Versatility of dithiophosphates in the syntheses of copper(I) complexes with bis(diphenylphosphino)alkanes: Abstraction of chloride from dichloromethane

Article abstract of DOI:10.1021/ic051166+

Reactions of [Cu(CH₃CN)₄]X (X = PF₆, BF₄) with bis(diphenylphosphino)methane (dppm = Ph ₂PCH₂PPh₂) and ammonium dialkyldithiophosphates, (NH₄)[S₂P(OR)₂] (R = Et, ⁱPr), yield a series of novel Cu^l polynuclear complexes, trinuclear [Cu₃(μ-dppm)₃(μ₃- Cl){S₂P(OEt)₂}] (PF₆) 1 and [Cu ₃(μ-dppm)₂{S₂P(OR)₂} ₂](PF₆) (R = Et, 2; ⁱPr, 3), tetranuclear [Cu₄(μ-dppm)₂ {S₂P(OEt)₂} ₄] 4, and hexanuclear [Cu₆(μ-dppm)₂(μ ₄-Cl){S₂P(OⁱPr)₂} ₄](BF₄) 5. Similarly, the reaction of [Cu ₂(μ-L-L)₂(CH₃CN)₂](PF ₆)₂ (L-L, dppm, dppe = Ph₂PCH ₂CH₂PPh₂) with (NH₄)[S ₂P(OR)₂] yields dinuclear [Cu₂(μ-dppm) ₂{S₂P(OR)₂}₂] 6 (R= ⁱPr, 6A; Et, 6B), trinuclear [Cu₃(μ-dppe)₃(μ-Cl) ₂{S₂P(OⁱPr)₂}] 9, and polymeric [Cu(μ₂-dppe){S₂P(OR)₂}]_n (R = Et, 7; ⁱPr, 8) complexes. The formation of 1 and 5 involved the abstraction of chloride from dichloromethane when the Cu/S₂P(OR) ₂ ratio exceeded 1, but when ratio was 1:1, no Cl abstraction occurred, as in compound 4. Compound 9, however, was obtained as a 12% byproduct in the synthesis of 8 using a 1:1:1 ratio of Cu/dppe/S₂P(O ⁱPr)₂. The chloride binds to Cu atoms in a μ₃-Cl mode by capping one face of the Cu₃ triangle of cluster 1. A μ₄-Cl caps a single tetragonal face of the trigonal prism of cluster 5, and in the cluster 9, two chlorides bond in μ₂-Cl modes. Both clusters 2 and 3 exhibit the μ₃-S mode of bonding for dtp ligands. Only cluster 5 exhibited close Cu...Cu contacts (2.997-3.0238 A). All of compounds were characterized by single-crystal X-ray diffraction and pertinent crystallographic data for 1, 5, and 9 are are follows: (1) C₇₉H₇₆ClCu₃F ₆O₂P₈S₂, triclinic, P1, a = 11.213(1) A, b = 14.142(1) A, c = 25.910(2) A, α = 95.328(2)°, β = 99.594(2)°, γ = 102.581-(2)°, V = 3918.2(6) A³, Z = 2; (5) C₇₄H ₁₀₀BClCu₆F₄O₈P₈S ₈, monoclinic, P2₁/n, a = 25.198(4) A, b = 15.990(3) A, c = 25.421(4) A, β = 106.027(3)°, V = 9845(3)A³, Z = 4; (9) C₈₄H₈₆Cl ₂Cu₃O₂P₇S₂, monoclinic, C2/c, with a = 24.965(3) A, b = 17.058(2) A, c = 20.253(2) A, β = 95.351(4)°, V = 8587.4(17)A³, Z = 4.

Full text of DOI:10.1021/ic051166+

Inorg. Chem. 2005, 44, 9921−9929
Versatility of Dithiophosphates in the Syntheses of Copper(I) Complexes
with Bis(diphenylphosphino)alkanes: Abstraction of Chloride from
Dichloromethane
Ben-Jie Liaw,‡ Tarlok S. Lobana,‡,# Ya-Wen Lin,‡ Ju-Chun Wang,§ and C. W. Liu*,†
Department of Chemistry, National Dong Hwa UniVersity, Hualien, Taiwan 974, Department of
Chemistry, Chung Yuan Christian UniVersity, Chung-Li, Taiwan 320, and Department of
Chemistry, Soochow UniVersity, Taipei, Taiwan 111, ROC.
Received July 13, 2005
Reactions of [Cu(CH3CN)4]X (X
ammonium dialkyldithiophosphates, (NH4)[S2P(OR)2] (R
trinuclear [Cu3( -dppm)3( 3-Cl) S2P(OEt)2
tetranuclear [Cu4( -dppm)2 S2P(OEt)2 4] 4, and hexanuclear [Cu6(
the reaction of [Cu2( -L L)2(CH3CN)2](PF6)2 (L L, dppm, dppe
dinuclear [Cu2( -dppm)2 S2P(OR)2 2] 6 (R
iPr, 6A; Et, 6B), trinuclear [Cu3(
polymeric [Cu( 2-dppe) S2P(OR)2 ]n (R
Et, 7; iPr, 8) complexes. The formation of 1 and 5 involved the abstraction
) PF6, BF4) with bis(diphenylphosphino)methane (dppm ) Ph2PCH2PPh2) and
)
Et, iPr), yield a series of novel CuI polynuclear complexes,
i
µ
µ
{
}
] (PF6) 1 and [Cu3(
µ
-dppm)2
-dppm)2(
Ph2PCH2CH2PPh2) with (NH4)[S2P(OR)2] yields
-dppe)3( -Cl)2 ] 9, and
S2P(OiPr)2
{
S2P(OR)2
}
2](PF6) (R
)
Et, 2; Pr, 3),
µ
{
}
µ
µ4-Cl)
{
S2P(OiPr)2
}4](BF4) 5. Similarly,
µ
−
−
)
µ
{
}
)
µ
µ
{
}
µ
{
}
)
of chloride from dichloromethane when the Cu/S2P(OR)2 ratio exceeded 1, but when ratio was 1:1, no Cl abstraction
occurred, as in compound 4. Compound 9, however, was obtained as a 12% byproduct in the synthesis of 8 using
a 1:1:1 ratio of Cu/dppe/S2P(OiPr)2. The chloride binds to Cu atoms in a
µ
3-Cl mode by capping one face of the
4-Cl caps a single tetragonal face of the trigonal prism of cluster 5, and in the cluster
2-Cl modes. Both clusters 2 and 3 exhibit the 3-S mode of bonding for dtp ligands. Only
cluster 5 exhibited close Cu‚‚‚Cu contacts (2.997 3.0238 Å). All of compounds were characterized by single-
crystal X-ray diffraction and pertinent crystallographic data for 1, 5, and 9 are are follows: (1) C79H76ClCu3F6O2P8S2,
triclinic, P1, a 11.213(1) Å, b 14.142(1) Å, c 25.910(2) Å, R ) 95.328(2) â ) 99.594(2) γ ) 102.581-
(2) , V 2; (5) C74H100BClCu6F4O8P8S8, monoclinic, P21/n, a 25.198(4) Å, b 15.990(3)
3918.2(6) Å3, Z
Å, c 25.421(4) Å, â ) 106.027(3) , V 4; (9) C84H86Cl2Cu3O2P7S2, monoclinic, C2/c, with a
9845(3)Å3, Z
20.253(2) Å, â ) 95.351(4) , V 4.
8587.4(17)Å3, Z
Cu3 triangle of cluster 1. A
9, two chlorides bond in
µ
µ
µ
−
h
)
)
)
°
,
°,
°
)
)
)
)
)
°
)
)
)
24.965(3) Å, b
)
17.058(2) Å, c
)
°
)
)
Scheme 1
Introduction
-
Dialkyldithiophosphates [dtp, (RO)2PS2 ] exhibit a variety
of coordination modes (Scheme 1),1-3 and their metal
complexes have important analytical, biochemical, and
* To whom correspondence should be addressed. E-mail: chenwei@
mail.ndhu.edu.tw. Fax: (+886)-3-8633570.
† National Dong Hwa University.
‡ Chung Yuan Christian University.
§ Soochow University.
# On leave (from January 18, 2005 to June 29, 2005) from the Guru
Nanak Dev University, Amritsar 143005, India.
(1) Haiduc, I.; Edelmann, F. T. Supramolecular Organometallic Chem-
istry; Wiley: Weinheim, Germany, 1999.
(2) Haiduc, I.; Sowerby, D. B.; Lu, S.-F. Polyhedron 1995, 14, 3389.
