Preparation and Solid-State Characterization of Mixed-Ligand Coordination/Organometallic Oligomers and Polymers of Copper(I) and Silver(I) Using Diphosphine and Mono- and Diisocyanide Ligands

Article abstract of DOI:10.1021/ic034806m

The dimers [Cu₂(dppm)₂(CN-t-Bu)₃](BF ₄)₂ and [Ag₂(dppm)₂(CN-t-Bu) ₂](X)₂ (X^- = BF₄^-, ClO₄^-) and the coordination polymers {[M(diphos)(CN-t-Bu)₂]BF₄}_n (M = Cu, Ag; diphos = bis(diphenylphosphino)butane (dppb), bis(diphenylphosphino)pentane (dpppen), bis(diphenylphosphino)hexane (dpph)), {[Ag₂(dppb) ₃(CN-t-Bu)₂](BF₄)₂}_n, and {[Ag(dpppen)(CN-t-Bu)]BF₄}_n have been synthesized and fully characterized as model materials for the mixed bridging ligand polymers which exhibit the general formula {[M(diphos)(dmb)]BF₄}_n (M = Cu, Ag; dmb = 1,8-diisocyano-p-menthane) and {[Ag(dppm)(dmb)]ClO ₄}_n. The identity of four polymers {[Ag(dppb)(CN-t-Bu)_x]BF₄}_n (x = 1, 2), {[Ag₂(dppb)₃(CN-t-Bu)₂](BF₄) ₂}_n, {[Ag(dppm)(dmb)]ClO₄}_n) and the two dimers has been confirmed by X-ray crystallography. The structure of {[Ag(dppm)(dmb)]ClO₄}_n exhibits an unprecedented 1-D chain of the type {[Ag(dmb)₂Ag(dppm)₂ ²⁺}_n , where d(Ag...Ag) values between tetrahedral Ag atoms are 4.028(1) and 9.609(1) A for the dppm and dmb bridged units, respectively. The {[[Ag(dppb)(CN-t-Bu)_x]BF ₄}_n polymers (x = 1, 2) form zigzag chains in which the Ag atoms are tri- and tetracoordinated, respectively. The {[Ag ₂(dppb)₃(CN-t-Bu)₂](BF₄) ₂}_n polymer, which is produced from the rearrangement of {[Ag(dppb)(CN-t-Bu)₂]BF₄}_n, forms a 2-D structure described as a honeycomb pattern, where large {Ag(dppb)⁺}₆ macrocycles each hosting two counterions and two acetonitrile guest molecules are observed. Properties such as glass transition temperature, morphology, thermal decomposition, and luminescence in the solid state at 293 K are reported. The luminescence bands exhibit maxima between 475 and 500 nm with emission lifetimes ranging between 6 and 55 μs. These emissions are assigned to a metal-to-ligand charge transfer (MLCT) of the type M(I) → π*(NC)/π*(PPh₂).

Full text of DOI:10.1021/ic034806m

Inorg. Chem. 2004, 43, 3127−3135
Preparation and Solid-State Characterization of Mixed-Ligand
Coordination/Organometallic Oligomers and Polymers of Copper(I) and
Silver(I) Using Diphosphine and Mono- and Diisocyanide Ligands
,1a
EÄric Fournier,1a Fre´de´ric Lebrun,1a Marc Drouin,1a Andreas Decken,1b and Pierre D. Harvey*
De´partement de chimie, UniVersite´ de Sherbrooke, Sherbrooke, Que´bec, Canada J1K 2R1, and
the Department of Chemistry, UniVersity of New Brunswick, Fredericton,
New Brunswick, Canada E3B 6E2
Received July 11, 2003
The dimers [Cu2(dppm)2(CN-t-Bu)3](BF ) and [Ag2(dppm)2(CN-t-Bu)2](X)2 (X- ) BF -, ClO -) and the coordination
4 2
4
4
polymers {[M(diphos)(CN-t-Bu)2]BF }n (M ) Cu, Ag; diphos ) bis(diphenylphosphino)butane (dppb), bis-
4
(diphenylphosphino)pentane (dpppen), bis(diphenylphosphino)hexane (dpph)), {[Ag2(dppb)3(CN-t-Bu)2](BF ) }n, and
4 2
{[Ag(dpppen)(CN-t-Bu)]BF }n have been synthesized and fully characterized as model materials for the mixed
4
bridging ligand polymers which exhibit the general formula {[M(diphos)(dmb)]BF }n (M ) Cu, Ag; dmb ) 1,8-
4
diisocyano-p-menthane) and {[Ag(dppm)(dmb)]ClO }n. The identity of four polymers ({[Ag(dppb)(CN-t-Bu)x]BF }n
4
4
(x ) 1, 2), {[Ag2(dppb)3(CN-t-Bu)2](BF ) }n, {[Ag(dppm)(dmb)]ClO }n) and the two dimers has been confirmed by
4 2
4
X-ray crystallography. The structure of {[Ag(dppm)(dmb)]ClO }n exhibits an unprecedented 1-D chain of the type
4
“{Ag(dmb)2Ag(dppm)22+}n”, where d(Ag Ag) values between tetrahedral Ag atoms are 4.028(1) and 9.609(1) Å for
...
the dppm and dmb bridged units, respectively. The {[Ag(dppb)(CN-t-Bu)x]BF }n polymers (x ) 1, 2) form zigzag
4
chains in which the Ag atoms are tri- and tetracoordinated, respectively. The {[Ag (dppb)3(CN-t-Bu)2](BF ) }n polymer,
2
4 2
which is produced from the rearrangement of {[Ag(dppb)(CN-t-Bu)2]BF }n, forms a 2-D structure described as a
4
“honeycomb” pattern, where large {Ag(dppb)+}6 macrocycles each hosting two counterions and two acetonitrile
guest molecules are observed. Properties such as glass transition temperature, morphology, thermal decomposition,
and luminescence in the solid state at 293 K are reported. The luminescence bands exhibit maxima between 475
and 500 nm with emission lifetimes ranging between 6 and 55 µs. These emissions are assigned to a metal-to-
ligand charge transfer (MLCT) of the type M(I) f π*(NC)/π*(PPh2).
+
Introduction
(dmb)2 }n polymers (0 e x e 1)5 and the “polymers of
clusters” {Pd4(dmb)4(dmb)2+}n and {Pt4(dmb)4(diphos)2+}n
(Charts 1 and 2).5i,j The use of two neutral ligands provides
a new and interesting strategy for the design of coordination
networks and deserves to be explored.
1-, 2-, and 3-D polymeric networks constructed from
polydentate ligands and transition metals comprise an area
that has experienced a tremendous increase in interest in
recent years.2 The field is overwhelmingly dominated by the
use of N-containing bridging ligands.3 The use of P- or CNR-
donor-containing assembling groups is far less extensive,4
and examples of mixed-ligand polymers of Cu(I) and Ag(I)
where the bridging ligands are both neutral are rather limited.
Recent related examples of this work provided by this group
We now wish to report the syntheses and characterization
of a series of mixed-ligand Cu(I) and Ag(I) diphosphine-
(2) (a) Holloday, B. J.; Mirkin, C. A. Angew. Chem., Int. Ed. 2001, 40,
2023. (b) Seidel, R. S.; Stang, P. J. Acc. Chem. Res. 2002, 35, 972.
(c) Eddaoui, M.; Moler, D. B.; Li, H.; Chen, B.; Reineke, T. M.;
O’Keefe, M.; Yaghi, O. M. Acc. Chem. Res. 2001, 34, 319. (d)
Moulton, B.; Zaworotko, M. J. Chem. ReV. 2001, 101, 1629. (e)
Khlobystov, A. N.; Blake, A. J.; Champness, N. R.; Lemenovskii, D.
