Solid-state and solution structural properties of copper(I) compounds with bidentate phosphane ligands

Article abstract of DOI:10.1002/(sici)1099-0682(199905)1999:5<777::aid-ejic777>3.0.co;2-a

The copper(I) compounds [Cu(dppe)₂]X [X = BF₄-, I^-; dppe = 1,2- bis(diphenylphosphanyl)ethane], [Cu(dppp)₂]X [X = BF₄-, I-; dppp = 1,3- bis(diphenylphosphanyl)propane], [Cu₂(dppe)₃I₂], and [Cu₂(dppe)₂I₂] have been prepared and their structural properties in solution and in the solid state have been determined. ¹H-, ¹³C-, and ³¹P-NMR spectra in solution [variable temperature and anion (I-) concentrations] and analyses of solids (mass spectra, elemental analyses, and CPMAS ³¹P-NMR spectra) are interpreted with equilibria in solution that involve two mono- and two dinuclear species. The structures of [Cu(dppe)₂]CIO₄, [Cu(dppp)₂]BF₄, and [Cu₂(dppe)₃I₂] · 2 CHCI₃ have been analyzed by X-ray crystallography. In all three structures the copper(I) center adopts a distorted tetrahedral geometry.

Full text of DOI:10.1002/(sici)1099-0682(199905)1999:5<777::aid-ejic777>3.0.co;2-a

FULL PAPER
Solid-State and Solution Structural Properties of Copper(I) Compounds
with Bidentate Phosphane Ligands
Peter Comba,*[a] Charis Katsichtis,[a] Bernd Nuber,[a] and Hans Pritzkow[a]
Keywords: Copper / Phosphane / Solution structure / P ligands / NMR spectroscopy / Coordination chemistry
The copper(I) compounds [Cu(dppe)2]X [X = BF4–, I–; dppe =
analyses of solids (mass spectra, elemental analyses, and
CPMAS 31P-NMR spectra) are interpreted with equilibria in
–
1,2-bis(diphenylphosphanyl)ethane], [Cu(dppp)2]X [X = BF4 ,
I–; dppp
=
1,3-bis(diphenylphosphanyl)propane], [Cu2- solution that involve two mono- and two dinuclear species.
(dppe)3I2], and [Cu2(dppe)2I2] have been prepared and their
structural properties in solution and in the solid state have
been determined. 1H-, 13C-, and 31P-NMR spectra in solution
[variable temperature and anion (I–) concentrations] and
The structures of [Cu(dppe)2]ClO4, [Cu(dppp)2]BF4, and
[Cu2(dppe)3I2] · 2 CHCl3 have been analyzed by X-ray
crystallography. In all three structures the copper(I) center
adopts a distorted tetrahedral geometry.
CH2Cl2 yields the compounds [Cu(dppp)2]BF4 (5) and
[Cu(dppp)2]I (6), respectively. X-ray quality crystals of 1 (as
the perchlorate salt), 3 (with two disordered chloroform
molecules in the lattice), and 5 were obtained by vapor dif-
fusion of diethyl ether into a solution of the complexes in
CH2Cl2 or CHCl3. The solids were studied by X-ray dif-
fractometry, mass spectrometry, elemental analysis,
Introduction
Detailed structural studies and the understanding of
solution equilibria and dynamics of copper(I) compounds
of bidentate phosphanes are of importance due to their po-
tential application as potent antitumor agents[1] and as free
radical scavengers in industrial processes.[2][3] There are a
number of published studies of solution equilibria and
structures that involve copper(I) compounds with phos-
phane ligands with variable copper(I)-to-ligand ratios.[4]
Similar equilibria have also been observed for silver(I) com-
pounds of bidentate phosphane ligands.[5] Mononucle-
ar[4e,4g,4iϪ4j,4l,4m,4p] and dinuclear phosphanecopper(I) com-
pounds[4aϪ4d,4k,4n,4o,4q] with coordinated and bridging hal-
ide anions and with phosphane ligands in various coordi-
nation modes have been isolated and characterized. There
is spectroscopic evidence that some of the structurally
characterized solids lead to complex equilibria in solution.
However, so far there is only relatively little thorough infor-
mation on structures and dynamics in solution.[1,4f] Here we
report our results from studies on the structural properties
of copper(I) compounds of dppe and dppp in the solid state
and in solution.