(3) (a) Haiduc, I. J. Organomet. Chem. 2001, 623, 29, and references
therein. (b) Liu, C. W.; Pitts, J. T.; Fackler, J. P., Jr. Polyhedron 1997,
16, 3899 and references therein.
industrial applications.4-15 Only a few CuI and AgI complexes
of dtp which have tertiary phosphines as co-ligands are
known, and none of them are bis(diphenylphosphino)alkanes,
such as PPh2P(CH2)nPPh2 (n ) 1, dppm; n ) 2, dppe, and
so on).1-3 Given the ability of diphosphines to act as P,P-
10.1021/ic051166+ CCC: $30.25
Published on Web 11/18/2005
© 2005 American Chemical Society
Inorganic Chemistry, Vol. 44, No. 26, 2005 9921

Liaw et al.
bridging ligands, researchers recently reported the cluster
cation, [Ag4(µ-dppm)2{S2P(OEt)2}3]+, which uniquely ex-
hibited three coordination modes (III, V, and VI) of dtp.16
Subsequently, the reaction that uses the dppe unit as the
bridging ligand in the cluster synthesis yielded two kinds of
polymeric species: the 1D zigzag chain, [Ag(dppe){S2P-
(OR)2}]n, and an unusual 2D honeycomb-shaped network,
[Ag4(µ3-Cl)(dppe)1.5{S2P(OR)2}3]n.17
Copper(I) is an important metal ion with soft Lewis acid
character. It has a strong tendency to form covalent bonds
with soft ligands (such as P and S donor atoms) and make
close Cu‚‚‚Cu contacts (i.e., cuprophilicity,18a-c less than
twice the van der Waals radius of Cu, 2.80 Å18d). These
characteristics of CuI have resulted in the formation of
oligomers and polymers with diverse coordination net-
works.19 Studies of inorganic-organic coordination networks
over the past decade have helped to develop new materials
which exhibit conducting, catalytic, and magnetic exchange
characteristics.20-28 As part of our program to study the
interaction of dtp with metals, in this investigation, the
influence of bis(diphenylphosphino)alkanes and the Cu/dtp
molar ratio are examined. Nine new complexes are reported
herein. These are trinuclear [Cu3(µ-dppm)3(µ3-Cl){S2P-
(OEt)2}](PF6) 1 and [Cu3(µ-dppm)2{S2P(OR)2}2](PF6) (R )
i
Et, 2; Pr, 3), tetranuclear [Cu4(µ-dppm)2{S2P(OEt)2}4] 4,
hexanuclear [Cu6(µ-dppm)2(µ4-Cl){S2P(OiPr)2}4](BF4) 5, di-
nuclear Cu2(µ-dppm)2[S2P(OiPr)2]2 6, polymeric [Cu(µ-
dppe){S2P(OR)2}]n (R ) Et, 7; iPr, 8), and trinuclear [Cu3(µ-
dppe)3(µ-Cl)2{S2P(OiPr)2}] 9. The formation of clusters 1,
5, and 9 involved the abstraction of chloride from CH2Cl2
or CHCl3.
Experimental Section
Materials and Measurements. All chemicals and reagents
obtained from commercial sources were purified and dried. CH2-
Cl2 and MeOH were distilled from P4O10 and Mg, respectively.
Hexane and diethyl ether were distilled from Na/K. All reactions
were performed in oven-dried Schlenk glassware using standard
inert-atmosphere techniques. The starting compounds, [Cu(CH3-
CN)4]X (X ) PF6,29a BF429b), [Cu2(µ-dppm)2(CH3CN)2](PF6)2,30a
[Cu2(µ-dppe)2(CH3CN)2](PF6)2,30b and (NH4)[S2P(OR)2] (R )Et,
iPr),31 were prepared according to literature methods or purchased
from Aldrich Chemicals. NMR spectra were recorded on Bruker
AC-F200 and Advance-300 Fourier transform spectrometers. The
31P{1H} NMR spectra are referenced externally against 85% H3-
PO4. The elemental analyses (C, H, S) were done using a Perkin-
Elmer 2400 analyzer.
(4) Barnes, A. M.; Bartle, K. D.; Thibon, V. R. A. Tribol. Int. 2001, 34,
389.
(5) Lubricant and Related Products; Klaman, D., Ed.; Verlag Chemie:
Weinheim, Germany, 1984.
(6) Rickelton, W.; Boyle, R. SolVent Extr. Ion. Exch. 1990, 8, 783.
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Chem. Soc. 2002, 124, 10662.
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R. J.; Fackler, J. P., Jr. Inorg. Chem. 2002, 41, 4579.
(10) Van Zyl, W. E.; Lopez-de-Luzuriaga, J. M.; Fackler, J. P., Jr. J. Mol.
Struct. 2000, 516, 99.
(11) Patnaik, P. A. ComprehensiVe Guide to the Hazardous Properies of
Chemical Substances; Van Nostrand Reinhold: New York, 1992;
Chapter 40 and references therein.
(12) Byrom, C.; Malik, M. A.; O’Brien, P.; White, A. J. P.; Williams, D.
J. Polyhedron 2000, 19, 211.
(13) Carmalt, C. J.; Mileham, J. D.; White, A. J. P.; Williams, D. J.; Steed,
J. W. Inorg Chem. 2001, 40, 6035.
(14) Eagle, A. A.; Laughlin, L. J.; Young, C. G.; Tiekink, E. R. T. J. Am.
Chem. Soc. 1992, 114, 9195.
[Cu3(dppm)3(µ3-Cl){S2P(OEt)2}](PF6) (1). The ligand NH4[S2P-
(OEt)2] (0.05 g, 0.27 mmol) was suspended in a solution of [Cu-
(CH3CN)4](PF6) (0.30 g, 0.81 mmol) and dppm (0.31 g, 0.81 mmol)
in dichloromethane (30 mL) in a Schlenk flask (100 mL). The
contents were stirred for 24 h at ambient temperature under a N2
atmosphere; then the mixture was filtered to separate insoluble NH4-
PF6 and unreacted ligand. The filtrate was transferred into a
separating funnel, and water (20 mL) was added to it to remove
water soluble unreacted ligand and NH4PF6; the dichloromethane
extract was evaporated to dryness to give a white residue. This
residue was then redissolved in dichloromethane (20 mL) and
layered with hexane (10 mL) which yielded crystalline 1 (0.20 g,
44%; mp 183-186°C). Anal. Calcd for C79H76ClCu3O2F6S2P8: C,
(15) Eagle, A. A.; Thomas, S.; Young, C. G. In Transition Metal Sulfur
Chemistry; Stiefel, E. I., Mutsumoto, K., Eds.; American Chemical
Society: Washington, DC, 1996; p 324, Chapter 20.
(16) Liu, C. W.; Liaw, B.-J. Liou, L.-S. Inorg. Chem. Comm. 2004, 7,
868.
(17) Liu, C. W.; Liaw, B.-J.; Liou, L.-S.; Wang, J.-C. Chem. Commun.
2005, 1983.
1
55.50; H, 4.48; S, 3.75. Found: C, 55.46; H, 4.45; S, 3.74. H
NMR (CDCl3): δ 0.82 (m, 6H, CH3), 3.47 (s, br, 6H, PCH2P),
4.62 (m, 4H, OCH2), 6.80-7.24 (m, 60H, P(C6H5)). 31P{1H} NMR
(CDCl3): δ 94.35 (s, P(OC2H5)), -15.98 (br, 6P, P(C6H5)), -143.7
(18) Sundararaman, A.; Zakharov, L. N.; Rheingold, A. L.; Jaekle, F. Chem.
Commun. 2005, 1708. (b) Zhang, J.-P.; Wang, Y.-B.; Huang, X.-C.;
Lin, Y.-Y.; Chen, X.-M. Chem.sEur. J. 2005, 11, 552. (c) Fu, W.-
F.; Gan, X.; Che, C.-M.; Cao, Q.-Y.; Zhou, Z.-Y.; Zhu, N.-Y. Chem.s
Eur. J. 2004, 10, 2228. (d) Huheey, J. E.; Keiter, E. A.; Keiter, R. L.
Inorganic Chemistry: Principles of Structure and ReactiVity, 4th ed.;
Harper Collins College Publishers: New York, 1993; Chapter 8, p
292.
(19) (a) Hanton, L. R.; Richardson, C.; Robinson, W. T.; Turnbull, J. M.
Chem. Commun. 2000, 2465. (b) Zhang, Q.-F.; Leung, W.-H.; Xin,
X. Q.; Fun, H. K. Inorg Chem. 2000, 39, 417. (c) Ahlrichs, R.;
Besinger, J.; Eichhoefer, A.; Fenske, D.; Gbureck, A. Angew. Chem.,
Int. Ed. 2000, 39, 3929. (d) Zhang, J.; Xiong, R. G.; Zuo, J. L.; You,
X. Z. Chem. Commun. 2000, 1495. (e) Zhang, J.; Xiong, R. G.; Zuo,
J. L.; Che, C. M.; You, X. Z. J. Chem. Soc., Dalton Trans. 2000,
2898. (f) Aakeroy, C. B.; Beatty, A. M.; Lorimer, K. R. J. Chem.