A.; Majouga, A. G.; Zyk, N. V.; Schro¨der, M. Coord. Chem. ReV.
2001, 222, 155. (f) Biradha, K.; Fujita, M. AdV. Supramol. Chem.
2000, 6, 1. (g) Braga, D. Acc. Chem. Res. 2000, 33, 601. (h) Leininger,
S.; Olenyuk, B.; Stang, P. J. Chem. ReV. 2000, 100, 853. (i) Swiegers,
G. F.; Melefetse, T. J. Chem. ReV. 2000, 100, 3483.
+
include the 1-D {M(dmb)2 }n (M ) Cu, Ag; dmb ) 1,8-
diisocyano-p-menthane) and the mixed-metal {CuxAg1-x
-
* Author to whom correspondence should be addressed. E-mail:
pharvey@USherbrooke.ca. Tel.: (819) 821-7092 or (819) 821-8000 ext.
2005. Fax: (819) 821-8017.
(1) (a) Universite´ de Sherbrooke. (b) University of New Brunswick.
10.1021/ic034806m CCC: $27.50 © 2004 American Chemical Society
Published on Web 04/10/2004
Inorganic Chemistry, Vol. 43, No. 10, 2004 3127

Fournier et al.
Chart 1
transition temperature (when it applies), morphology, thermal
decomposition, and luminescence in the solid state are
reported.
Experimental Section
Materials. 1,8-Diisocyano-p-menthane (dmb),6 [Cu2(dppm)2-
- 8
(NCCH3)4](BF4)2,7 and [Ag2(dppm)2](X)2 (X- ) BF4-, ClO4
)
Chart 2
were prepared according to literature procedures. The [M2(diphos)2]-
(BF4)2 dimers (M ) Cu, Ag; diphos ) dppb, dpppen, dpph) were
also prepared according to published methods except that, for [Ag2-
(dppp)2](NO3)2 (dppp ) bis(diphenylphosphino)methane),9 [Ag2-
(dppb)2](ClO4)2, and [M2(dpph)2](ClO4)2 (M ) Cu, Ag),10 AgBF4
and [Cu(NCMe)4]BF4 were used instead of AgNO3, AgClO4, and
[Cu(NCMe)4]ClO4. Their identity of the dimers was verified by
1H, 31P NMR, and IR spectroscopy. The solvents used in the
syntheses (acetone (Fisher), dichloromethane (ACP), and diethyl
ether (ACP)) were purified according to established procedures.11
AgBF4, AgClO4, Cu(BF4)2‚xH2O, t-BuNC, dppm, dppb, dpppen,
and dpph (Aldrich Chemical Co.) and Cu(m) (Anachemia) were
used as received. All air- or moisture-sensitive materials were
handled inside an inert-atmosphere glovebox, and all reactions were
performed using standard Schlenk techniques or a high-vacuum
manifold system.
Table 1. List of Investigated Compounds and Numbering
formula
code
formula
code
[Cu2(dppm)2(CN-t-Bu)3](BF4)2 (1). [Cu2(dppm)2(NCCH3)4]-
(BF4)2 (272 mg, 0.254 mmol) was dissolved in 100 mL of degassed
acetonitrile. A 115 µL (1.02 mmol) volume of t-BuNC was added
dropwise using a microsyringe. The colorless solution was stirred
for 2 h prior to concentrating it in vacuo until a volume of 20 mL
was obtained. A 100 mL volume of diethyl ether was added to the
remaining solution to precipitate a white solid, which was filtered
off and dried. Yield: 95% (319 mg). 1H NMR (CD2Cl2): δ 7.30-
[Cu2(dppm)2(CN-t-Bu)3](BF4)2
1
[Ag2(dppm)2(CN-t-Bu)2](BF4)2
[Ag2(dppm)2(CN-t-Bu)2](ClO4)2 2b
2a
{[Cu(dppb)(CN-t-Bu)2]BF4}n
{[Cu(dpppen)(CN-t-Bu)2]BF4}n
3
6
9
{[Ag(dppb)(CN-t-Bu)2]BF4}n
{[Ag2(dppb)3(CN-t-Bu)2]BF4}n
{[Ag(dpppen)(CN-t-Bu)2]BF4}n
{[Ag(dpppen)(CN-t-Bu)]BF4}n
{[Ag(dpph)(CN-t-Bu)2]BF4}n
4
5
7
8
{[Cu(dpph)(CN-t-Bu)2]BF4}n
{[Cu(dppm)(dmb)]BF4}n
10
12a
12b
14
16
18
11 {[Ag(dppm)(dmb)]BF4}n
{[Ag(dppm)(dmb)]ClO4}n
13 {[Ag(dppb)(dmb)]BF4}n
15 {[Ag(dpppen)(dmb)]BF4}n
17 {[Ag(dpph)(dmb)]BF4}n
{[Cu(dppb)(dmb)]BF4}n
{[Cu(dpppen)(dmb)]BF4}n
{[Cu(dpph)(dmb)]BF4}n
(4) For Cu(I) and Ag(I) coordination polymers, see for recent examples:
(a) Adolf, A.; Gonsior, M.; Krossing, I. J. Am. Chem. Soc. 2002, 124,
7111. (b) Kuang, S.-M.; Zhang, Z.-Z.; Wang, Q.-G.; Mak, T. C. W.
Chem. Commun. 1998, 581. (c) Ino, I.; Zhong, J. C.; Manukata, M.;
Kudora-Sowa, T.; Maekawa, M.; Suenaga, Kitamori, Y. Inorg. Chem.
2000, 39, 4273.
(5) (a) Perreault, D.; Drouin, M.; Michel, A.; Harvey, P. D. Inorg. Chem.
1992, 31, 3688. (b) Fortin, D.; Drouin, M.; Turcotte, M.; Harvey, P.
D. J. Am. Chem. Soc. 1997, 119, 531. (c) Fortin, D.; Drouin, M.;
Harvey, P. D. J. Am. Chem. Soc. 1998, 120, 5351. (d) Fortin, D.;
Drouin, M.; Harvey, P. D. Inorg. Chem. 2000, 39, 2758. (e) Turcotte,
M.; Harvey, P. D. Inorg. Chem. 2002, 41, 1739. (f) Fortin, D.; Harvey,
P. D. Coord. Chem. ReV. 1998, 171, 351. (g) Harvey, P. D. Coord.
Chem. ReV. 2001, 219-221, 17-52. (h) Harvey, P. D. Macromol.
Symp. 2003, 196, 173. (i) Lebrun, F. M. Sc. Dissertation, Universite´
de Sherbrooke, 2001. (j) Zhang, T.; M. Drouin, M.; Harvey, P. D.
Inorg. Chem. 1999, 38, 1305. (k) Zhang, T.; Drouin, M.; Harvey, P.
D. Inorg. Chem. 1999, 38, 957.
dmb coordination polymers, using the bridging diphosphine
ligands dppm, dppb, dpppen, and dpph (Table 1). The highly
crystalline model compounds in which dmb is replaced by
two t-BuNC ligands have been investigated and provide ideal
material for X-ray structure analysis. Properties such as glass
(3) For Cu(I) and Ag(I) coordination polymers, see for recent examples:
(a) Abrahams, B. F.; Batten, S. R.; Hoskins, B. F.; Robson, R. Inorg.
Chem. 2003, 42, 2654. (b) Wang, Q.-M.; Mak, T. C. W. Inorg. Chem.
2003, 42, 1637. (c) Shin, D. M.; Lee, I. S.; Lee, Y.-A.; Chung, Y. K.
