S. Muñoz et al. / Journal of Organometallic Chemistry 696 (2011) 2736e2741
2737
photographic applications (less used nowadays for the increase of
new technologies) and finally of gold for its organometallic appli-
cations [25].
In order to enlarge the few quantity of structures of Cu(I) and
Ag(I) published and to increase knowledge of the coordination
behaviour of metals of Group 11 with oxidation state þ1 against
N-pyrazole, P-phosphine ligands, in this paper we present the
synthesis and characterisation of complexes of Cu(I), Ag(I) and
Au(I) with the ligand (3,5-dimethyl-1H-pyrazol-1-yl)ethyldiphenyl-
phosphine (L) [14].
n
(CeH)ar, 2922,
n
(CeH)al, 1550
n
(C]C/C]N)ar, 1432
d
(C]C/C]N)ar,
838
n(PeF), 739, 698
d
(CeH)oop. 1H NMR (CDCl3 at 298 K, 250 MHz):
d
¼ 7.59e7.17 (m, 20H, C6H5), 5.77 (s, 2H, pz-CH), 4.43 (br, 4H, pz-
CH2CH2eP), 2.77 (br, 4H, pz-CH2CH2eP), 2.34 (s, 6H, pz-CH3), 1.39
(s, 6H, pz-CH3) ppm. 13C{1H} NMR (CDCl3 at 298 K, 63 MHz)
: 148.7,
d
140.9 (pzCeCH3), 132.4e127.1 (C6H5), 105.1 (pz-CH), 42.4 (pz-
CH2CH2eP), 26.9 (pz-CH2CH2eP), 12.3, 10.6 (pz-CH3) ppm. 31P{1H}
NMR (CDCl3 at 298 K, 81 MHz)
d: ꢀ14.2 (s, P(C6H5)2), ꢀ146.8 (sp,
1JFP ¼ 706 Hz, PF6ꢀ) ppm.
2.2.2. [Ag(L)]2(PF6)2$2C2H4Cl2$2C4H10O (2)
2. Experimental
A solution of L (0.325 mmol, 0.100 g) dissolved in dry CH2Cl2
(10 mL) was added to a solution of AgPF6 (0.320 mmol, 0.081 g) in
dry CH2Cl2 (15 mL) protected from light. The mixture was stirred
during 12 h and the solution was concentrated to dryness and
washed with cold dry diethyl ether. The white powder obtained
corresponds to 2. The complex was then crystallised in a 1,2-
dichloroethane/diethyl ether mixture (1:10). Complex 2 decom-
poses slowly in solid or solution to [Ag(L)]2(PF2O2)2.
2.1. General details
All reactions were performed with the use of vacuum line and
Schlenk techniques. All reagents were commercial grade and were
used without further purification. All solvents were dried and
distilled by standard methods when it was necessary. The elemental
analyses (C, H, N) were carried out by the staff of the Chemical
Analyses Service of the Universitat Autònoma de Barcelona, or in the
University of Leeds microanalytical service, using a Carlo Erba CHNS
EA-1108 instrument separated by chromatographic column and
thermoconductivity detector. Conductivity measurements were
performed at room temperature in 10ꢀ3 M acetonitrile solutions
Yield: 30%, 0.096 mmol, 0.054 g. Anal. Calc. for
C38H42N4P4F12Ag2$2C2H4Cl2$2C4H10O: C, 40.89; H, 4.80; N, 3.82.
Found C, 41.27; H, 4.42; N, 3.74%. Conductivity (1.05 ꢁ 10ꢀ3 M in
acetonitrile): 211
U
ꢀ1cm2 molꢀ1. MS [ESI (þ)]: m/z (%) 723 (100%)
[AgL2]þ. IR: (KBr, cmꢀ1) 3055
n
(CeH)ar, 2922
n
(CeH)al, 1554
n
(C]C/
C]N)ar, 1437 d(C]C/C]N)ar, 841 n(PeF), 743, 695 d(CeH)oop.
NMR (CD3CN at 298 K, 250 MHz):
1H
employing
a
CyberScan CON 500 (Eutech instrument) con-
d
¼ 7.85e7.17 (m, 20H, C6H5), 5.74
ductimeter. Infrared spectra were run in a Perkin Elmer FT-2000
spectrophotometer as KBr pellets. The 1H, 13C{1H} and 31P{1H}
NMR spectra and bidimensional NMR spectra were run on an NMR-
FT Bruker AC-250 spectrometer. All NMR experiments were recor-
ded on CDCl3 or CD3CN solvents under nitrogen. 1H and 13C{1H}
(s, 2H, pz-CH), 4.22 (m, 4H, pz-CH2CH2eP), 2.70 (m, 4H, pz-
CH2CH2eP), 2.10 (s, 6H, pz-CH3), 2.01 (s, 6H, pz-CH3) ppm. 13C{1H}
NMR (CD3CN at 298 K, 63 MHz)
d: 148.9, 141.9 (pzCeCH3),
2
133.7e128.7 (C6H5), 106.4 (pz-CH), 45.2 (d, JPC ¼ 9.9 Hz, pz-
1
CH2CH2eP), 28.2 (d, JPC ¼ 17.3 Hz, pz-CH2CH2eP), 13.2, 10.6 (pz-
NMR chemical shifts (
d
) were determined relative to internal TMS
CH3) ppm. 31P{1H} NMR (CD3CN at 298 K, 81 MHz)
d: ꢀ1.4 (s,
and are given in ppm. 31P{1H} NMR chemical shifts (
d) were
P(C6H5)2), ꢀ17.2 (t, JFP ¼ 952, PF2O2ꢀ), ꢀ146.8 (sp, JFP ¼ 706 Hz,
1
1
determined relative to external 85% H3PO4 and are given in ppm.