Soc., Dalton Trans. 2000, 3869. (g) Graham, P. M.; Pike, R. D.; Sabat,
M.; Bailey, R. D.; Pennington, W. T. Inorg. Chem. 2000, 39, 5121.
(20) Fortin, D.; Drouin, M.; Harvey, P. D. Inorg. Chem. 2000, 39, 2758
and references therein.
(PF6). ∆δ ) δComplex - δ
) - 20.45 ppm; ∆δ ) δComplex
Ligand(S2P)
- δ
) 3.52 ppm.
Ligand(PPh2)
The use of CHCl3 in place of CH2Cl2 also gave the same
compound, confirmed by NMR and elemental analysis.1H NMR
(23) Munakata, M.; Wu, L. P.; Kuroda-Sowa, T. AdV. Inorg. Chem. 1999,
46, 173.
(24) Janiak, C. Angew. Chem., Int. Ed. Engl. 1997, 36, 1431.
(25) Mitzi, D. B. Prog. Inorg. Chem. 1999, 48, 1.
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123.
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2003, 42, 7728.
(29) Kubas, G. J. Inorg. Synth. 1979, 19, 90.
(21) Carlucci, L.; Ciani, G.; Moret, M.; Proserpio, D. M.; Rizzato, S. Angew.
Chem., Int. Ed. 2000, 39, 1506.
(22) Robson, R.; Abrahams, B. F.; Batten, S. R.; Gable, R. W.; Hoskins,
B. F.; Liu, J. Supramolecular Architecture; American Chemical
Society: Washington, DC, 1992; Chapter 19.
(30) Diaz, J.; Gamasa, M. P.; Gimeno, J.; Tiripicchio, A.; Camellini, M.
T. J. Chem. Soc., Dalton Trans. 1987, 1275. (b) Vijayashree, N.;
Samuelson, A. G.; Nethaji, M. Current Science 1993, 65, 57.
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1956, 21, 707.
9922 Inorganic Chemistry, Vol. 44, No. 26, 2005

CuI Complexes with Bis(diphenylphosphino)alkanes
(CDCl3): δ 0.86 (m, 6H, CH3), 3.47 (s, br, 6H, PCH2P), 4.62
(m, 4H, OCH2), 6.80-7.24 (m, 60H, P(C6H5)).31P{1H} NMR
(CDCl3): δ 94.59 (s, P(OC2H5)), -15.85 (br, 6P, P(C6H5)), -143.7
(PF6).
-19.43 (br, 4P, P(C6H5)). ∆δ ) δComplex - δLigand(S P) ) - 16.48
2
ppm; ∆δ ) δComplex - δLigand(PPh ) ) 2.12 ppm.
2
[Cu2(dppm)2{S2P(OEt)2}2] (6b). Compound 6b was prepared
using the same method that was used for the preparation of 6a
(0.203 g, 70%; mp 173-174 °C). Anal. Calcd for C58H64-
Cu2O4S4P6: C, 55.13; H, 5.09; S, 10.13. Found: C, 54.70; H, 5.31;
[Cu3(dppm)2{S2P(OEt)2}2](PF6) (2). This complex was prepared
in a similar manner using THF in place of dichloromethane and
reacting [Cu(CH3CN)4](PF6) with dppm and (NH4)[S2P(OEt)2] in
a 3:2:2 molar ratio (0.18 g, 48%; mp 191-193 °C). Anal. Calcd
for C58H64Cu3O4F6S4P7: C, 47.23; H, 4.37; S, 8.70. Found: C,
1
S, 10.06. H NMR (CDCl3): δ 1.15 (d, 12H, CH3), 3.03 (t, 4H,
PCH2P), 3.90 (m, 8H, OCH2), 6.93-7.38 (m, 40H, P(C6H5)). 31P
{1H} NMR (CDCl3): δ 96.70 (s, 2P, P(OEt)), -17.38 (s, 4P,
1
P(C6H5)). ∆δ ) δComplex - δ
) - 18.10 ppm; ∆δ ) δComplex
Ligand(S2P)
46.35; H, 4.31; S, 8.93. H NMR (acetone-d6): δ 1.23 (d, 12H,
- δLigand(PPh ) ) 0.07 ppm.
CH3), 3.24 (br, 4H, PCH2P), 4.52 (m, 8H, OCH2), 6.80-7.32 (m,
40H, P(C6H5)). 31P{1H} NMR (acetone-d6): δ 93.90 (t, br, 2P,
P(OEt)), -14.46 (t, br, 4P, P(C6H5)), -143.7 (PF6). ∆δ ) δComplex
- δLigand(S P) ) - 20.90 ppm; ∆δ ) δComplex - δLigand(PPh ) ) 5.04
2
[Cu(dppe){S2P(OEt)2}]n (7). This complex was prepared by the
method used to prepare compound 6 with dppm replaced by dppe
(0.11 g, 78%; mp 175-177 °C). Anal. Calcd. for C30H34-
CuO2S2P3‚CH2Cl2: C, 50.85; H, 4.96; S, 8.76. Found: C, 50.43;
H, 5.35; S, 8.62. 1H NMR (CDCl3): δ 1.33 (d, 6H, CH3), 2.34 (br,
4H, PCH2CH2P), 4.12 (m, 4H, OCH2), 7.20-7.62 (m, 20H,
P(C6H5)). 31P {1H} NMR (CDCl3): δ 92.28 (s, 1P, P(OEt)), -12.04
2
2
ppm.
[Cu3(dppm)2{S2P(OiPr)2}2](PF6) (3). This complex was ob-
tained by the same method as for 2 using (NH4)[S2P(OiPr)2] (0.17
g, 42%; mp 192-194 °C). Anal. Calcd for C62H72Cu3O4F6S4P7:
(s, br, 2P, P(C6H5)). ∆δ ) δComplex - δLigand(S P) ) - 22.52 ppm;
1
2
C, 48.64; H, 4.74; S, 8.38. Found: C, 48.13; H, 4.83; S, 8.75. H
∆δ ) δComplex - δLigand(PPh ) ) 0.66 ppm.
2
NMR (acetone-d6), δ 1.22 (t; 24H, CH3), 3.32 (br; 4H, PCH2P),
4.72 (m; 4H, OCH), 6.88-7.48 (m; 40H, P(C6H5)). 31P{1H} NMR
(acetone-d6) δ 91.48 (s, br, 2P, P(OiPr)), -13.90 (t, br, 4P, P(C6H5)),
[Cu(dppe){S2P(OiPr)2}]n (8). This complex was prepared by the
method used to prepare 7 with (NH4)[S2P(OiPr)2] (0.10 g, 68%;
mp 173-175 °C). Anal. Calcd for C32H38CuO2S2P3‚CH2Cl2: C,
-143.7 (PF6). ∆δ ) δComplex-δLigand(S P) ) - 19.90 ppm; ∆δ )
2
1
52.14; H, 5.30; S, 8.43. Found: C, 51.55; H, 5.35; S, 8.79. H
δ
Complex-δLigand(PPh ) ) 5.60 ppm.
2
NMR (CDCl3): δ 1.33 (d, 12H, CH3), 2.34 (br, 4H, PCH2CH2P),
4.82 (m, 2H, OCH ), 7.10-7.62 {m, 20H, P(C6H5)}. 31P {1H} NMR
(CDCl3): δ 90.04 (s, 1P, P(OiPr)), -12.11 {br, 2P, P(C6H5)}. ∆δ
[Cu4(dppm)2{S2P(OEt)2}4] (4). This complex was prepared by
the method used for 1 by reacting [Cu(CH3CN)4](PF6) with dppm
and (NH4)[S2P(OEt)2] in a 2:1:2 molar ratio (0.22 g, 62%; mp 189-
192 °C). Anal. Calcd for C66H84Cu4O8S8P8: C, 44.94; H, 4.79; S,
) δComplex - δ
) 0.59 ppm.