Inorg. Chem. 2003, 42, 2977. (d) Effendy; Marchetti, F.; Pettinari,
C.; Pettinari, R.; Skelton, B. W.; White, A. H. Inorg. Chem. 2003,
42, 112. (e) Tong, M.-M.; Wu, Y.-M.; Ru, J.; Chen, X.-M.; Chang,
H.-C.; Kitagawa, S. Inorg. Chem. 2002, 41, 4846. (f) Konaka, H.;
Wu, L. P.; Munakata, M.; Kuroda-Sowa, T.; Maekawa, M.; Suenaga,
Y. Inorg. Chem. 2002, 41, 1928. (g) Dong, Y.-B.; Ma, R.-P.; Huang,
R.-Q. Inorg. Chem. 2003, 42, 294. (h) Reger, D. L.; Semeniue, R. F.;
Smith, M. D. Inorg. Chem. 2001, 40, 6545. (i) Bu, X.-H.; Liu, H.;
Du, M.; Wong, K. M.-C.; Yam, V. W.-W.; Shionoya, M. Inorg. Chem.
2001, 40, 4143. (j) Carlucci, L.; Ciani, G.; Proserpio, D. M.; Rizzato,
S. New J. Chem. 2003, 27, 483. (k) Muthu, S.; Yip, J. H. K.; Vittal,
J. J. J. Chem. Soc., Dalton Trans. 2002, 4561. (l) Hamilton, B. H.;
Ziegler, C. J. Chem. Commun. 2002, 842. (m) Carlucci, L.; Ciani, G.;
Proserpio, D. M.; Rizzato, S. Cryst. Eng. Commun. 2002, 4, 121. (n)
Ferlay, S.; Koenig, S.; Hosseini, M. W.; Pansanel, J.; De Cian, A.;
Kyritsakas, N. Chem. Commun. 2002, 218. (o) Patra, G. K.; Goldberg,
I. J. Chem. Soc., Dalton Trans. 2002, 1051. (p) Horikoshi, R.;
Mochida, T.; Maki, N.; Yamada, S.; Morivana, H. J. Chem. Soc.,
Dalton Trans. 2002, 28. (p) Caradoc-Davies, P. L.; Hanton, L. R.
Chem. Commun. 2001, 1098. (q) Blake, A. J.; Champness, N. R.;
Cooke, P. A.; Nicolson, J. E. B. Chem. Commun. 2000, 665. (r) Bu,
W.-M.; Ye, L.; Fan, Y.-G. Chem. Lett. 2000, 152.
(6) Weber, W. D.; Gokel, G. W.; Ugi, I. K. Angew. Chem., Int., Ed. Engl.
1972, 11, 530.
(7) (a) Huang, K.-C.; Shieh, M.-H.; Jang, R.-J.; Peng, S.-M.; Lee, G.-H.;
Shieh, M. Organometallics 1998, 17, 5202. (b) Tan, W.; Zheng, H.;
Jin, Q.; Jin, G.; Ji, W.; Long, D.; Xin, X. Polyhedron 2000, 19, 1545.
(c) See also: Wu, M.-M.; Zhang, L.-Y.; Qin, Y.-H.; Chen, Z.-N. Acta
Crystallogr., Sect. E: Struct. Rep. Online 2003, E59, m195. (d) Diez,
J.; Gamasa, M. P.; Gimeno, J.; Tiripicchio, A.; Tiripicchio, C. M. J.
Chem. Soc., Dalton Trans. 1987, 1275.
(8) (a) Birte, A.; Jones, P. G. Acta Crystallogr. 1998, C54, 16. (b) Van
Der Ploeg, A. F. M. J.; Van Koten, G. Inorg. Chim. Acta 1981, 51,
225.
(9) Ruina, Y.; Yimin, H.; Baoyu, X.; Dongmei, W.; Douman, J. Transition
Met. Chem. 1996, 21, 28.
(10) Kitagawa, S.; Kondo, M.; Kawata, S.; Wada, S.; Maekawa, M.;
Munakata, M. Inorg. Chem. 1995, 34, 1455.
(11) (a) Perrin, D. D.; Armarego, W. L. F.; Perrin, D. R. Purifications of
laboratory chemicals; Pergamon Press: Oxford, U.K., 1966. (b)
Gordon, A. J.; Ford, R. A. The chemist’s companion, a handbook of
practical data, techniques, and references; Wiley: New York, 1972;
p 436.
3128 Inorganic Chemistry, Vol. 43, No. 10, 2004

Oligomers and Polymers of Copper(I) and SilWer(I)
7.14 (m, 40H, Ph), 3.32 (m, 4H, CH2P), 1.48 (s, 32H, CH3). 31P-
{1H} NMR (CD2Cl2): δ -2.13. 13C{1H} NMR (CD2Cl2): δ 138.5,
132.3, 130.9, 129.2, 58.4, 30.0. IR (KBr): ν 2176 (CtN), 1061
cm-1 (BF4). Raman (neat solid): ν 2175 cm-1 (CtN). Anal. Calcd
for Cu2C65H71N3P4B2F8: C, 59.19; H, 5.43; N, 3.19. Calcd for
Cu2C65H71N3P4B2F8 + 0.5 C5H9N: C, 59.59; H, 5.59; N, 3.60.
Found: C, 59.68; H, 5.93; N, 3.68. Crystals suitable for X-ray
analysis were obtained by slow evaporation of an acetonitrile
31P{1H} NMR (CD2Cl2): δ -3.69. 13C{1H} NMR (CD2Cl2): δ
134.71, 132.65, 130.47, 129.18, 57.43, 30.00, 26.30, 29.97, 25.72,
21.82. IR (KBr): ν 1059 (BF4), 2172 cm-1 (CtN). Raman (neat
solid): ν 2173 cm-1 (CtN). Anal. Calcd for CuC39H48N2P2BF4:
C, 61.87; H, 6.39; N, 3.70. Found: C, 61.72; H, 6.52; N, 3.70.
{[Ag(dpppen)(CN-t-Bu)2]BF4}n (7). The complex was prepared
in the same manner as 1, except [Cu2(dppm)2(NCCH3)4](BF4)2 was
1
replaced by [Ag2(dpppen)2](BF4)2. Yield: 72%. H NMR (CD2-
1
solution. The X-ray data confirmed the indentity of 1, and the H
Cl2): δ 7.47-7.35 (m, 20H, Ph), 2.22 (m, 4H, CH2P), 1.62 (m,
2H, CH2CH2CH2P), 1.49 (m, 4H, CH2CH2P), 1.34 (s, 18H, CH3).
31P{1H} NMR (CD2Cl2): δ 2.45. 13C{1H} NMR (CD2Cl2): δ 142.3,
132.7, 130.7, 129.3, 57.3, 30.0, 26.8, 24.4. IR (KBr): ν 1056
(BF4-), 2178 cm-1 (CtN). Raman (neat solid): ν 2178 cm-1 (Ct
N). Anal. Calcd for CuC39H48N2P2BF4: C, 58.45; H, 6.04; N, 3.50.
Found: C, 58.11; H, 5.95; N, 4.07.
NMR spectroscopic signature was identical with that described
above, except that the integration for t-BuNC corresponds with the
structure.
[Ag2(dppm)2(CN-t-Bu)2](BF4)2 (2a). The complex was prepared
in the same manner as 1, except [Cu2(dppm)2(NCCH3)4](BF4)2 was
replaced by [Ag2(dppm)2](BF4)2. Yield: 75%. 1H NMR (CD2Cl2):
δ 7.42-7.23 (m, 40H, Ph), 3.42 (m, 4H, CH2P), 1.46 (s, 18H, CH3).
