity and
ionicity, the nuclearity of both metal complexes with
PP3 being not altered. The closed structures found for
A complete set of X-ray crystallographic studies for
the structures have been deposited with the Cambridge
Crystallographic Data Centre, CCDC 195347 (1),
195348 (7) and 195349 (11). Copies of the data can be
obtained free of charge on application to The Director,
CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK
(fax:
serv@ccdc.cam.ac.uk; e-mail for deposition: depos-
it@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk). Fig. S1 shows the 31P{1H}
NMR spectra in CD2Cl2 for 3, (4)×3H2O and 5 at 183
K. Fig. S2 displays the 31P{1H} NMR spectra for
ꢂ
/
44-1223-336-033; e-mail for inquiry: file-
mononuclear compounds CuLCl lead to a partial (Lꢁ
CP3) or total (LꢁNP3) retention of the CuP3 arrange-
ments by addition of the corresponding polyphosphine.
/
/
/

216
M.I. Garc´ıa-Seijo et al. / Inorganica Chimica Acta 353 (2003) 206ꢀ216
/
[13] S.J. Berners-Price, P.J. Sadler, Inorg. Chem. 25 (1986)
3822.
Cu3(CP3)X3 complexes in CDCl3 (Xꢁ
DMSO-d6 (XꢁI) with and without solvation. Figs. S3
and S4 contain the titrations followed by 31P{1H} NMR
of complexes 3a (CDCl3) and 9a (CDCl3ꢀDMSO-d6),
/
Cl, Br) or
/
[14] B.J. Gregory, C.K. Ingold, J. Chem. Soc., Sect.
276.
B (1969)
/
[15] M.I. Garc´ıa-Seijo, A. Habtemariam, P. del S. Murdoch, R.O.
Gould, M.E. Garc´ıa-Ferna´ndez, Inorg. Chim. Acta 335 (2002) 52.
[16] P. Sevillano, M.E. Garc´ıa, A. Habtemariam, S. Parsons, P.J.
Sadler, Met. Based Drugs 6 (1999) 211.
respectively with the appropriate polyphosphine.
[17] J. Zank, A. Schier, H. Schmidbaur, Z. Naturforsch. 52 (1997)
1471.
[18] J. Cosier, A.M. Glaze´, J. Appl. Crystallogr. 19 (1986) 205.
Acknowledgements
We thank Xunta de Galicia for financial support.
Crystallographic data for complex 1 were measured at
the University of Edinburgh, UK and intensity mea-
surements of crystals for complexes 7 and 11 were
performed at the Unidade de Raios X, RIAIDT,
University of Santiago de Compostela, Spain.
[19] SMART and SAINT
, Area Detector Control and Integration
Software, Analytical X-ray Instruments Inc, Madison, WI,
USA, 1997.
[20] G.M. Sheldrick, SADABS, Program for Empirical Absorption
Correction of Area Detector Data, University of Gottingen,
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[21] G.M. Sheldrick, SHELX-97, An Integrated System for Solving and
Refining Crystal Structures from Diffraction Data, University of
Gottingen, Germany, 1997.
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[22] A. Altomare, G. Cascatano, C. Giacovazzo, A. Guagliardi, J.
Appl. Crystallogr. 26 (1993) 343.
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