) - 21.34 ppm; ∆δ ) δComplex - δ
Ligand(S2P)
Ligand(PPh2)
1
14.51. Found: C, 44.87; H, 4.85; S, 14.52. H NMR (CDCl3): δ
[Cu3(µ-dppe)3(µ-Cl)2{S2P(OiPr)2}] (9). After the formation of
8, new crystals were obtained from the filtrate in a 12% (0.07 g)
yield (mp 189-192 °C). Anal. Calcd for C84H86Cu3O2S2P7Cl2: C,
1.33 (d, 24H, CH3), 3.22 (br, 4H, PCH2P), 4.23 (m, 16H, OCH2),
7.10-7.41 (m, 40H, P(C6H5)). 31P{1H} NMR (CDCl3): δ 95.06
(s, br, 4P, P(OEt)), -11.95 (m, br, 4P, PPh2). ∆δ ) δComplex
-
1
60.41; H, 5.19; S, 3.84. Found: C, 58.79; H, 5.35; S, 4.02. H
δLigand(S P) ) - 19.74 ppm; ∆δ ) δComplex - δLigand(PPh ) ) 7.55
2
2
NMR (CDCl3): δ 1.31 (d, 12H, CH3), 3.14 (br, 12H, PCH2CH2P),
4.82 (m, 2H, OCH), 7.04-7.27 {m, 60H, P(C6H5)}. 31P {1H} NMR
(CDCl3): δ 92.41 (s, 1P, P(OiPr)), 8.76 (br, 6P, P(C6H5)). ∆δ )
ppm.
[Cu6(dppm)2(µ4-Cl){S2P(OiPr)2}4](BF4) (5). This complex was
prepared by the same method as 1 by reacting [Cu(CH3CN)4](BF4)
with dppm and (NH4)[S2P(OiPr)2] in a 3:1:2 molar ratio (0.10 g,
36%; mp 196-198 °C). Anal. Calcd for C74H100Cu6O8S8P8BF4Cl:
C, 41.83; H, 4.71; S, 12.07. Found: C, 42.29; H, 4.89; S, 11.85.
1H NMR (CDCl3): δ 1.32 (m, 48H, CH3), 3.13 (m, 4H, PCH2P),
4.82 (m, 8H, OCH), 6.80-7.34 (m, 40H, P(C6H5)). 31P{1H} NMR
(CDCl3): δ 97.67, 92.68 (4P, P(OiPr)), -13.94 (s, 4P, P(C6H5)).
δComplex - δ
) - 18.93 ppm; ∆δ ) δComplex - δ
Ligand(S2P)
Ligand(PPh2)
) 21.46 ppm.
Alternative Method for 9. The NH4[S2P(OiPr)2] (0.06 g, 0.27
mmol) ligand was suspended in a solution of [Cu(CH3CN)4](PF6)
(0.30 g, 0.81 mmol) and dppe (0.320 g, 0.81 mmol) in dichlo-
romethane (30 mL) in a Schlenk flask (100 mL). The contents were
stirred for 24 h at ambient temperature under a N2 atmosphere;
then the mixture was filtered to separate insoluble NH4PF6 and
unreacted ligand. Then the filtrate was evaporated to dryness to
give a white residue. This residue was treated with methanol (10
mL) and filtered, and the solid obtained was dried (0.300 g, 40%;
∆δ ) δComplex - δLigand(S P) ) -13.71, -18.70 ppm; ∆δ ) δComplex
2
- δLigand(PPh ) ) 5.56 ppm.
2
The use of CHCl3 in place of CH2Cl2 also gave compound 5, as
1
confirmed by NMR and elemental analysis. H NMR (CDCl3): δ
1.31 (m, 48H, CH3), 3.18 (br, 4H, PCH2P), 4.88 (m, 8H, OCH),
6.90-7.21 (m, 40H, P(C6H5)). 31P{1H} NMR (CDCl3): δ 97.61,
92.62 (s, P(OiPr)), -12.60 (br, 4P, P(C6H5)).
1
mp 189-192 °C). H NMR (CDCl3): δ 1.33 (d, 12H, CH3), 3.20
(br, 12H, PCH2CH2P), 4.82 (m, 2H, OCH), 7.1-7.27 {m, 60H,
P(C6H5)}. 31P {1H} NMR (CDCl3): δ 92.62 (s, 1P, P(OiPr)), 8.89
(br, 6P, P(C6H5)).
[Cu2(dppm)2{S2P(OiPr)2}2] (6a). The NH4S2P(OiPr)2 (0.13 g,
0.46 mmol) ligand was suspended in a solution of [Cu2(dppm)2(CH3-
CN)2](PF6)2 (0.30 g, 0.23 mmol) in dichloromethane (30 mL) in a
Schlenk flask (100 mL). The contents were stirred for 24 h at
ambient temperature and filtered to separate insoluble NH4PF6 and
unreacted ligands. The resulting solution was evaporated to dryness
at room temperature and recrystallized using CH3OH (20 mL) at
room temperature, which gave a white precipitate of 6a in a short
period of time (0.23 g, 79%; mp 176-179 °C). Anal. Calcd for
C62H72Cu2O4S4P6‚0.5CH2Cl2: C, 55.00; H, 5.39; S, 9.39. Found:
X-ray Structure Determination. The structures of 1-9 were
obtained by single-crystal X-ray diffraction. Crystals of 1, 4, 5,
and 6-9 were grown using dichloromethane-hexane solvents,
while crystal of 2 and 3 were grown from a thf-hexane mixture.
The crystals were mounted on the tips of glass fibers with epoxy
resin. Data for compounds 7 and 8 were collected at 293 K on a
Siemens P4 diffractometer equipped with Mo KR radiation (λ )
0.71073 Å). The data were collected using the 2θ-ω scan
technique. The data reduction was performed with SAINT,32 which
1
C, 55.13; H, 5.69; S, 9.11. H NMR (CDCl3): δ 1.23 (d, 24H,
CH3), 2.94 (br, 4H, PCH2P), 4.62 (m, 4H, OCH), 6.80-7.32 (m,
(32) SAINT, version 4.043; Bruker Analytical X-ray System: Madison,
40H, P(C6H5)). 31P {1H} NMR (CDCl3): δ 94.90 (s, 2P, P(OiPr)),
WI, 1995.
Inorganic Chemistry, Vol. 44, No. 26, 2005 9923

Liaw et al.
Table 1. Crystallographic Data for Compounds 1-9
1
2
3
4
5
formula
fw
cryst syst
space group
a (Å)
C79H76ClCu3F6O2P8S2
1709.35
triclinic
P1h
11.213(1)
14.142(1)
25.910(2)
95.328(2)
99.594(2)
102.581(2)
3918.2(6)
2
1.449
0.71073
1.117
298(2)
0.0391
C58H64Cu3F6O4P7S4
1474.74
triclinic
P1h
12.812(2)
15.221(3)
17.100(3)
82.275(3)
83.963(3)
89.726(3)
3285.8(9)
2
1.491
0.71073
1.320
298(2)
0.0484
C62H72Cu3 F6O4P7S4
1530.85
triclinic
P1h
12.896(2)
16.661(2)
16.876(2)
81.230(2)
84.472(2)
87.297(2)
3564.9(8)
2
1.426
0.71073
1.219
298(2)
0.0456
C66H84Cu4 O8P8S8
1763.73
monoclinic
P21/n
13.473(1)
23.888(1)
24.648(1)
90
95.986(1)
90
7889.7(6)
4
1.485
0.71073
1.487
298(2)
0.0348
C74H100BCl Cu6F4O8P8S8
2125.40
monoclinic
P21/n
25.198(4)
15.990(3)
25.421(4)
90
106.027(3)
90
9845(3)
4
1.456
0.71073
1.675
298(2)
0.0609
b (Å)
c (Å)
R (deg)
â (deg)
γ (deg)
V (Å3)
Z
F
calcd (g cm-3
λ(Mo KR) (Å)
)
µ (mm-1
T (K)
R1a
)
wR2b
0.0996
0.1186
0.1140
0.0859
0.1615
6‚CH2Cl2
7‚1/2CH2Cl2
30.5H35Cl CuO2P3S2
689.64
triclinic
P1h
8‚CH2Cl2
9
formula
fw
C63H74Cl2Cu2 O4P6S4
C
C33H40Cl2 CuO2P3S2
760.12
monoclinic
C2/c
C84H86Cl2 Cu3O2P7S2
1669.96
monoclinic
C2/c
1407.36
orthorhombic
Pbcn
cryst syst
space group
a (Å)
b (Å)
c (Å)
R (deg)
â (deg)
γ (deg)
V (Å3)
Z
18.5958(11)
15.5449(9)
24.486(2)
90
90
90
7078.3(7)
4
1.319
0.71073
0.972
298(2)
0.0474
0.1311
11.752(2)
13.127(2)
13.268(3)
61.126(2)
76.858(8)
68.480(1)
1664.2(6)
2
1.375
0.71073
1.032
293(2)
0.0663
0.1642
19.672(4)
17.197(2)
13.680(5)
90
126.67(2)
90
3711.9(16)
4
1.360
0.71073
1.002
293(2)
0.0622
0.1342
24.965(3)
17.058(2)
20.253(2)
90
95.351(4)
90
8587.4(17)
4
1.292
0.71073
1.021
298(2)
0.0422
0.0945
F
calcd (g cm-3
)
λ(Mo KR) (Å)
µ (mm-1
T (K)
R1a
)
wR2b
2
2
2
a R1 ) ||Fo| - |Fc||/|Fo|. b wR2 ) [w(Fo - Fc )2]/[w(Fo )2]1/2
.