1
CPMAS 31P-NMR and IR spectroscopy. H, 13C, and 31P
NMR was used to establish the solution structures of the
compounds.
ORTEP[6] plots of the experimentally determined struc-
tures of [Cu(dppe)2]ClO4 (1), [Cu2(dppe)3I2] (3), and
[Cu(dppp)2]BF4 (5) are presented in Figure 1, and selected
structural parameters are given in Table 1. As expected, the
copper(I) center adopts a distorted tetrahedral geometry in
these structures. The copper(I)Ϫphosphane distances are in
the range expected from other known structures[4b,4e,4g,4r]
but there is a rather large variation in the individual dis-
tances, also within each complex. The degree of distortion
from tetrahedral geometry depends primarily on the chelate
ring size (dppe vs. dppp), with bite angles of the five-mem-
bered chelate rings of approximately 90° and bite angles of
the six-membered rings of approximately 98°, and this leads
to a flattening of the tetrahedral chromophores (deviation
of the angles θ in Table 1 from 90°). All chelate rings are
puckered, and the six-membered rings have the expected
chair conformations.
Results and Discussion
Syntheses and Properties of the Solids
There is no crystal structural analysis of [Cu2(dppe)2I2]
(4). The structural assignment given in Scheme 1 is based
on the reported structures of [Cu2(dppf)2I2][7] [dppf: 1,1Ј-
bis(diphenylphosphanylferrocene)] and [Cu2(PhPH2)4I2][8]
(PhPH2: phenylphosphane). The signals in the CPMAS 31P-
NMR spectra of the copper(I) complexes are rather broad,
due to distortion from tetrahedral symmetry, unresolved
coupling to the copper nuclei, quadrupole interactions in-
volving the copper centers and the presence of two isotopes
(63Cu, 65Cu);[9] nevertheless, the observed spectra (see Table
2 for chemical shift data) are qualitatively in good agree-
Reaction of [Cu(CH3CN)4]BF4 with dppe in CH2Cl2 in
a 1:2 ratio yields [Cu(dppe)2]BF4 (1). [Cu(dppe)2]I (2),
[Cu2(dppe)3I2] (3), and [Cu2(dppe)2I2] (4) are prepared un-
der similar conditions from CuI and dppe in CH2Cl2 or
CHCl3 (1:2, 2:3, and 1:1 CuI-to-ligand ratios). Reaction of
dppp with [Cu(CH3CN)4]BF4 and CuI in a 2:1 ratio in
[a]
Anorganisch-Chemisches Institut der Universität,
Im Neuenheimer Feld 270, D-69120 Heidelberg, Germany,
Fax: (internat.) ϩ 49(0)6221/546617
E-mail: comba@akcomba.oci.uni-heidelberg.de
Eur. J. Inorg. Chem. 1999, 777Ϫ783
WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999
1434Ϫ1948/99/0505Ϫ0777 $ 17.50ϩ.50/0
777

P. Comba, C. Katsichtis, B. Nuber, H. Pritzkow
FULL PAPER
Table 1. Selected structural parameters of [Cu(dppe)2]ClO4 (1),
[Cu(dppp)2]BF4 (5), and [Cu2(dppe)3I2] · 2 CHCl3 (3)
Parameter
[Cu(dppe)2]ClO4 [Cu(dppp)2]BF4 [Cu2(dppe)3I2] ·
2 CHCl3
˚
˚
˚
Cu(1)ϪP(1)
Cu(1)ϪP(2)
Cu(1)ϪP(3)
Cu(1)ϪP(4)
Cu(1)ϪI(1)
2.259(2) A
2.303(1) A
2.315(2) A
˚
˚
˚
2.301(2) A
2.298(1) A
2.321(2) A
˚
˚
˚
2.300(2) A
2.296(1) A
2.273(2) A
˚
˚
2.270(2) A
2.317(1) A
Ϫ
˚
Ϫ
Ϫ
2.623(1) A
P(1)ϪCu(1)ϪP(2) 90.34(7)°
P(1)ϪCu(1)ϪP(3) 120.38(8)°
P(2)ϪCu(1)ϪP(3) 103.95(8)°
P(3)ϪCu(1)ϪP(4) 90.58(7)°
98.22(5)°
120.29(5)°
122.83(5)°
97.66(5)°
Ϫ
Ϫ
Ϫ
81.44°
77.74°
89.82(8)
116.24(7)
109.70(7)
Ϫ
P(1)ϪCu(1)ϪI(1)
P(2)ϪCu(1)ϪI(1)
P(3)ϪCu(1)ϪI(1)
Ϫ
113.88(6)
116.29(6)
109.79(5)
80.15°
Ϫ
Ϫ
87.69°
[a]
θ1[a]
θ2
74.43°
76.79°
[a]
Tetrahedral twist angles (tetrahedral, θ ϭ 90°; θ2: planes invol-
ving the chelate rings).