31P{1H} NMR (CD2Cl2): δ 6.2. 13C{1H} NMR (CD2Cl2): δ 141.1,
132.7, 131.4, 129.4, 58.0, 30.0, 26.2. IR (KBr): ν 2181 (CtN),
1056 cm-1 (BF4-). Raman (neat solid): ν 2178 cm-1 (CtN). Mass-
FAB: m/z 1071 (Ag2(dppm)2, m/z 1071.4). Anal. Calcd for
Ag2C60H62N2P4B2F8: C, 54.41; H, 4.72; N, 2.12. Found: C, 54.40;
H, 5.00; N, 2.17.
{[Ag(dpppen)(CN-t-Bu)]BF4}n (8). Polymer 7 was dissolved
in a minimal amount of acetone, and the solution was exposed to
tert-butyl methyl ether by slow diffusion over a few months.
Colorless and irregular shaped crystals were obtained which were
1
characterized from X-ray crystallography. H NMR (CD2Cl2): δ
7.50-7.37 (m, 20H, Ph), 2.31 (m, 4H, CH2P), 1.71-1.46 (m, 15H,
CH2CH2P, CH2CH2CH2P, CCH3).
[Ag2(dppm)2(CN-t-Bu)2](ClO4)2 (2b). The complex is prepared
in the same manner as 2a, except that [Ag2(dppm)2](ClO4)2 was
used instead of [Ag2(dppm)2](BF4)2. Crystals were obtained by slow
vapor diffusion of tert-butyl methyl ether in an acetonitrile solution.
Yield: 80%. 1H NMR (CD2Cl2): δ 7.40-7.35 (m, 40H, Ph), 3.59
(m, 4H, CH2P), 1.46 (s, 18H, CH3). 31P{1H} NMR (CD2Cl2): δ
6.2. 13C{1H} NMR (CD2Cl2): δ 142.3, 133.1, 131.5, 130.9, 129.5,
57.9, 29.7, 24.9. IR (KBr): ν 2178 (CtN), 1090 cm-1 (ClO4-).
Raman (neat solid): ν 2178 cm-1 (CtN).
{[Cu(dpph)(CN-t-Bu)2]BF4}n (9). The complex was prepared
in the same manner as 1, except [Cu2(dppm)2(NCCH3)4](BF4)2 was
replaced by [Cu2(dpph)2](BF4)2. Yield: 73%. H NMR (CD2Cl2):
δ 7.50-7.29 (m, 20H, Ph), 2.18 (m, 4H, CH2P), 1.75 (m, 4H, CH2-
CH2P), 1.41 (m, 4H, CH2CH2CH2P), 1.34 (s, 18H, CH3). 31P{1H}
NMR (CD2Cl2): δ -1.61. 13C{1H} NMR (CD2Cl2): δ 140.22,
134.03, 132.49, 130.47, 129.16, 57.60, 32.66, 30.06, 28.24, 26.09.
IR (KBr): ν 1060 (BF4), 2174 cm-1 (CtN). Raman (neat solid):
ν 2178 cm-1 (CtN). Anal. Calcd for CuC40H50N2P2BF4: C, 62.30;
H, 6.54; N, 3.63. Found: C, 62.18; H, 6.64; N, 3.60.
1
{[Cu(dppb)(CN-t-Bu)2]BF4}n (3). The complex was prepared
in the same manner as 1, except [Cu2(dppm)2(NCCH3)4](BF4)2 was
{[Ag(dpph)(CN-t-Bu)2]BF4}n (10). The complex was prepared
in the same manner as 1, except [Cu2(dppm)2(NCCH3)4](BF4)2 was
1
replaced by [Cu2(dppb)2](BF4)2. Yield: 55%. H NMR (CD2Cl2):
1
δ 7.50-7.42 (m, 20H, Ph), 2.36 (m, 4H, CH2P), 1.81 (m, 4H, CH2-
CH2P), 1.29 (s, 18H, CH3). 31P{1H} NMR (CD2Cl2): δ -0.63. 13C-
{1H} NMR (CD2Cl2): δ 134.83, 132.55, 130.53, 129.25, 57.48,
30.05, 25.27, 23.97. IR (KBr): ν 1061 (BF4), 2174 cm-1 (CtN).
Raman (neat solid): ν 2178 cm-1 (CtN). Anal. Calcd for
CuC38H46N2P2BF4: C, 61.42; H, 6.24; N, 3.77. Found: C, 61.03;
H, 6.37; N, 3.81.
replaced by [Ag2(dpph)2](BF4)2. Yield: 84%. H NMR (CD2Cl2):
δ 7.42-7.33 (m, 20H, Ph), 2.10 (m, 4H, CH2P), 1.40 (s, 18H, CH3),
1.26-1.25 (m, 8H, CH2CH2P + CH2CH2CH2P). 31P{1H} NMR
(CD2Cl2): δ 2.80. 13C{1H} NMR (CD2Cl2): δ 143.15, 132.60,
130.53, 129.13, 57.0, 30.78, 30.12, 27.68, 25.68. IR (KBr): ν 2174,
2135 (CtN), 1055 cm-1 (BF4). Raman (neat solid): ν 2181 cm-1
(CtN). Anal. Calcd for CuC40H50N2P2BF4: C, 58.92; H, 6.18; N,
3.44. Found: C, 59.07; H, 6.18; N, 3.48.
{[Cu(dppm)(dmb)]BF4}n (11). [Cu2(dppm)2(NCMe)4](BF4)2
(222.1 mg, 0.18 mmol) was dissolved in 30 mL of acetonitrile. A
69.0 mg (0.36 mmol) amount of dmb was dissolved separately in
a round flask containing 60 mL of acetonitrile. This latter colorless
solution was slowly added dropwise to the former. The mixture
was stirred for 2 h prior to being reduced to 15 mL in vacuo. A
150 mL volume of diethyl ether was added to the reaction mixture
precipitating the white product, which was filtered off and dried in
vacuo. Yield: 74% (260.2 mg). 1H NMR (CD2Cl2): δ 7.31-7.14
(m, 40H, Ph), 3.26 (m, 4H, CH2P), 1.96-0.93 (m, 36H dmb). 31P-
{1H} NMR (CD2Cl2): δ -4.50. 13C{1H} NMR (CD2Cl2): δ 140.58,
132.60, 131.20, 129.41, 66.00, 60.54, 44.20, 36.23, 28.45, 27.41,
22.72, 15.43. IR (KBr): ν 1103 (BF4), 2181 cm-1 (CtN). Raman
(neat solid): ν 2171 cm-1 (CtN). Anal. Calcd for CuC37H40N2P2-
BF4: C, 61.29; H, 5.56; N, 3.86. Found: C, 61.31; H, 5.61; N,
3.96.
{[Ag(dppb)(CN-t-Bu)2]BF4}n (4). The complex was prepared
in the same manner as 1, except [Cu2(dppm)2(NCCH3)4](BF4)2 was
1
replaced by [Ag2(dppb)2](BF4)2. Yield: 91%. H NMR (CD2Cl2):
δ 7.42-7.35 (m, 20H, Ph), 2.05 (m, 4H, CH2P), 1.42 (m, 4H, CH2-
CH2P), 1.38 (s, 18H, CH3). 31P{1H} NMR (CD2Cl2): δ 3.24. 13C-
{1H} NMR (CD2Cl2): δ 142.6, 132.6, 130.5, 129.1, 57.0, 30.0,
27.0, 26.7. IR (KBr): ν 2184 (CtN), 1057 cm-1 (BF4). Raman
(neat solid): ν 2187 cm-1 (CtN). Anal. Calcd for AgC38H46N2P2-
BF4: C, 57.96; H, 5.89; N, 3.56. Found: C, 58.06; H, 5.88; N,
3.47.