Scheme 2a
corrects for Lorentz and polarization effects. An empirical absorp-
tion correction (Ψ scans) was applied. The crystal data for
compounds 1-6 and 9 were collected at 298 K on a Siemens
SMART CCD diffractometer. The data were measured with ω scans
of 0.3ï per frame for 60 s. A total of 1271 frames were collected
with a maximum resolution of 0.84 Å. Cell parameters were
retrieved with SMART software33 and refined with SAINT software
on all observed reflections (I > 10σ(I)). Data reduction was
performed with SAINT, which corrects for Lorentz and polarization
effects. An empirical absorption correction was applied for all
compounds. All structures were solved by the use of direct methods,
and the refinement was performed by the least-squares methods
on F2 with the SHELXL-97 package,34 incorporated in SHELXTL/
PC, version 5.10.35 Selected crystal data for the compounds (1-9)
are summarized in Table 1.
Results and Discussion
Synthesis. Schemes 2 and 3 show the formation of CuI
polynuclear complexes by the reaction of copper(I) salts with
bisphosphines and dtp ligands. The reaction of [Cu(CH3CN)4]-
a The following synthetic conditions apply: (i) (NH4)[S2P(OEt)2], x )
y ) 3, Z ) PF6, CH2Cl2, RT (1); (ii) 2 (NH4)[S2P(OR)2], x ) 3, y ) 2, Z
) PF6, THF, RT (2, 3); (iii) 4(NH4)[S2P(OEt)2], x ) 4, y ) 2, Z ) PF6,
CH2Cl2, RT (4); and (iv) 4(NH4)[S2P(OiPr)2], x ) 6, y ) 2, Z ) BF4,
CH2Cl2, RT (5).
(33) SMART, version 4.043; Bruker Analytical X-ray System: Madison,
WI, 1995.
(34) Sheldrick, G. M. SHELXL-97: Program for the Refinement of Crystal
Structure; University of Go¨ttingen: Go¨ttingen, Germany, 1997.
(35) SHELXL: Program Library for Structure Solution and Molecular
Graphics, version 5.10 (PC version); Bruker Analytical X-ray
System: Madison, WI, 1998.
(PF6) with dppm and (NH4)[S2P(OEt)2] in dichloromethane
with a 3:3:1 molar ratio yielded the trinuclear cluster [Cu3-
9924 Inorganic Chemistry, Vol. 44, No. 26, 2005

CuI Complexes with Bis(diphenylphosphino)alkanes
Scheme 3a
found to be true in the formation of clusters 1 and 5 and in
the formation of 9; after the polymeric species have been
isolated, a low dtp content, which again favors the chloride
abstraction, is present. Notably, replacing CH2Cl2 with CHCl3
in the synthesis of 1 and 5, also resulted in the abstraction
of chloride from CHCl3, as verified by NMR spectroscopy
and elemental analyses (see Experimental Section). Cluster
9 was also obtained by reacting [Cu(CH3CN)4](PF6), dppe,
and (NH4)[S2P(OiPr)2] in a 3:3:1 molar ratio with a 40%
yield, determined by NMR spectroscopy. Compounds 6-8
included CH2Cl2 in the lattice (vide infra); this fact further
supports the claim that the complexes are stable in CH2Cl2
and that abstraction occurs when necessitated by a low molar
ratio of dithiophosphate. All clusters and polymers discussed
above are colorless, stable to air and moisture, and do not
melt; rather, they decompose in the range of ∼170-200 °C.
Molecular Structures of 1-9. Table 1 presents the
crystallographic data of the compounds, while Table 2 lists
some important bond parameters of the compounds. The
Supporting Information includes the bond parameters of
compounds 3 and 8, which are isostructural with compounds
2 and 7, respectively. Figures 1-7 display the molecular
structures of the compounds. The compounds crystallize in
triclinic (1, 2, 3, and 7), monoclinic (4, 5, 8 and 9), and
orthorhombic (6a) crystal systems.
Clusters 1-3, 5, and 9. The formation of clusters 1, 5,
and 9 involves the abstraction of chloride from dichlo-
romethane. Three Cu atoms of cluster 1 form a Cu3 triangle
bridged by three dppm ligands (Figure 1). The dithiophos-
phate anion, [S2P(OEt)2]- adopts bonding Mode IV; accord-
ingly, S(1) binds to Cu(1) [Cu(1)-S(1), 2.464(1) Å ], and
S(2) bridges the other two Cu atoms [Cu(2)-S(2), 2.3902-
(9) Å; Cu(3)-S(2), 2.352(1) Å]. The chloride abstracted from
CH2Cl2 connects three Cu atoms in a µ3-Cl mode with
approximately equal Cu-Cl bond lengths [2.4603(8), 2.4782-
(8), 2.4988(8) Å], and bond angles at Cl(1) [92.21(3), 91.63-
(3), 76.57(2)°], suggesting a face-capped Cu3 triangle. The
Cu-Cl bond distances are less than the sum of the covalent
radii, 2.58 Å,18d and other CuI complexes with µ3-Cl (e.g.,
(2.408-2.589 Å)37,38 in [Cu3(µ-dppm)3(µ3-SR)(µ3-Cl)](PF6)
and [Cu3(µ-dppm)3(µ3-η1-CtCtBu)(µ3-Cl)]+ have similar
bond lengths. The geometry around each Cu center is
distorted tetrahedral.
a The following synthetic conditions apply: (i) 2(NH4)[S2P(OR)2], L-L
) dppm, CH2Cl2, RT (6) and (ii) 2(NH4)[S2P(OR)2], L-L ) dppe, CH2Cl2,
RT (6-9).
(µ-dppm)3(µ3-Cl){S2P(OEt)2}](PF6), 1, and the reaction
involved the abstraction of chloride from CH2Cl2. When
[Cu(CH3CN)4](PF6) was reacted with dppm and (NH4)[S2P-
i
(OR)2] (R ) Et, Pr) in a 3:2:2 molar ratio in THF solvent,
the analogous [Cu3(µ-dppm)2{S2P(OR)2}2](PF6) (R ) Et, 2;
iPr, 3) clusters were produced. Tetranuclear [Cu4(µ-dppm)2-
{S2P(OEt)2}4], 4, was formed by reacting [Cu(CH3CN)4](PF6)
with dppm and (NH4)[S2P(OEt)2] in a 2:1:2 molar ratio in
dichloromethane. Similarly, the reaction of [Cu(CH3CN)4]-
(BF4) with dppm and (NH4)[S2P(OiPr)2] in CH2Cl2 in a 3:1:2
molar ratio yielded a hexanuclear cluster, [Cu6(µ-dppm)2-
(µ4-Cl){S2P(OiPr)2}4](BF4) 5, and its formation also involved
the abstraction of one chloride. The photoinduced extraction
of chloride from a chlorocarbon solvent by iron complexes
has also been reported.36
The formation of compounds 6a and 6b from Cu2(dppm)2-
(CH3CN)2(PF6)2 and (NH4)[S2P(OR)2] (R) Pr, 6a; Et, 6b)
involves the replacement of weakly coordinated CH3CN by
chelating [S2P(OR)2]- ligands; the central P,P-bridged di-
nuclear Cu(µ-P,P-dppm)2Cu framework is retained (Scheme
3). Finally, the reaction of Cu2(dppe)2(CH3CN)2(PF6)2 with
(NH4)[S2P(OR)2] in a 1:1 molar ratio yielded [Cu(µ-dppe)-
i
i
{S2P(OR)2}]n (R ) Et, 7; Pr, 8) polymers, as well as a
trinuclear cluster, [Cu3(µ-dppe)3(µ-Cl)2{S2P(OiPr)2}] 9, with
a yield of ∼12%. The formation of 9 involved the abstraction
of two chloride ions from the solvent, and the structure thus
produced is analogous to that of [Cu3(µ-dppe)3(µ2-I)2(I)(2-
SC5H4NH)],28 which was isolated from the reaction of CuI
with pyridine-2-thione in the presence of dppe. This is in
sharp contrast to the above-mentioned silver work where
CH2Cl2 acts as a source of capping chlorine atoms in the
formation of starburst clusters, [Ag4(µ3-Cl)(dppe)1.5{S2P-
(OR)2}3], which in turn propagate to produce a 2D hexagonal
network.17
Cluster 9 is composed of three dppe ligands that bridge
the Cu3 triangle, and the S2P(OiPr)2 anion chelates with the
Cu(1) center (Mode I) (Figure 2). The 2-fold rotational axis
passes through the Cu(1) and P(1) atoms. Interestingly, two
chloride anions extracted from CH2Cl2 bridge two Cu centers,
Cu(2) and Cu(2A) [Cu(2)-Cl(1) ) 2.398(1) Å, Cu(2)-Cl-
(1A) ) 2.472(1) Å], to achieve tetracoordination for both
Cu atoms. As before, the geometry around each Cu center
is distorted tetrahedral. The Cu2Cl2 core does not lie in a
plane but is bent with a dihedral angle of 17.07° between
The above reactions indicate dppm typically favors the
formation of clusters, and when the Cu/dtp ratio exceeds 1,
the abstraction of chloride from CH2Cl2 yields [Mn]+ (n )
3, 6) cations balanced by PF6 or BF4 counteranions. It is
(36) Kunkely, H.; Vogler, A. J. Photochem. Photobiol. A: Chem. 2003,
154, 289. (b) Stegge, J. M.; Woessner, S. M.; Hoggard, P. E. Inorg.