1
Table 2. H- and 31P-NMR chemical shifts of CuI compounds of
dppe and dppp
Compound
1H NMR
δ(CH2) [ppm]
31P NMR
δ(P) [ppm]
CPMAS
31P NMR
δ(P) [ppm]
dppe
2.09
Ϫ12.47
Ϫ12.1
dppp
2.21; 1.58
2.46
Ϫ17.18; Ϫ17.26 Ϫ20.5; Ϫ24.4
[Cu(dppe)2]ϩ
[Cu(dppe)(P-
dppe)I]
ϩ7.5
Ϫ9.5
ϩ10.3
Ϫ
Ϫ
[Cu2(dppe)3I2] 2.27
[Cu2(dppe)2I2] 2.56
[Cu(dppp)2]BF4 2.29; 1.62
Ϫ5.0
Ϫ12.5
Ϫ8.5
Ϫ
Ϫ20.0
Ϫ10.1
Ϫ10.0
[Cu(dppp)2]I
2.28; 2.05; 1.64 Ϫ8.8; Ϫ17.5
Equilibria in Solution
dppe Compounds
1
A broad signal at δ ϭ 2.46 is observed in the H-NMR
spectrum of [Cu(dppe)2]BF4 (1) in CD2Cl2. It is assigned to
the methylene protons of the coordinated dppe ligands. The
line broadening suggests unresolved 31P-1H coupling (rel-
evant chemical shift data are assembled in Table 2). The
31P-NMR spectrum of 1 in CD2Cl2 consists of a very broad
signal centered at δ ϭ ϩ7.5. It is assigned to the four phos-
Figure 1. ORTEP[6] plots of the structures of the molecular cations
of [Cu(dppe)2]ClO4 (1), [Cu(dppp)2]BF4 (5), and of the dinuclear
compound [Cu2(dppe)3I2] · 2 CHCl3 (3)
ment with the X-ray structures of 1, 3, 5 (Figure 1), the phorus atoms coordinated to the copper(I) center. Lowering
putative structure of 4 (Scheme 1), published NMR data of of the temperature leads to a significant decrease of ∆ν1/2
[CuP4]ϩ and the structural assignments based on the solu- (2500 Hz at 298 K vs. 250 Hz at 193 K) and a small upfield
tion NMR data (see below).
shift (∆δ ഠ 0.9) of this signal. This variation as a function
of temperature is similar to that reported for
[Cu(dppey)2]ϩ[4p] [dppey ϭ cis-bis(diphenylphosphanyl)-
ethene] and consistent with the line shapes that have been
calculated for fast quadrupolar relaxation[10] of a CuP4
complex. No splitting is observed over the whole tempera-
ture range and the 31P-NMR chemical shifts in the solid
state and in solution are similar (Table 2). This suggests
that only one species is present in solution, that is, the struc-
ture of 1 (see Figure 1) is conserved.
Scheme 1. Putative structure of [Cu2(dppe)2I2] (4) in solid state and
in solution
778
Eur. J. Inorg. Chem. 1999, 777Ϫ783

Solid-State and Solution Structural Properties of Copper(I) Compounds
FULL PAPER
The high-field region of the 1H-NMR spectrum of
[Cu(dppe)2]I (2) is presented in Figure 2. There are three
broad signals at δ ϭ 2.56, 2.46, and 2.26, the latter is split
into two signals at δ ϭ 2.27 and 2.24. Three broad reso-
nances at δ ഠ ϩ7.5, Ϫ5, and Ϫ12.5 are observed in the 31P-
NMR spectrum of 2 (Figure 3a). The signals at δ ϭ 2.46
(1H NMR) and ϩ7.5 (31P NMR) are due to the molecular
cation observed in the solids of 1 and 2, that is, to the struc-
ture that is conserved from the solid state; the other signals
must be due to other species in solution, which is indicative
of a chemical exchange process.