{[Ag2(dppb)3(CN-t-Bu)2]BF4}n (5). Polymer 4 was dissolved
in a minimum amount of acetonitrile and exposed to tert-butyl
methyl ether by slow diffusion for a few months. Colorless and
irregular shaped crystals were obtained which were characterized
1
by X-ray crystallography. H NMR (CD2Cl2): δ 7.42-7.28 (m,
60H, Ph), 2.21 (m, 12H, CH2P), 1.58 (m 12H, CH2CH2P), 1.41 (s,
18H,CH3).
{[Cu(dpppen)(CN-t-Bu)2]BF4}n (6). The complex was prepared
in the same manner as 1, except [Cu2(dppm)2(NCCH3)4](BF4)2 was
replaced by [Cu2(dpppen)2](BF4)2. Yield: 89%. H NMR (CD2-
Cl2): δ 7.48-7.33 (m, 20H, Ph), 2.31 (m, 4H, CH2P), 1.36 (m,
4H, CH2CH2P), 1.29 (s, 18H, CH3), 1.23 (m, 2H, CH2CH2CH2P).
{[Ag(dppm)(dmb)]BF4}n (12a). This polymer was prepared in
the same manner as 11, except [Cu2(dppm)2(NCCH3)4](BF4)2 was
replaced by [Ag2(dppm)2](BF4)2. Yield: 54%. 1H NMR (CD2Cl2):
δ 7.42-7.21 (m, 40H, Ph), 3.36 (m, 4H, CH2P), 1.84 (m, 8H, dmb),
1.48-1.34 (m, 28H, dmb). 31P{1H} NMR (CD2Cl2): δ 5.71. 13C-
1
Inorganic Chemistry, Vol. 43, No. 10, 2004 3129

Fournier et al.
{1H} NMR (CD2Cl2): δ 146.59, 144.95, 132.78, 131.51, 129.56,
63.90, 60.72, 43.19, 36.50, 28.34, 26.76, 22.39. IR (KBr): ν 1059
(BF4), 2180, 2134 cm-1 (CtN). Raman (neat solid): ν 2178 cm-1
(CtN). Anal. Calcd for AgC37H40N2P2BF4: C, 57.76; H, 5.24; N,
3.64. Found: C, 57.23; H, 5.28; N, 3.64. Mass-FAB: m/z 1071
(Ag2(dppm)2(BF4), m/z 1071.4).
{[Ag(dppm)(dmb)]ClO4}n (12b). This polymer was prepared
in the same manner as 11, except [Cu2(dppm)2(NCCH3)4](BF4)2
was replaced by [Ag2(dppm)2](ClO4)2. Yield: 93%. 1H NMR (CD3-
CN): δ 7.45-7.10 (m, 40H, Ph), 3.55 (s, 4H, CH2P), 2.20-1.97
(m, 12H, dmb), 1.64-1.40 (m, 24H, dmb). 31P{1H} NMR (CD3-
CN): δ 9.85. 13C{1H} NMR (CD3CN): δ 145.8, 144.3, 133.1,
131.6, 129.4, 65.8, 65.0, 61.6, 42.3, 36.0, 27.4, 26.6, 25.4, 22.4,
15.1. IR (KBr): ν 1090 (ClO4), 2178 cm-1 (CtN). Anal. Calcd
for AgC31H31N2P2ClO4: C, 54.21; H, 4.55; N, 2.04. Found: C,
54.24; H, 4.76; N, 2.24. Mass-FAB: m/z 1274 (Ag2(dppm)2(dmb)-
(ClO4), m/z 1274.3).
(CD2Cl2): δ 3.63. 13C{1H} NMR (CD2Cl2): δ 146.26, 145.55,
132.74, 130.72, 129.32, 63.31, 60.60, 44.17, 36.98, 30.47, 28.95,
27.61, 26.55, 25.45, 22.77. IR (KBr): ν 2169, 2130 (CtN), 1057
cm-1 (BF4). Raman (neat solid): ν 2172 cm-1 (CtN). Anal. Calcd
for C42H50N2P2BF4Ag: C, 60.09; H, 6.00; N, 3.34. Found: C, 59.89;
H, 6.20; N, 3.36. Mass-FAB: m/z 1277 (Ag2(dpph)(dmb)2(CN)2-
(BF4)2, m/z 1276.5).
Apparatus. NMR spectra were acquired using a Bruker AC-
300 spectrometer (1H, 300.15 MHz; 13C, 75.48 MHz; 31P, 121.50
MHz) using the solvent as chemical shift standard, except in 31P
NMR, where the chemical shifts are referenced to D3PO4 (85% in
D2O). All chemical shifts (δ) and coupling constants (J) are given
in ppm and Hertz, respectively. IR spectra were acquired using a
Bomem FT-IR MB series spectrometer equipped with a baseline-
diffused reflectance. Emission spectra and emission lifetimes were
measured using a nanosecond N2 laser system from PTI (model
GL-3300 pumping a dye laser model GL-302) with an excitation
wavelength of 311 nm. Emission spectra were also measured using
a SPEX Fluorolog II. Glass transition temperatures (Tg) were
measured using a Perkin-Elmer 5A DSC7 equipped with a thermal
controller 5B TAC 7/DS, employing water and indium as calibration
standards. FT-Raman spectra were acquired using a Bruker RFS
100/S spectrometer. XRD were acquired using a Rigaku/USA Inc.
diffractometer with a copper lamp operating under a 30 mA current
and a 40 kV tension. TGA were obtained under N2 using a TGA
7 Perkin-Elmer instrument, with a temperature range of 50-650
°C increasing by at 3°/min. Chemical analyses were performed at
the Universite´ de Montre´al and the University of Toronto.
{[Cu(dppb)(dmb)]BF4}n (13). This polymer was prepared in
the same manner as 11, except [Cu2(dppm)2(NCCH3)4](BF4)2 was
1
replaced by [Cu2(dppb)2](BF4)2. Yield: 70%. H NMR (CD2Cl2):
δ 7.43 (m, 20H, Ph), 2.35 (m, 4H, CH2P), 2.10-1.07 (m, 22H,
CH2CH2P + dmb). 31P{1H} NMR (CD2Cl2): δ -0.38, -2.78. 13C-
{1H} NMR (CD2Cl2): δ 134.60, 132.50, 130.67, 129.35, 63.18,
61.14, 43.90, 37.11, 29.34, 28.04, 26.06, 22.91. IR (KBr): ν 2170
(CtN), 1061 cm-1 (BF4). Raman (neat solid): ν 2171 cm-1 (Ct
N).
{[Ag(dppb)(dmb)]BF4}n (14). This polymer was prepared in
the same manner as 11, except [Cu2(dppm)2(NCCH3)4](BF4)2 was
1
Crystallography. Crystals were obtained by slow evaporation
(12b) from acetonitrile solution or by vapor diffusion using
acetonitrile-tert-butyl methyl ether at 23 °C (1, 5, 7). Data for
12b and 1 were collected at 293(2) K on an Enraf-Nonius CAD-4
automatic diffractometer at the Universite´ de Sherbrooke. The
NRCCAD program was used for centering, indexing, and data
collection.12 Two standard reflections were measured every 60 min,
and no significant decay was observed during data collection. The
NRCVAX programs were used for crystal structure solution by
application of direct methods.13 The SHELX-97 program was used
for refinement by full-matrix least squares of F2.14 Empirical
absorption corrections were made on the basis of a ψ scan. Isotropic
extinction coefficients were included in the refinement to account
for secondary extinction effects.15 Hydrogen atoms were geo-
metrically placed, and the respective final refinements included
anisotropic thermal parameters for non-hydrogen atoms and iso-
tropic thermal parameter for the hydrogen atoms. Single crystals
of 5, 7, and 8 were coated with Paratone-N oil, mounted using a
glass fiber, and frozen in the cold nitrogen stream of the goniometer.