Chim. Acta 1996, 250, 385. (c) Miessler, G. L.; Zoebisch, E.; Pignolet,
L. H. Inorg. Chem. 1978, 17, 3636. (d) Miessler, G. L.; Stuk, G.;
Smith, T. P.; Given, K. W.; Palazzotto, M. C.; Pignolet, L. H. Inorg.
Chem. 1976, 15, 1982.
(37) Yam, V. W. W.; Lam. C.-H.; Fung, W. K.-M.; Cheung, K.-K. Inorg.
Chem. 2001, 40, 3435.
(38) Yam, V. W. W.; Lee, W.-K., Lai, T.-F. Organometallics 1993, 12,
2383. (b) Diez, J.; Gamasa, M. J.; Gimeno, J.; Lastra, E.; Aguirre,
A.; Garcia-Granda, S. Organometallics. 1993, 12, 2213.
Inorganic Chemistry, Vol. 44, No. 26, 2005 9925

Liaw et al.
Table 2. Bond Lengths (Å) and Angles(deg) for Compounds 1-9a
compound 1
Cu(1)-P(7)
Cu(1)-P(2)
Cu(1)-Cl(1)
Cu(1)-S(1)
Cu(2)-P(3)
P(1)-S(1)
2.2783(9)
2.2795(8)
2.4603(8)
2.4643(10)
2.2606(8)
1.9514(13)
Cu(2)-P(4)
Cu(2)-S(2)
Cu(2)-Cl(1)
Cu(3)-Cl(1)
Cu(3)-S(2)
P(1)-S(2)
2.2909(8)
2.3902(9)
2.4782(8)
2.4988(8)
2.3515(9)
2.0198(12)
P(7)-Cu(1)-P(2)
P(7)-Cu(1)-Cl(1)
P(2)-Cu(1)-Cl(1)
P(7)-Cu(1)-S(1)
P(2)-Cu(1)-S(1)
Cl(1)-Cu(1)-S(1)
Cu(1)-Cl(1)-Cu(2)
Cu(1)-Cl(1)-Cu(3)
137.42(3)
103.94(3)
103.36(3)
96.26(3)
95.38(3)
123.24(3)
92.21(3)
91.63(3)
P(3)-Cu(2)-P(4)
P(3)-Cu(2)-S(2)
P(4)-Cu(2)-S(2)
P(3)-Cu(2)-Cl(1)
P(4)-Cu(2)-Cl(1)
S(1)-Cu(2)-Cl(1)
Cu(2)-Cl(1)-Cu(3)
124.39(3)
119.86(3)
101.69(3)
110.64(3)
98.69(3)
96.24(3)
76.57(2)
compound 2
Cu(1)-P(3)
Cu(2)-P(5)
Cu(3)-P(4)
Cu(3)-P(6)
Cu(1)-S(1)
Cu(2)-S(1)
P(2)-S(3)
2.2256(13)
2.2120(12)
2.2694(13)
2.2760(14)
2.2785(13)
2.2873(13)
1.982(2)
Cu(3)-S(1)
Cu(1)-S(3)
Cu(2)-S(4)
Cu(3)-S(2)
P(1)-S(1)
P(1)-S(2)
P(2)-S(4)
2.6968(14)
2.2676(13)
2.2629(14)
2.4697(15)
2.0369(16)
1.953(2)
P(3)-Cu(1)-S(3)
P(3)-Cu(1)-S(1)
S(3)-Cu(1)-S(1)
P(5)-Cu(2)-S(4)
P(5)-Cu(2)-S(1)
S(4)-Cu(2)-S(1)
P(4)-Cu(3)-P(6)
P(4)-Cu(3)-S(2)
P(6)-Cu(3)-S(1)
122.42(5)
131.03(5)
106.39(5)
128.10(5)
123.12(5)
108.78(5)
124.55(5)
100.94(5)
115.60(4)
P(6)-Cu(3)-S(2)
P(4)-Cu(3)-S(1)
S(2)-Cu(3)-S(1)
P(1)-S(1)-Cu(1)
P(1)-S(1)-Cu(2)
Cu(1)-S(1)-Cu(2)
Cu(2)-S(1)-Cu(3)
P(1)-S(1)-Cu(3)
Cu(1)-S(1)-Cu(3)
108.69(6)
114.40(4)
81.35(5)
116.25(6)
121.26(7)
111.94(5)
76.76(4)
75.64(6)
85.47(4)
1.993(2)
compound 4
Cu(1)-P(12)
Cu(1)-S(1)
Cu(1)-S(4)
Cu(1)-S(8)
Cu(2)-S(1)
Cu(2)-S(3)
Cu(2)-S(6)
Cu(3)-P(10)
Cu(3)-S(7)
Cu(3)-S(4)
Cu(4)-P(14)
2.2532(8)
2.307(8)
Cu(4)-S(2)
Cu(4)-S(3)
Cu(4)-S(5)
P(7)-S(4)
2.3980(8)
2.3358(8)
2.3479(9)
1.9907(10)
1.9962(11)
2.0005(11)
2.0076(10)
1.9825(12)
1.9896(12)
1.9730(12)
1.9915(12)
P(12)-Cu(1)-S(1)
P(12)-Cu(1)-S(4)
P(12)-Cu(1)-S(8)
S(4)-Cu(1)-S(1)
S(8)-Cu(1)-S(1)
S(8)-Cu(1)-S(4)
P(9)-Cu(2)-S(1)
P(9)-Cu(2)-S(3)
P(9)-Cu(2)-S(6)
S(3)-Cu(2)-S(1)
S(3)-Cu(2)-S(6)
S(6)-Cu(2)-S(1)
107.30(3)
114.10(3)
109.79(3)
113.73(3)
105.41(3)
106.13(3)
103.29(3)
113.66(3)
106.07(3)
116.60(3)
105.79(3)
111.08(3)
P(10)-Cu(3)-S(2)
P(10)-Cu(3)-S(4)
P(10)-Cu(3)-S(7)
S(4)-Cu(3)-S(2)
S(7)-Cu(3)-S(2)
S(7)-Cu(3)-S(4)
P(14)-Cu(4)-S(2)
P(14)-Cu(4)-S(3)
P(14)-Cu(4)-S(5)
S(3)-Cu(4)-S(2)
S(3)-Cu(4)-S(5)
S(5)-Cu(4)-S(2)
104.17(3)
116.44(3)
105.21(3)
111.66(3)
114.90(3)
104.66(3)
106.28(3)
115.95(3)
108.89(3)
114.85(3)
105.33(3)
104.90(3)
2.3714(8)
2.3462(8)
2.3926(8)
2.3334(8)
2.3579(9)
2.2499(9)
2.3393(8)
2.3450(9)
2.2656(8)
P(7)-S(3)
P(13)-S(1)
P(13)-S(2)
P(17)-S(8)
P(17)-S(7)
P(19)-S(5)
P(19)-S(6)
compound 5
Cu(1)-P(5)
Cu(1)-S(3)
Cu(1)-S(1)
Cu(1)-Cl(1)
Cu(2)-S(4)
Cu(2)-S(1)
Cu(4)-S(7)
Cu(4)-S(5)
Cu(5)-S(7)
Cu(6)-P(6)
Cu(6)-S(2)
Cu(5)-Cl(1)
S(1)-P(1)
2.2276(18)
2.3444(19)
2.3531(17)
2.5029(17)
2.2551(17)
2.2624(17)
2.2466(17)
2.2648(17)
2.2948(18)
2.2360(18)
2.4263(17)
2.6955(18)
2.0195(19)
1.951(2)
Cu(2)-S(5)
Cu(2)‚‚‚Cu(4)
Cu(3)-P(7)
Cu(3)-S(4)
Cu(3)-S(6)
Cu(3)-Cl(1)
Cu(2)-S(2)
Cu(5)-P(8)
Cu(5)-S(6)
Cu(6)-S(8)
Cu(3)‚‚‚Cu(5)
Cu(6)-Cl(1)
S(2)-P(1)
2.2675(19)
3.0238(12)
2.2370(17)
2.2925(17)
2.4008(19)
2.7078(18)
2.2501(17)
2.2446(16)
2.4811(17)
2.3338(19)
2.9971(13)
2.5894(17)
2.0049(19)
2.022(2)
P(5)-Cu(1)-S(3)
P(5)-Cu(1)-S(1)
S(3)-Cu(1)-S(1)
P(5)-Cu(1)-Cl(1)
S(4)-Cu(2)-S(1)
S(4)-Cu(2)-S(5)
S(1)-Cu(2)-S(5)
P(7)-Cu(3)-S(4)
106.33(7)
115.49(6)
109.02(6)
123.93(6)
122.32(6)
115.77(6)
119.17(6)
131.04(6)
S(3)-Cu(1)-Cl(1)
S(1)-Cu(1)-Cl(1)
P(7)-Cu(3)-S(6)
S(4)-Cu(3)-S(6)
P(7)-Cu(3)-Cl(1)
S(4)-Cu(3)-Cl(1)
S(6)-Cu(3)-Cl(1)
100.08(6)
100.48(5)
97.11(6)
109.14(6)
116.11(6)
98.85(5)
101.05(5)
S(3)-P(2)
S(4)-P(2)
S(5)-P(3)
S(7)-P(4)
2.010(2)
2.035(3)
S(6)-P(3)
S(8)-P(4)
2.002(2)
1.934(3)
compound 6
Cu(1)-P(1)
Cu(1)-P(2)
S(1)-P(3)
2.2726(9)
2.2748(10)
1.9776(13)
Cu(1)-S(1)
Cu(1)-S(2)
S(2)-P(3)
2.3990(11)
2.5070(10)
1.9815(14)
P(1)-Cu(1)-P(2)
P(1)-Cu(1)-S(1)