Figure 3. Temperature-dependent 31P-NMR spectra (81 MHz) of
[Cu(dppe)2]I (2) (CDCl3; 85% H3PO4)
1
Figure 2. H-NMR spectrum (200 MHz) of [Cu(dppe)2]I (2) (298
K; CDCl3)
two chelated and one bridging phosphane ligand (Scheme
2). Further addition of dppe leads to decreasing intensity
of the signal at δ ϭ 2.56 (1H NMR), a sharpening of the
signal at δ ϭ Ϫ12.5 (31P NMR) and two additional signals
at δ ϭ 2.46 (1H NMR) and δ ϭ ϩ7.5 (31P NMR). That is,
addition of dppe to [Cu2(dppe)2I2] produces [Cu(dppe)2]ϩ
via [Cu2(dppe)3I2].
From variable-temperature 31P-NMR spectra of 2 (Fig-
ure 3) it emerges that (i) there is a significant decrease in
the line width and a small upfield shift of the signal at δ ϭ
ϩ7.5, assigned to [Cu(dppe)2]ϩ (see above); (ii) there is an
additional multiplet at δ ϭ Ϫ9.5 which has maximum rela-
tive intensity around 240 K; (iii) at lower temperatures the
relative intensity of the signal at δ ϭ ϩ7.5 increases. The
multiplet at δ ϭ Ϫ9.5 is tentatively assigned to a mononu-
clear intermediate with one bidentate and one monodentate
dppe ligand, that is, a species that results from substitution
of one phosphane donor by IϪ. This is consistent with the
chemical shift data (see below and Table 2), the concen-
tration profile (relative intensities, see Figure 3 and above)
and the NMR titration experiments (see below).
1
Scheme 2. Solution structure of [Cu2(dppe)3I2] based on H- and
31P-NMR spectroscopy
There is a broad signal at δ ϭ 2.56 in the 1H-NMR spec-
trum of 4 (see Table 2). This is assigned to the methylene
In a similar experiment 1H- and 31P-NMR spectra of
protons of the bidentate dppe ligands. A broad resonance [Cu2(dppe)3I2] (3) were measured in dependence of the con-
1
at approximately δ ϭ Ϫ12.5 (close to that of the metal-free centration of added dppe. The two signals in the H-NMR
ligand) is observed in the corresponding 31P-NMR spec- spectrum of 3 at δ ϭ 2.46 and 2.27 are assigned to the
trum. A similar observation was made in NMR studies of complexes [Cu(dppe)2]I and [Cu2(dppe)3I2], respectively. In
[Cu2(dppf)2I2], which was characterized by an X-ray crystal the 31P-NMR spectra there are signals at δ ϭ ϩ7.5 and
structure.[7] Addition of metal-free dppe to a solution of 4 Ϫ5.0, respectively. Addition of excess dppe results in the
in CDCl3 leads to additional signals at δ ϭ 2.27 and Ϫ5 in disappearance of the resonances at δ ϭ 2.27 (1H NMR)
the 1H- and 31P-NMR spectra, respectively (Figure 4). and Ϫ5.0 (31P NMR). That is, as expected, the equilibrium
These new signals are tentatively assigned to a species with is shifted towards [Cu(dppe)2]ϩ. Hence, the signals at δ ϭ
Eur. J. Inorg. Chem. 1999, 777Ϫ783
779

P. Comba, C. Katsichtis, B. Nuber, H. Pritzkow
FULL PAPER
Figure 4. 1H- and 31P-NMR spectra (200 MHz, 81 MHz) of [Cu2(dppe)2I2] (4) with different concentrations of added ligand [CDCl3;
298 K; a small amount of impurity at δ(31P) ഠ 33 is due to phosphane oxide]
2.27 (1H NMR) and Ϫ5.0 (31P NMR) are assigned to the dppp Compounds
same compound, that is, to [Cu2(dppe)3I2].