A hemisphere of data was collected on a Bruker AXS P4/SMART
1000 diffractometer (University of New Brunswick) using ω and
θ scans with a scan width of 0.3° and 30 (7, 8) or 25 s (5) exposure
times. The detector distance was 6 (7, 8) or 5 cm (5). The data
were reduced and corrected for absorption.16,17 The structure was
solved by direct methods and refined by full-matrix least squares
on F.18 For 7, the space group was checked using MISSYM in
replaced by [Ag2(dppb)2](BF4)2. Yield: 85%. H NMR (CD2Cl2):
δ 7.40-7.28 (m, 20H, Ph), 2.22 (m, 4H, CH2P), 1.88-1.81 (m,
4H, dmb), 1.61-1.42 (m, 18H, dmb + CH2CH2P). 31P{1H} NMR
(CD2Cl2): δ 4.42. 31P{1H} NMR (DMF-d7): δ 7.62. 13C{1H} NMR
(DMF-d7): δ 151.47, 137.15, 134.86, 133.42, 66.8, 64.12, 48.14,
40.82, 32.68, 30.67, 29.51, 26.79. 13C{1H} NMR (DMSO-d6): δ
147.29, 146.75, 132.49, 130.36, 128.87, 61.76, 59.29, 43.25, 36.07,
28.44, 26.30, 24.91, 22.03. IR (KBr): ν 2167, 2132 (CtN), 1060
cm-1 (BF4). Raman (neat solid): ν 2172 cm-1 (CtN). Anal. Calcd
for C40H46N2P2BF4Ag: C, 59.21; H, 5.71; N, 3.45. Found: C, 58.95;
H, 5.90; N, 3.31. Mass-FAB: m/z 1238 (Ag(dppb)2(dmb)(BF4), m/z
1238.0).
{[Cu(dpppen)(dmb)]BF4}n (15). This polymer was prepared in
the same manner as 11, except [Cu2(dppm)2(NCCH3)4](BF4)2 was
replaced by [Cu2(dpppen)2](BF4)2. Yield: 67%. IR (KBr): ν 1061
(BF4), 2168 cm-1 (CtN). Raman (neat solid): ν 2173 cm-1 (Ct
N). Anal. Calcd for CuC41H48N2P2BF4: C, 63.04; H, 6.19; N, 3.59.
Found: C, 62.97; H, 6.30; N, 3.61.
{[Ag(dpppen)(dmb)]BF4}n (16). This polymer was prepared as
for 11, except [Cu2(dppm)2(NCCH3)4](BF4)2 was replaced by [Ag2-
(dpppen)2](BF4)2. Yield: 64%. IR (KBr): ν 1056 (BF4), 2176, 2130
cm-1 (CtN). Raman (neat solid): ν 2178 cm-1 (CtN). Anal. Calcd
for AgC41H48N2P2BF4: C, 59.66; H, 5.86; N, 3.39. Found: C, 59.18;
H, 6.05; N, 3.43. Mass-FAB: m/z 1183 (Ag2(dpppen)2](BF4), m/z
1183.6).
{[Cu(dpph)(dmb)]BF4}n (17). This polymer was prepared in
the same manner as 11, except [Cu2(dppm)2(NCCH3)4](BF4)2 was
replaced by [Cu2(dpph)2](BF4)2. Yield: 85%. IR (KBr): ν 2170
(CtN), 1057 cm-1 (BF4). Raman (neat solid): ν 2172 cm-1 (Ct
N).
(12) Le Page, Y.; White, P. S.; Gabe, E. J. Proc. Am. Crystallogr. Hamilton
Meet. 1986, Abstract PA23.
(13) (a) Gabe, E. J.; Le Page, Y.; Charland, J.-P.; Lee, F. L.; White, P. S.
J. Appl. Crystallogr. 1989, 22, 384. (b) Le Page, Y. J. Appl.
Crystallogr. 1987, 20, 264.
(14) Sheldrick, G. M. SHELX-97; University of Gottingen: Gottingen,
Germany, 1997.
(15) Larson, A. C. Crystallographic Computing; Munksgaard: Copenhagen,
Denmark, 1970; p 291.
{[Ag(dpph)(dmb)]BF4}n (18). This polymer was prepared in
the same manner as 11, except [Cu2(dppm)2(NCCH3)4](BF4)2 was
1
replaced by [Ag2(dpph)2](BF4)2. Yield: 65%. H NMR (CD2Cl2):
δ 7.41-7.33 (m, 20H, Ph), 2.18 (m, 4H, CH2P), 1.88-1.73 (m,
(16) SAINT 6.02; Bruker AXS, Inc.: Madison, WI, 1997-1999.
(17) Sheldrick, G. SADABS1999; Bruker AXS, Inc.: Madison, WI, 1999.
4H, dmb), 1.51-1.23 (m, 24H, dmb + CH2CH2P). 31P{1H} NMR
3130 Inorganic Chemistry, Vol. 43, No. 10, 2004

Oligomers and Polymers of Copper(I) and SilWer(I)
Table 2. Crystal Data for 1, 4, 7, 8, and 12b
[Cu2(dppm)2(CN-t-Bu)3]- {[Ag2(dppb)3(CN-t-Bu)2]- {[Ag(dpppen)(CN-t-Bu)2]- {[Ag(dpppen)(CN-t-Bu)]- {[Ag(dppm)(dmb)]-
(BF4)2 (1)
(BF4)4}n (5)
(BF4)}n (7)
(BF4)}n (8)
ClO4}n (12b)
empirical formula
fw
C
65H71B2Cu2F8N3P4
C98H108Ag2B2F8N4 P6
1917.06
C39H48AgBF4N2P2
801.41
C68H69Ag2B2F8N2P4
1427.49
C74H80Ag2Cl2N4O8P4
1563.94
1318.83
description
cryst size (mm)
temp (K)
cryst system
space group
a (Å)
colorless, parall
0.40 × 0.35 × 0.30
293(2)
monoclinic
P21/a
20.395(3)
15.287(2)
21.022(4)
90
92.347(14)
90
colorless, irregular
0.20 × 0.30 × 0.35
173(1)
triclinic
P1h
11.4175(12)
17.7558(19)
23.465(3)
90.565(2)
92.498(2)
94.076(2)
4740.0(9)
2
colorless, irregular
0.18 × 0.18 × 0.33
198(1)
triclinic
P1
8.7574(9)
14.8390(16)
16.7222(18)
86.462(2)
77.099(2)
73.170(2)
2027.5(4)
2
colorless, irregular
0.20 × 0.30 × 0.30
173(1)
monoclinic
P21
11.147(1)
18.423(2)
16.169(2)
90
91.619(2)
90
colorless, needle
0.20 × 0.20 × 0.20
293(2)
triclinic
P1h
13.1321(19)
13.3093(18)
13.4611(16)
103.780(12)
107.349(11)
115.764(11)
1828.0(4)
1
b (Å)
c (Å)
R (deg)
â (deg)
γ (deg)
V (Å3)
6548.6(18)
4
3319.0(7)
2
Z
radiatn
Cu KR
1.540 60
1.338
ω/2θ
2728
Mo KR
Mo KR
Mo KR
0.710 73
1.428
ω and φ
1454
Cu KR
wavelength (Å)
calcd density (Mg/m3)
scan mode
F(000)
0.710 73
0.710 73
1.540 60
1.343
ω and φ
1980
1.313
ω and φ
828
1.421
ω/2θ
804
abs coeff (mm-1
θ range (deg)
limiting indices
)
2.256
0.577
0.622
0.75
6.249
2.10-71.98
-25 e h e 18
0 e k e 18
0 e l e 25
12 096
0.87-27.50
-14 e h e 13
-23 e k e 22
-29 e l e 30
31 368
1.25-25.00
-10 e h e 10
-15 e k e 17