P(2)-Cu(1)-S(1)
111.00(4)
121.15(4)
122.13(4)
P(2)-Cu(1)-S(2)
P(1)-Cu(1)-S(2)
S(1)-Cu(1)-S(2)
106.35(4)
104.76(4)
83.89(4)
compound 7
Cu(1)-P(3)
Cu(1)-P(2)
S(1)-P(1)
2.291(2)
2.297(2)
1.979(3)
Cu(1)-S(1)
Cu(1)-S(2)
S(2)-P(1)
2.466(2)
2.451(2)
1.964(3)
P(3)-Cu(1)-P(2)
P(3)-Cu(1)-S(2)
P(2)-Cu(1)-S(2)
112.32(7)
114.49(8)
117.82(8)
P(3)-Cu(1)-S(1)
P(2)-Cu(1)-S(1)
S(1)-Cu(1)-S(2)
112.59(8)
112.62(8)
84.03(8)
compound 9
Cu(1)-P(2)
Cu(2)-P(3)
Cu(2)-P(4)
Cu(1)-S(1)
2.2626(10)
2.2551(9)
2.2606(9)
2.4615(11)
Cu(2)-Cl(1)
Cu(2)-Cl(1)#1
S(1)-P(1)
2.3976(10)
2.4715(9)
1.9656(15)
P(3)-Cu(2)-P(4)
P(3)-Cu(2)-Cl(1)
P(4)-Cu(2)-Cl(1)
P(3)-Cu(2)-Cl(1)#1
P(4)-Cu(2)-Cl(1)#1
Cl(1)-Cu(2)-Cl(1)#1
127.44(4)
107.85(3)
111.15(3)
111.88(3)
99.05(3)
94.17(3)
P(2)#1-Cu(1)-S(1)
P(2)#1-Cu(1)-P(2)
P(2)-Cu(1)-S(1)
S(1)-Cu(1)-S(1)#1
Cu(2)-Cl(1)-Cu(2)#1
113.17(4)
114.89(5)
114.47(4)
82.72(6)
83.34(3)
a Symmetry transformations used to generate equivalent atoms: #1 -x, y, -z + 1/2.
the planes formed by Cu(2), Cl(1), and Cl(1A) and Cu(2A),
Cl(1), and Cl(1A). The structure of 9 is analogous to that of
Cu3I3(dppe)3(2-SC5H4NH).28
In cluster 2, two sides of the Cu3 triangle are bridged by
dppm ligands and the third side is bridged by a dtp anion
(Mode II) (Figure 3). The second dtp anion exhibits mode
9926 Inorganic Chemistry, Vol. 44, No. 26, 2005

CuI Complexes with Bis(diphenylphosphino)alkanes
Figure 1. Thermal ellipsoid drawing (30% probability level) of 1 with
atomic numbering scheme (with phenyl rings and ethyl groups omitted for
clarity).
Figure 4. Thermal ellipsoid drawing (30% probability level) of 5 with
atomic numbering scheme (with phenyl rings and isopropyl groups omitted
for clarity).
of the monothiocarboxylato moieties in [Cu3(µ-dppm)3{µ3-
SC(O)Ph-S}{µ3-SC(O)Ph-S, O}](ClO4).39
Cluster 5 exhibits a trigonal prismatic arrangement of Cu6
atoms; two dppm ligands bridge the two opposite sides of
the tetragonal plane formed by the Cu1, Cu3, Cu5, and Cu6
atoms (Figure 4). Two dtp ligands bridge the top (Cu1, Cu2,
Cu3) and bottom (Cu4, Cu5, Cu6) triangles of the prism, in
tridentate mode IV. The other two dtp ligands act as
tetradentates (Mode VII) and bind to four Cu atoms, each
along the tetragonal planes formed by Cu1, Cu2, Cu4, and
Cu6 and Cu2, Cu3, Cu5, and Cu4 atoms. Four copper atoms,
Cu1, Cu3, Cu5, and Cu6, complete tetracoordination by
abstracting a single chloride from the solvent; this chloride
in fact caps (µ4-Cl) the tetragonal plane. The Cu-µ4-Cl bond
lengths (mean 2.624; 2.503-2.708 Å) exceed the sum of
covalent radii, 2.58 Å.18d The other two tricoordinated copper
atoms, Cu2 and Cu4, form a relatively close Cu‚‚‚Cu contact
with a length 3.024(1) Å. Another close contact is between
Cu3 and Cu5 [2.997(1) Å], but both of these contacts are
longer than the sum of the van der Waals radii of the Cu
atom, 2.80 Å.18d
Figure 2. Thermal ellipsoid drawing (30% probability level) of 9 with
atomic numbering scheme (with phenyl rings and isopropyl groups omitted
for clarity).
The trigonal-prismatic metal core observed in 5 is ex-
tremely unusual in cluster chemistry. Most hexanuclear
clusters or cage molecules prefer an octahedral metal core
over a trigonal prismatic core. However, M6 clusters that
contain interstitial main group elements such as [M6(µ6-C)-
(CO)15]2- (M ) Co, Rh),40 [M6(µ6-N)(CO)15]- (M ) Co,
Rh),41 [Os6(µ6-P)(CO)18]-,42 and [H2Ru6(µ6-B)(CO)18]-43 do
Figure 3. Thermal ellipsoid drawing (30% probability level) of 2 with
atomic numbering scheme (with phenyl rings and alkyl groups omitted for
clarity). The structure of 3 is similar.
VI of bonding, and replacing CH2Cl2 with THF stabilized
trinuclear cluster 2 with two different geometries around the
Cu centers. The geometry around each Cu(1) and Cu(2)
center is distorted trigonal planar [106.39(5)-131.03(5)°] and
that around the Cu(3) center is distorted tetrahedral (ca. 81-
124°). The angles around the triply bridging sulfur atom of
the dtp ligand are in the range of 75.64(6)-121.26(7)° (Table
2). The Cu-(µ3-S) bond lengths are unequal and Cu(3)-
S(1) distance, 2.6968(14) Å, is quite long, even exceeding
2.589(2)Å of the Cu-(µ3-S) bond as determined from one
(39) Deivaraj. T. C.; Vittal, J. J. J. Chem. Soc., Dalton Trans. 2001, 322.
(40) Martinengo, S.; Strumolo, D.; Chini, P.; Albano, V. G.; Braga, D. J.
Chem. Soc., Dalton Trans. 1985, 35. (b) Albano, V. G.; Sansoni, M.;
Chini, P.; Martinengo, S. J. Chem. Soc., Dalton Trans. 1973, 651.