The observations from temperature-dependent and li-
Two broad signals for [Cu(dppp)2]BF4 (5) with an inten-
gand-concentration-dependent 1H-NMR and 31P-NMR sity ratio of 2:1 are observed in the H-NMR spectrum at
data, and observations based on the solid-state samples are δ ϭ 2.29 and 1.62 (methylene groups of the coordinated
assembled in Scheme 3. The mononuclear compound dppp ligands). A broad signal at δ ϭ Ϫ8.5 (upfield shift of
[Cu(dppe)2]I is in equilibrium with the putative interme- approximately 8.7 ppm with respect to the metal-free li-
diate [Cu(dppe)(P-dppe)I], which only is observed at low gand) is observed in the 31P-NMR spectrum of 5 in
temperature. Dissociation of one or two ligand molecules CD2Cl2. This is assigned to the four coordinated phos-
leads to the dinuclear compounds [Cu2(dppe)3I2] and phorus atoms. The 31P-chemical shifts in the solid state and
[Cu2(dppe)2I2], respectively, which have been observed in in solution are similar (see Table 2) and thus the structure
1
the solid.
of 5 (see Figure 1) is conserved in solution.
Scheme 3. Proposal for the solution equilibria of copper(I) compounds of dppe with two mono- and two dinuclear species
780 Eur. J. Inorg. Chem. 1999, 777Ϫ783

Solid-State and Solution Structural Properties of Copper(I) Compounds
FULL PAPER
In the high-field region of the 1H-NMR spectrum of groups of the six-membered ring in a frozen chair confor-
[Cu(dppp)2]I (6) in CD2Cl2 there are multiplets at δ ϭ 2.28 mation. This is in agreement with the two signals in the
and 1.64 and some signals of lower intensity at δ ϭ 2.05. 31P-NMR spectrum, and these may be assigned to the two
The 31P-NMR spectrum has a broad signal at δ ϭ Ϫ8.80 nonequivalent phosphorus atoms of the bidentate ligand.
1
and a signal at Ϫ17.5. The low-intensity signals in the H- This interpretation is also supported by the [13C-1H] spec-
and 31P-NMR spectra of 6 suggest that chemical exchange trum of 5 in CD2Cl2.
processes, similar to those of [Cu(dppe)2]I, take place. Un-
fortunately, the proximity of the 31P-NMR signals, due to
the smaller chemical shift of the six-membered ring
bisphosphane compounds, makes an identification of inter-
mediate compounds in the region between δ ϭ Ϫ8 and
Ϫ17.5 difficult. Thus, a thorough investigation of the solu-
Experimental Section
Materials: 1,2-Bis(diphenylphosphanyl)ethane (dppe) and 1,3-
bis(diphenylphosphanyl)propane (dppp) were purchased from Ald-
rich; CuI was obtained from Fluka and Cu(BF4)2 · x H2O from
tion equilibrium was not appropriate.
ABCR Chemicals.
The low-temperature 31P-NMR spectrum of [Cu-
(dppp)2]BF4 (5) in CD2Cl2 (Figure 5) has features that are
significantly different from those of [Cu(dppe)2]BF4 (1) (see
Table 2). Below 213 K the signal at δ ϭ Ϫ8.5 splits into
two signals (δ ϭ Ϫ5.84 and Ϫ10.36 at 193 K). The iodine
salt 6 in CD2Cl2 leads to identical spectroscopic results; the
signal at δ ϭ Ϫ17.5 (room temperature) disappears at low
temperature (193 K). An interpretation of these obser-
vations emerges from temperature-dependent 1H-NMR
spectroscopy. The two signals at δ ϭ 2.29 and 1.62 (CD2Cl2,
298 K), assigned to the methylene protons of 5, are split
into five signals at δ ϭ 2.85, 2.53, 2.20, 1.47, and 0.88
(CD2Cl2, 193 K) with an intensity ratio of 1:1:2:1:1. The
13C-NMR spectrum (CD2Cl2, 193 K) has three signals at
δ ϭ 26.97, 25.91, and 16.62. These may be assigned to the
three chemically and magnetically nonequivalent methylene
Measurements: 1H-, 13C-, and 31P-NMR spectra at 200.13 or
300.13, 50.32 or 75.47, and 81.03 or 121.5 MHz, respectively, were
measured with a Bruker AS 200 or a Bruker WH300 instrument
with dichloromethane or chloroform as internal reference. H3PO4
(85%) was used as external reference for 31P-NMR spectra. The
1H-COSY and [13C-1H] spectra at 500.13 and 125.77 MHz were
obtained with a Bruker Advance 500 instrument. Ϫ Infrared spec-
tra (KBr pellets) were measured with a Perkin-Elmer 16PC FT-IR
instrument. Ϫ Elemental analyses were obtained from the micro-
analytical laboratory of the chemical institutes of the University of
Heidelberg. Ϫ Mass spectra (FAB or FD) were measured with a
Finnigan 8400 (nitrobenzyl alcohol matrix) or a Jeol JMS-700 in-
strument.