-19 e l e 19
10 516
1.26-25.00
-13 e h e 13
-21 e k e 20
-18 e l e 19
17 191
3.80-69.93
-16 e h e 13
0 e k e 16
-16 e l e 15
6931
reflcns collcd
indpndnt reflcns
12 096
20 217
9001
9324
5990
data/restraints/params
goodness-of-fit on F2
final R indices [I > 2σ(I)]a
12 096/0/758
1.051
20 217/0/1117
1.056
9001/3/922
1.036
9324/1/803
1.113
6931/0/425
1.062
R1 ) 0.0669
wR2 ) 0.1997
R1 ) 0.0822
wR2 ) 0.2159
1.142
R1 ) 0.0582
wR2 ) 0.1901
R1 ) 0.0879
wR2 ) 0.2092
2.983
R1 ) 0.0402
wR2 ) 0.1053
R1 ) 0.0415
wR2 ) 0.1068
1.906
R1 ) 0.0593
wR2 ) 0.1571
R1 ) 0.0618
wR2 ) 0.1583
1.471
R1 ) 0.0484
wR2 ) 0.1542
R1 ) 0.0625
wR2 ) 0.2051
1.017
R indices (all data)a
largest diff peak and hole (e Å-3
)
-1.305
-1.170
-0.458
-0.78
-1.210
2
2
4
2
2
2
a R1 ) ∑|Fo| - |Fc|/∑|Fo|; wR2 ) (∑[w(Fo - Fc )2]/∑[Fo ])1/2; w ) 1/[σ2(Fo ) + (AP)2 + (BP)], where P ) (max(Fo , 0) + 2Fc )/3: 1, A ) 0.1617,
B ) 4.7121; 4, A ) 0.1342, B ) 0.000; 7, A ) 0.0657, B ) 1.600; 8, A ) 0.0557, B ) 19.3282, 12b, A ) 0.1478, B ) 1.9468.
PLATON97 included in WINGX.13b No extra crystallographic
Chart 3
symmetry was detected. The space group is P1. One of the BF4
anions exhibited disorder, and the site occupancy was determined
using an isotropic model by fixing 0.65 (F(6)-F(8)) and 0.35
(F(6a)-F(8a)) in subsequent refinement cycles. All non-hydrogen
atoms were refined anisotropically. Hydrogen atoms were included
in calculated positions and refined using a riding model. For 5,
one of the solvent molecules and one butyl bridge exhibited disorder
and the site occupancy was determined using an isotropic model
by fixing 0.65 (C(73)-C(74)), 0.35 (C(73A)-C(74A), 0.5 (C(97)-
C(98)), and 0.5 (C(97A)-C(98A)) in subsequent refinement cycles.
Hydrogen atoms were included in calculated positions and refined
using a riding model. Hydrogen atoms for the solvent molecules
were omitted. For 8, one of the tert-butyl groups exhibited disorder
and the site occupancy was determined using an isotropic model
by fixing 0.55 (C(3)-C(5)) and 0.45 (C(3A)-C(5A) in subsequent
refinement cycles. All non-hydrogen atoms were refined anisotro-
groups. The former is consistent with the structure of the
pically. Hydrogen atoms were included in calculated positions and
starting materials, and there is precedence for complexes of
refined using a riding model.
the type “Cu2(dppm)2(L)3” or “Cu2(dppm)2(L)2(L′)”.19 The
Results and Discussion
structure of 1 was confirmed by X-ray crystallography
(Tables 2 and 3; Figure 1). The structure consists of two Cu
atoms, separated by 3.1003(9) Å, bridged by two dppm
ligands and one t-BuNC group. The ligand sphere of the
metal centers is completed by two terminal t-BuNC groups.
The Cu-C distances are 2.059(4) and 2.376(4) Å, indicating
dppm-Containing Dimers. 1 (Chart 3) is prepared from
[Cu2(dppm)2(NCCH3)4](BF4)2 in the presence of an excess
of t-BuNC. Both the 1H NMR and elemental analysis of the
crude product indicate a nonstoichiometric formulation
(∼“[Cu2(dppm)2(CN-t-Bu)3.5](BF4)2”) suggesting the pres-
ence of a mixture of dimers containing either 4 or 3 t-BuNC
(19) (a) Bera, J. K.; Nethaji, M.; Samuelson, A. G. Inorg. Chem. 1999,
38, 218. (b) Bera, J. K.; Nethaji, M.; Samuelson, A. G. Inorg. Chem.
1999, 38, 1725.
(18) Sheldrick, G. SHELXTL 5.1; Bruker AXS, Inc.: Madison, WI, 1997.
Inorganic Chemistry, Vol. 43, No. 10, 2004 3131

Fournier et al.
Table 3. Selected Bond Lengths (Å) and Angles (deg) for 1, 5, 7, 8,
and 12b
[Cu2(dppm)2(CN-t-Bu)3](BF4)2 (1) {[Ag2(dppb)3(CN-t-Bu)2]BF4}n (5)
Cu(1)-P(1)
Cu(1)-P(4)
Cu(2)-P(2)
Cu(2)-P(3)
Cu(1)-C(61)
Cu(1)-C(56)
Cu(2)-C(51)
Cu(2)-C(56)
2.2810(10) Ag(1)-P(1)
2.2631(10) Ag(1)-P(2)
2.2528(9) Ag(1)-P(3)
2.2639(10) Ag(2)-P(4)
2.5190(11)
2.5000(11)
2.4814(11)
2.4670(11)
2.5022(11)
2.5141(12)
2.243(5)
1.969(4)
2.059(4)
1.953(4)
2.376(5)
Ag(2)-P(5)
Ag(2)-P(6)
Ag(1)-C(1)
Ag(2)-C(90)
2.255(5)
P(4)-Cu(1)-P(1)
117.74(4)
P(3)-Ag(1)-P(2) 123.07(4)
P(3)-Ag(1)-P(1) 113.87(4)
C(61)-Cu(1)-P(4) 104.25(12)
C(56)-Cu(1)-P(4) 114.08(11)
C(61)-Cu(1)-P(1) 103.27(11)
C(56)-Cu(1)-P(1) 111.01(12)
C(61)-Cu(1)-C(56) 104.71(18)
P(2)-Ag(1)-P(1)
98.88(4)
C(1)-Ag(1)-P(2) 105.51(12)
C(1)-Ag(1)-P(3) 110.20(12)
C(1)-Ag(1)-P(1) 103.09(13)
P(4)-Ag(2)-P(5) 122.89(4)
P(4)-Ag(2)-P(6) 114.48(4)
+
P(2)-Cu(2)-P(3)
121.75(4)
Figure 2. (A) ORTEP diagram of one Ag(dpppent)(CN-t-Bu)2 unit of
C(51)-Cu(2)-P(2) 109.53(11)
C(51)-Cu(2)-P(3) 105.25(11)
P(2)-Cu(2)-C(56) 112.10(10)
P(3)-Cu(2)-C(56) 103.69(10)
C(51)-Cu(2)-C(56) 102.70(15)
polymer 7. The H atoms and counterions are not shown for clarity. (B)
ORTEP diagram of a segment of polymer 7. The H atoms and counterions
are omitted for clarity. The ellipsoids are shown in 50% probability.