(41) Martinengo, S.; Ciani, G.; Sironi, A.; Heaton, B. T.; Masion, J. J.
Am. Chem. Soc. 1979, 101, 7095. (b) Bonfichi, R.; Ciani, G.; Sironi,
A.; Martinengo, S. J. Chem. Soc., Dalton Trans. 1983, 253.
(42) Colbran, S. P.; Lahor, F. J.; Raithby, P. R.; Lewis, J.; Johnson, B. F.
G.; Cardin, C. J. J. Chem. Soc., Dalton Trans. 1988, 173.
Inorganic Chemistry, Vol. 44, No. 26, 2005 9927

Liaw et al.
Figure 6. Thermal ellipsoid drawing (30% probability level) of 4 with
atomic numbering scheme (with phenyl rings and ethyl groups omitted for
clarity).
Figure 5. Thermal ellipsoid drawing (30% probability level) of 6 with
atomic numbering scheme (with phenyl rings and ethyl groups omitted for
clarity).
exhibit a trigonal-prismatic arrangement of six metal atoms.
[(η3-C4H7)6Pd6Se3] contains a slightly distorted Pd6 trigonal
prism whose Pd4 tetragonal faces are capped by µ4-Se
ligands.44 The anionic cluster, [Cu6(µ3-phenylimido)2(µ-
phenyamido)3]-,45 also has a trigonal-prismatic Cu6 core
whose two triangular faces are capped by imido ligands.
Therefore compound 5 is the first neutral M6 cluster in which
a chloro (µ4-Cl) and four dtp ligands cap all five faces of a
trigonal prism.
Dinuclear 6, Cluster 4, and Polymer 7. Dinuclear
compound 6 has bridging dppm and chelating dtp ligands
with tetracoordinated Cu atoms. The lattice contains one CH2-
Cl2 molecule. The eight-membered ring, consisting of two
bridging dppm ligands and two copper atoms adopts the boat
conformation, as shown in Figure 5a. The angles at Cu vary
over a wide range: the S-Cu-S angle is the smallest and
the other angles lie in a wide range, ca. 104-122° (Table
2), and the geometry is distorted tetrahedral (Figure 5). The
literature reports similar P,P-bridged dimers with the dithio-
carboxylate ligand, [Cu2(µ-dppm)2{S2C-C6H4-X }2](X) H,
o-, m-, and p-CH3).46
Figure 7. Thermal ellipsoid drawing (30% probability level) of 7 with
atomic numbering scheme (with phenyl rings and alkyl groups omitted for
clarity). The structure of 8 is similar.
Cu atom is bonded to one P and three S atoms. The other
two dtp ligands bond to the four Cu atoms by the front and
back face of the square, according to bonding mode VII.
The angles around the Cu centers lie in the range of 103-
116°, forming a shape that was closer to the tetrahedron than
the several near-tetragonal copper centers discussed above.
No close Cu‚‚‚Cu contact is shorter than ca. 3.50 Å. The
core geometry in 4 is similar to those of [Cu4(dppm)4{S2-
CC(CN)P(O)(OEt)2}2]47 and [Cu4(dppm)4(CS3)2].48
In polymers 7 and 8, dtp ligands chelate to Cu centers,
and dppe serves as a bridging ligand; CH2Cl2 molecules are
present in the lattice. Because of the difference in the number
of CH2 groups connecting the Ph2P moieties in dppm and
dppe, the latter ligand formed the polymers and trinuclear
cluster 9, obtained at low yield. The geometry around each
Cu center is distorted tetrahedral and the zigzag chain
structure (Figure 7) is similar that of its silver analogues,
[Ag(dppe){S2P(OR)2}]n.17
In cluster 4, four copper atoms forms a tetragon with sides
that are alternatively bridged by dppm and dtp ligands in
the two-up and two-down conformation (Figure 6). Thus each
(43) Housecroft, C. E.; Matthews, D. M.; Rheingold, A. L.; Song, X. J.
Chem. Soc., Chem. Comm. 1992, 842.
(44) Fenske, D.; Hollnagel, A.; Merzweiler, K. Z. Naturforsch., B: Chem.
Sci. 1988, 43, 634.
Table 2 demonstrates that the mean P-(µ3-S) bond length
(2.038(2) Å) of all complexes that exhibit µ3-S bonding
(45) Reiss, P.; Fenske, D.; Z. Anorg. Allg. Chem. 2000, 626, 1317.
(46) (a) Manotti, L.; Anna, M.; Ugozzli, F.; Camus, A.; Marsich, N. Inorg.
Chim. Acta 1985, 99, 111. (b) Camus, A.; Marsich, N.; Pellizer, G. J.
Organomet. Chem. 1983, 259, 367. (c) Pellizer, G.; Marsich, N.;
Camus, A. Inorg. Chim. Acta 1989, 155, 167.
(47) Liu, C. W.; Liaw, B. J.; Wang, J. C.; Liou, L. S.; Keng, T. C. J.
Chem. Soc., Dalton Trans. 2002, 1058.
(48) Lanfredi, A. M. M.; Tiripicchio, A.; Camus, A.; Marish, N. J. Chem.
Soc., Chem. Comm. 1983, 1126.
9928 Inorganic Chemistry, Vol. 44, No. 26, 2005

CuI Complexes with Bis(diphenylphosphino)alkanes
exceeds that of those with P-(µ2-S) bonding (2.004(2) Å),
which in turn exceeds that of those with P-(η1-S) bonding
(1.968(2) Å).
5 exhibits remarkable stability in solution and its structure
matches well with that in the solid state. Polymers 7 and 8
show singlet but somewhat broad signals for the dtp and
dppe ligands. Finally, cluster 9 exhibits a very broad signal
associated with dppe resulting from unresolved peaks from
different chemical environments of this ligand, and the
-S2P(OiPr)2 group showed a very sharp signal. However,
the large coordination shift for the dppe component (∆δ )
NMR Spectroscopy. The proton NMR data of compounds
1-9 show peaks attributed to the ethyl and isopropyl groups
of dtp and the -(CH2)- and phenyl groups of dppm and
dppe in their characteristic groups, as indicated in the
Experimental Section. 31P NMR spectroscopy is more
interesting and provides valuable information about the
complexes. The spectrum of 1 includes a sharp peak at 94.35
ppm because of -S2P(OEt)2 with a upfield coordination shift
δComplex - δLigand(PPh ) ) 21.46 ppm) implies that this ligand
2
binds copper atoms very strongly and appears to be
responsible for the stability of such triangular clusters.28
In conclusion, dithiosphosphates in copper(I) compounds
1-9 exhibit a variety of coordination modes. The modes,
with the corresponding compounds in parentheses, are as
follows: Mode I (6-9), Mode II (2-4), Mode IV (1, 5),
Mode VI (2, 3), and Mode VII (4, 5). Clusters 2 and 3 exhibit
a µ3-S bonding for dtp. This finding is the first of its kind in
copper chemistry. The ratio of metal salt to dtp ligand appears
to affect the abstraction of a chloride ion from the CH2Cl2
or CHCl3 solvent. Cluster 5 with the capping of the tetragonal
face of the trigonal prism by µ4-Cl, is a rare structure in
cluster chemistry.
(∆δ ) δComplex - δLigand(S P)) of -20.45 ppm relative to the
2
dtp ligand itself. The dppm component undergoes a down-
field coordination shift (∆δ ) δComplex - δLigand(Ph P) of 3.52
2
ppm. Other compounds, 2-9, showed coordination shifts in
the range of -16.5 to -22.5 ppm for S2P(OR)2 groups;
dppm/dppe components revealed the coordination shift
ranges: (i) 3.5-7.5 ppm for 1-5, (ii) 0.07-2.12 ppm for
6-8, and (iii) 21.5 ppm for 9. Complexes 2 and 3 have two
types of copper atoms so PPh2 groups are expected to be in
the form of a pair of doublet of doublets in each case;
however, the lack of resolution causes the peaks to appear
as a partially resolved broad triplet for 3 and a well resolved
broad triplet for 2. Likewise, unresolved broad signals from
the -S2P(OR)2 groups were obtained. The spectrum of 4
also shows broad signals for both types of ligands, revealing
that in solution it probably dissociates and more than one
species, the identities of which are not yet clear, are present.
Two types of dtp groups in compound 5 show clear sharp
signals in each type at 92.68 and 97.67 ppm. Thus, complex
Acknowledgment. We thank the National Science Coun-
cil of Taiwan for the financial support (NSC 94-2113-M-
259-010).
Supporting Information Available: X-ray crystallographic files
in CIF format for compounds 1-9. This material is available free
of charge via the Internet at http://pubs.acs.org.
IC051166+
Inorganic Chemistry, Vol. 44, No. 26, 2005 9929