Syntheses: All manipulations were carried out under Ar, using
standard Schlenk techniques. CH2Cl2, CHCl3, and diethyl ether
were degassed by bubbling Ar through the solutions for 20 min.
[Cu(CH3CN)4]BF4 was prepared as reported in the literature.[11]
[Cu(dppe)2]BF4 ·0.5 H2O (1): [Cu(CH3CN)4]BF4 (0.395 g, 1.26
mmol) was dissolved in CH2Cl2 (4 mL). The ligand dppe (1 g, 2.51
mmol) in CH2Cl2 (6 mL) was added (15 min) and the solution was
stirred for 15 min at room temperature. After removing approxi-
mately 6 mL of the solvent and adding diethyl ether (10 mL), the
solution was kept at Ϫ15°C over night. The resulting white precipi-
tate was filtered off, recrystallized from methanol/water, and dried
in vacuo. Yield (recrystallized): 0.63 g (0.66 mmol; 52%). Ϫ
C52H48BCuF4P4 · 0.5 H2O (956.2): calcd. C 65.32, H 5.16, P 12.96;
found C 65.43, H 5.13, P 13.03. Ϫ IR (KBr): ν˜ [cmϪ1] ϭ 3050 (m,
CarϪH), 2918 (m, CH2) 1482 (m, CarϭCar), 1434 (s, PϪPh), 1054
(s, BF4Ϫ), 740, 694 (s, CarϪH, 5 H neighboring). Ϫ MS (FAB); m/z
(%): 859 (100) [M Ϫ BF4], 646 (7) [M Ϫ BF4 Ϫ CH2CH2PPh2],
461 (98) [M Ϫ BF4 Ϫ CH2CH2PPh2 Ϫ PPh2].
[Cu(dppe)2]I·0.5 H2O (2): A solution of dppe (1 g, 2.51 mmol) in
CHCl3 (6 mL) was slowly added to a suspension of CuI (0.239 g,
1.26 mmol) in CHCl3 (2 mL). After stirring for 45 min, a pale
yellow solution was obtained. The volume was reduced to 2 mL
and diethyl ether was carefully added, until a white solid started to
precipitate. After keeping at Ϫ15°C over night, the white precipi-
tate was filtered off, recrystallized from methanol/water, and dried
in vacuo. Yield (recrystallized): 0.43 g (0.43 mmol; 34%). Ϫ
C52H48CuIP4 · 0.5 H2O (996.3): calcd. C 62.69, H 4.96, P 12.44;
found C 62.42, H 4.97, P 12.33. Ϫ IR (KBr): ν˜ [cmϪ1] ϭ 3044 (m,
CarϪH), 2924 (m, CH2) 1480 (m, CarϭCar), 1432 (s, PϪPh), 740,
700 (s, CarϪH, 5 H neighboring).