Electrospray Mass spectra (ESIþ) were carried out by the staff of the
Chemical Analysis Service of the Universitat Autònoma de Barcelona
in an Esquire 3000 ion trap mass spectrometer from Bruker Dal-
tonics. Mass experiments were done on CH3CN solvent. Matrix
assisted laser desorption/ionization (MALDI) time-of-flight (TOF)
mass spectrometry were carried out by the staff of the Institut de
Biotecnologia i Medicina of the Universitat Autònoma de Barcelona
on a positive ion mode on a Bruker-Daltonics Ultraflex time-of-
flight instrument. Ion acceleration was set to 25 kV. All mass
spectra were externally calibrated using a standard peptide mixture.
The sample was dissolved in CHCl3 and mixed with 2,5-dihydrox-
PF6ꢀ) ppm.
2.2.3. [AuCl(L)]2 (3)
A solution of L (0.325 mmol, 0.100 g) dissolved in dry CH2Cl2
(10 mL) was added to a solution of [AuCl(SC4H8)] (0.320 mmol,
0.103 g) in dry CH2Cl2 (15 mL). The mixture was stirred during 12 h
and the solution was concentrated to dryness and washed with cold
dry diethyl ether. The white powder obtained corresponds to 3.
Yield: 90%, 0.288 mmol, 0.156 g. Anal Calc. for
C38H42N4P2Cl2Au2: C, 42.20; H, 3.91; N, 5.18. Found C, 41.95; H, 3.72;
N, 4.88%. Conductivity (1.09
ꢁ
10ꢀ3
M in acetonitrile):
14
U
ꢀ1cm2 molꢀ1. MS [ESI (þ)]: m/z (%) 1045 (100%) [Au2ClL2]þ, 813
ybenzoic acid (DHB) solution matrix (0.5
ml sample:0.5
ml matrix).
(35%) [AuL2]þ. IR: (KBr, cmꢀ1) 3047
n(CeH)ar, 2959 n(CeH)al, 1552
The mixed solution was applied on a ground steel plate (1
m
l).
n
(C]C/C]N)ar, 1435
d
(C]C/C]N)ar, 800
n
(PeC), 742, 690
¼ 7.92e7.04 (m,
The precursor complex AgPF6 is commercially available,
[Cu(CH3CN)4](PF6) [26] and [AuCl(SC4H8)] [27] and the ligand 2-
(3,5-dimethyl-1H-pyrazol-1-yl)ethyldiphenylphosphine (L) [14]
were prepared as described in the literature.
d
(CeH)oop. 1H NMR (CDCl3 at 298 K, 250 MHz):
d
20H, C6H5), 5.61 (s, 2H, pz-CH), 4.27 (m, 4H, pz-CH2CH2eP), 3.01 (m,
4H, pz-CH2CH2eP), 2.12 (s, 6H, pz-CH3), 2.08 (s, 6H, pz-CH3) ppm.
13C{1H} NMR (CDCl3 at 298 K, 63 MHz)
d: 148.5, 140.0 (pzCeCH3),
2
134.3e127.9 (C6H5), 106.1 (pz-CH), 44.6 (d, JPC ¼ 7.9 Hz, pz-
2.2. Synthesis and characterisation of complexes 1e3
CH2CH2-P), 29.6 (d, 1JPC ¼ 36.8 Hz, pz-CH2CH2-P), 13.7, 11.8 (pz-CH3)
ppm. 31P{1H} NMR (CDCl3 at 298 K, 81 MHz)
ppm.
d
: þ22.9 (P(C6H5)2)
2.2.1. [Cu(L)2](PF6) (1)
A solution of L (0.325 mmol, 0.100 g) dissolved in dry CH2Cl2
(10 mL) was added to a solution of [Cu(CH3CN)4](PF6) (0.160 mmol,
0.060 g) in dry CH2Cl2 (15 mL). The mixture was stirred during 12 h,
the solution was concentrated to 5 mL and precipitated with 5 mL
of cold dry diethyl ether. Filtration of the powder leads a white solid
that corresponds to 1. The complex was then crystallised in an
acetone/diethyl ether mixture (1:10).
2.3. X-ray crystal structures of 1 and 2
Suitable colourless crystals for X-ray diffraction of 1 and 2 were
obtained from solutions of 1 in acetone and 2 in 1,2-dichloroethane
by slow diffusion of diethyl ether vapour (1:10). Diffraction data for
1 were measured using a Bruker X8 Apex diffractometer, with
Yield: 80%, 0.134 mmol, 0.106 g. Anal. Calc. for C38H42N4P3F6Cu:
C, 55.31; H, 5.13; N, 6.79. Found C, 55.20; H, 5.15; N, 6.65%. MS
(MALDI-TOF): m/z (%) 679 (100%) [CuL2]þ. IR: (KBr, cmꢀ1) 3055
graphite-monochromated Mo-Ka radiation (
ated by a rotating anode. Diffraction data for 2 were carried out on
a Nonius KappaCCD area detector diffractometer, using graphite-
l
¼ 0.71073 Å) gener-