[Cu2(dppe)3I2] (3): A solution of dppe (1 g, 2.51 mmol) in CH2Cl2
(2 mL) was added to a suspension of CuI (0.319 g, 1.67 mmol) in
CH2Cl2 (8 mL). The resulting colorless solution was stirred for 15
min, when a white solid started to precipitate. After storage at
Figure 5. Temperature-dependent 31P-NMR spectra (81 MHz) of
[Cu(dppp)2]BF4 (5) (CD2Cl2; 85% H3PO4)
Eur. J. Inorg. Chem. 1999, 777Ϫ783
781

P. Comba, C. Katsichtis, B. Nuber, H. Pritzkow
Table 3. Crystallographic data for [Cu(dppe)2]ClO4 (1), [Cu2(dppe)3I2] · 2 CHCl3 (3), and [Cu(dppp)2]BF4 (5)[13]
FULL PAPER
Empirical formula
Formula mass
C52H48ClCuO4P4
959.8
C80H74Cl6Cu2I2P6
1814.9
C54H52BCuF4P4
975.3
Crystal dimensions [mm]
Crystal system
0.60 ϫ 0.50 ϫ 0.50
monoclinic
12.169(3)
40.640(9)
19.738(5)
90
0.95 ϫ 0.45 ϫ 0.30
triclinic
0.60 ϫ 0.55 ϫ 0.40
monoclinic
17.432(3)
15.273(3)
18.209(4)
90
˚
a [A]
11.828(4)
12.341(7)
15.691(8)
77.03(5)
71.64(3)
67.47(4)
1993.8(17)
PϪ1
˚
b [A]
˚
c [A]
α [°]
β [°]
γ [°]
97.25(2)
90
99.86(2)
90
Ϫ3
˚
V [A
]
9683.3(40)
P21/c
4776.3(16)
P21/c
Space group
Z
8
2
4
Calcd. density [g cmϪ3
]
1.317
1.511
1.356
Absorption coeff. [mmϪ1
F(000)
]
0.682
1.671
0.644
3984
910
2024
θ range [°]
1.69Ϫ22.50
Mo-Kα (0.71073)
0.062
1.80Ϫ28.81
Mo-Kα (0.71073)
0.072
1.75Ϫ25.00
Mo-Kα (0.71073)
0.061
˚
Radiation (λ [A])
R1[a] [I > 2σ(I)]
wR2[b] (all data)
No. of reflections
Measured
0.158
0.186
0.151
13116
12449 [R(int) ϭ 0.032]
8133
1150
1.131
10401
10400 [R(int) ϭ 0.023]
6652
444
1.057
8702
Unique
8411 [R(int) ϭ 0.060]
Obsd. [I > 2σ(I)]
No. of variables
Goodness of fit on F2
6067
782
1.063
R1 ϭ ΣԽԽFoԽ Ϫ ԽFcԽԽ/ΣԽFoԽ. Ϫ wR2 ϭ [(Σw(ԽFoԽ Ϫ ԽFcԽ)2/ΣwFo2)]1/2
.
[a]
[b]
Ϫ15°C over night, the product was filtered off, recrystallized from
[Cu(dppp)2]I·0.5 H2O (6): A white suspension of CuI (0.231 g, 1.21
methanol/water, and dried in vacuo. Yield (recrystallized): 0.8 g mmol) in CH2Cl2 (2 mL) was added to a solution of dppp (1 g,
(0.51 mmol; 61%). Ϫ C78H72Cu2I2P6 (1576.2): calcd. C 59.43, H
4.60, P 11.80; found C 59.72, H 4.77, P 11.63. Ϫ IR (KBr): ν˜
[cmϪ1] ϭ 3046 (m, CarϪH), 2902 (w, CH2) 1482 (s, CarϭCar), 1432
(s, PϪPh), 747, 705 (s, CarϪH, 5 H neighboring). Ϫ MS (FD); m/z
2.43 mmol) in CH2Cl2 (6 mL). After stirring for 15 min, a colorless
solution was obtained. Addition of diethyl ether and storage at
Ϫ15°C over night resulted in a white precipitate, which was filtered
off, recrystallized from methanol/water, and dried in vacuo. Yield
(recrystallized): 1.03 g (1.00 mmol; 83%). Ϫ C54H52CuIP4 · 0.5 H2O
(1824.3): calcd. C 63.32, H 5.21, P 12.09; found C 63.24, H 5.14,
P 12.12. Ϫ IR (KBr): ν˜ [cmϪ1] ϭ 3047 (m, CarϪH), 2912 (m, CH2)
1489 (m, CarϭCar), 1439 (s, PϪPh), 746, 699 (s, CarϪH, 5 H
neighboring).
(%): 1449 (5) [M
Ph2PCH2CH2PPh2, 63/65Cu], 859 (100) [M
Ph2PCH2CH2PPh2
CuI, 63/65Cu], 461 (5) [M
Ϫ
I, 63/65Cu], 1051 (17) [M
Ϫ
I
Ϫ
Ϫ
Ϫ
Ϫ
I
Ϫ
Ϫ
I
Ph2PCH2CH2PPh2 Ϫ CuI Ϫ Ph2PCH2CH2 Ϫ PPh2, 63/65Cu].
[Cu2(dppe)2I2]·0.2 CH2Cl2 (4): A suspension of CuI (0.239 g, 1.26
mmol) in CH2Cl2 (2 mL) was treated with a solution of dppe (0.5
g, 1.26 mmol) in CH2Cl2 (3 mL). After addition of CHCl3 (5 mL)
and stirring for 30 min at room temperature, diethyl ether was lay-
ered onto the colorless solution, which was kept over night at
Structure Determinations: Intensity-measurement data were ob-
tained with a Syntex R3 diffractometer, using Mo-Kα radiation and
operating in the ω-scan mode at room temperature. Data were cor-
rected for Lp and absorption effects (ψ scan). The structures were
Ϫ15°C. The white precipitate was filtered off, washed with cold solved by direct methods (SHELXS 86[12a]) and refined by full-
diethyl ether, and dried in vacuo. Yield: 0.85 g (0.72 mmol; 57%).
Ϫ C52H48Cu2I2P4 · 0.2 CH2Cl2 (1194.7): calcd. C 53.03, H 4.11, P anisotropic thermal parameters for all non-hydrogen atoms. Hydro-
10.52; found C 51.94, H 4.06, P 10.22. Ϫ IR (KBr): ν˜ [cmϪ1] ϭ
gen atoms were placed in calculated positions, but their parameters
3043 (m, CarϪH), 2924 (m, CH2) 1481 (m, CarϭCar), 1432 (s, were not refined. The CHCl3 solvent molecules in [Cu2(dppe)3I2] ·
matrix least-squares methods based on F2 (SHELXL 97[12b]), using
Ϫ
PϪPh), 1096 (s, CarϭCar), 739, 692 (s, CarϪH, 5 H neighboring).
2 CHCl3 and the BF4 anion in [Cu(dppp)2]BF4 are disordered.
Ϫ MS (FAB); m/z (%): 1051 (6) [M Ϫ I, 63/65Cu], 859 (100) [M Ϫ
The crystallographic data for [Cu(dppe)2]ClO4, [Cu2(dppe)3I2] · 2
I Ϫ CuI], 653 (39) [M Ϫ I Ϫ Ph2PCH2CH2PPh2, 63/65Cu], 461 (70) CHCl3 and [Cu(dppp)2]BF4 are summarized in Table 3.
[M Ϫ I Ϫ CuI Ϫ Ph2PCH2CH2PPh2].
[Cu(dppp)2]BF4 (5): A pale yellow solution of dppp (1 g, 2.43 mmol)
in CH2Cl2 (5 mL) was slowly added to
a solution of
Acknowledgments
[Cu(CH3CN)4]BF4 (0.382 g, 1.21 mmol) in CH2Cl2 (4 mL). After
stirring for 15 min, the volume was reduced to 5 mL and diethyl
ether was layered onto the solution. The resulting gum was solidi-
fied by scratching in ice-cold CH2Cl2, recrystallized from methanol/
water, and dried in vacuo. Yield (recrystallized): 0.91 g, (0.93 mmol;
77%). Ϫ C54H52BCuF4P4 (975.3): calcd. C 66.50, H 5.37, P 12.70;
found C 66.03, H 5.34, P 12.61. Ϫ IR (KBr): ν˜ [cmϪ1] ϭ 3064 (m,
CarϪH), 2929 (m, CH2) 1498 (m, CarϭCar), 1439 (s, PϪPh), 1067
(s, BF4Ϫ), 746, 704 (s, CarϪH, 5 H neighboring). Ϫ MS (FAB); m/z
(%): 887 (51) [M Ϫ BF4], 475 (100) [M Ϫ BF4 Ϫ Ph2P(CH2)3PPh2].
We are grateful to Dr. Voelkel (BASF) for the CPMAS 31P-NMR
spectra, to Dr. Schilling for the HH- and CH-COSY spectra of
[Cu(dppp)2]BF4 and to the BASF AG, Ludwigshafen, for finan-
cial support.
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