P(5)-Ag(2)-P(6)
99.49(4)
C(90)-Ag(2)-P(4) 112.69(12)
C(90)-Ag(2)-P(5) 101.51(12)
C(90)-Ag(2)-P(6) 103.14(13)
ligands. The Cu-C≡N angles strongly deviate from linearity
(147.8 and 162.9° for the tetra- and tricoordinate metals,
respectively), where the tert-butyl groups are directed away
from each other, providing evidence for intramolecular steric
hindrance. In comparison with the more symmetrically
bridged [Cu2(dppm)2(NCNMe2)2(µ-ClO4)]+ (3.424(5) Å),
[Cu2(dppm)2(NCNMe2)(Cl)(µ-Cl)] (3.293(1) Å), and Cu2-
(dppm)2(NCNMe2)32+ (3.143(2) Å) species, the observed Cu‚
‚‚Cu distance in 1 is the shortest of its kind.19 We propose
that, despite the presence of an excess of t-BuNC in the
reaction, the presence of the unsaturated complex 1 in the
crude mixture is due to ligand lability.
{[Ag(dpppen)(CN-t-Bu)2]BF4}n (7)
{[Ag(dppm)(dmb)]ClO4}n (12b)
Ag(1)-C(6)
Ag(1)-C(1)
Ag(1)-P(1)
Ag(1)-P(2)
2.189(7)
2.335(8)
2.4706(15) Ag-P(1)
2.5136(16) Ag-P(2)
Ag-C(9)
Ag-C(1)
2.251(6)
2.331(6)
2.4672(14)
2.4921(15)
C(6)-Ag(1)-C(1)
C(6)-Ag(1)-P(1)
C(1)-Ag(1)-P(1)
C(6)-Ag(1)-P(2)
C(1)-Ag(1)-P(2)
P(1)-Ag(1)-P(2)
109.0(3)
114.30(17)
117.6(2)
112.69(19)
96.2(2)
105.56(5)
C(9)-Ag-C(1)
99.0(2)
C(9)-Ag-P(1)
C(1)-Ag-P(1)
C(9)-Ag-P(2)
C(1)-Ag-P(2)
P(1)-Ag-P(2)
118.58(17)
97.57(18)
98.14(18)
98.90(18)
136.48(4)
{[Ag(dpppen)(CN-t-Bu)]BF4}n (8)
2a,b are synthesized in the same manner as 1, but even in
the presence of excess t-BuNC, these complexes are the sole
products observed. Poor quality crystals, though suitable for
X-ray analysis (40% of all reflections were observed), were
obtained for 2b (Chart 2 and Supporting Information). The
structure shows similarities to that of [Cu2(dppm)2(NCNMe2)2-
(µ-ClO4)]+,19 where two tricoordinate metal atoms are held
almost face-to-face with a Ag‚‚‚Ag separation of 3.2227-
Ag(1)-C(35)
Ag(1)-C(1)
Ag(1)-P(1)
2.178(11)
2.195(13)
2.425(2)
Ag(1)-P(2)
Ag(2)-P(3)
Ag(2)-P(4)
2.454(3)
2.458(2)
2.453(3)
P(1)-Ag(1)-P(2)
P(1)-Ag(1)-C(1)
P(2)-Ag(1)-C(1)
128.01(8)
120.0(3)
107.2(4)
P(3)-Ag(2)-P(4)
P(3)-Ag(2)-C(35)
P(4)-Ag(2)-C(35)
125.85(8)
113.9(3)
119.3(3)
-
(13) Å, both interacting with an O atom of one of the ClO4
anions. The Ag-O distances (∼2.61 Å) are indicative of
important ionic interactions. The fact that no other t-BuNC
groups is found in the coordination sphere of Ag strongly
contrasts with the structures of the {Ag(dppm)(dmb)+}n
+
(described below) and {M(dmb)2 }n polymers shown in
Chart 1.
t-BuNC Polymers. Compounds 3, 4, 6, 7, 9, and 10 are
prepared in reasonable yields from the reaction between the
starting materials [M2(diphos)2](BF4)2 (M ) Cu, Ag; diphos
) dppb, dpppen, dpph) and an excess of t-BuNC. Crystals
suitable for X-ray analysis were obtained for 7 (Tables 2
and 3; Figure 2). The X-ray structure reveals two crystal-
lographically independent zigzag {Ag(dpppen)+}n chains/
asymmetric unit. These chains differ slightly by the orien-
tation of the Ph and t-BuNC groups. The Ag atoms are placed
in a zigzag geometry and describe a plane, where the P and
C (CNR) atoms are located above and below the plane,
respectively. d(Ag...Ag) is 8.757(1) Å, and P3 is 87.5°. This
structure is not unprecedented as a similar polymer has been
Figure 1. ORTEP diagram of the structure of for [Cu2(dppm)2(NCCH3)3]-
(BF4)2 (1) using 50% probability ellipsoids. The H atoms and counterions
are omitted for clarity.
an unprecedented Cu-CNR semibridging coordination. The
complex is best described as a dimer containing distorted
tetra- and tricoordinate metal centers bridged by two dppm
3132 Inorganic Chemistry, Vol. 43, No. 10, 2004

Oligomers and Polymers of Copper(I) and SilWer(I)
Figure 3. (A) ORTEP diagram of a segment of polymer 8 showing the
skeleton of the chain. The H atoms, counterions, and tert-butyl and phenyl
groups are omitted for clarity. (B) ORTEP diagram of a segment of 8
showing the tricoordinate Ag atoms. The H atoms and counterions are
omitted for clarity. The ellipsoids are shown in 50% probability.
Figure 4. Ball and stick diagram of a segment of 5 showing the 2-D
“Ag2(dppb)32+” repetitive unit. The H atoms, MeCN crystallization
molecules, counterion, and t-BuNC ligand are omitted for clarity.
reported for {Hg(dpppen)I2}n.20 On the basis of the charac-
terization data (Experimental Section) and the physical
properties described below, it is assumed that 3, 4, 6, 9, and
10 are polymeric as well, with similar structures.
When 7 is redissolved and left to recrystallize for several
months, new crystals are obtained. Despite the poor quality
of the crystals, the data again reveal a zigzag polymeric Ag-
dpppen structure, but 7 has lost a t-BuNC ligand to form 8
(Figure 3; Tables 2 and 3).21 The 1:1 dpppen/t-BuNC ratio
1
is consistent with the H NMR data. The repetitive unit
contains two dpppen ligands exhibiting different alkyl chain
conformations and two planar tricoordinate Ag atoms. The
d(Ag...Ag) values for the Ag-dpppen-Ag units are 7.721-
(1) and 8.997(1) Å. The Ag3 value is 83.3°. This zigzag
structure exhibits some similarities with the polymer {Ag-
(dpph)O2CCF3}n (dpph ) bis(diphenylphosphino)hexane),
recently reported by Brandys and Puddephatt.22
Figure 5. Ball and stick diagram of a large segment of 5 showing the
2-D structure. The H atoms and counterion are not shown for clarity. Two
of the MeCN molecules of crystallization are shown. These are related by
symmetry.
When 4 is dissolved in acetonitrile and tert-butyl methyl
ether is slowly diffused into the solution, irregular-shaped
1
crystals are obtained which exhibit a different H NMR
integration for the dppb and t-BuNC ligands in comparison
with the starting material. The X-ray analysis reveals the
presence of a new polymer, where a 2-D structure is observed
(Figures 4 and 5). This structure can be described as a
“honeycomb” or “chicken wire” pattern consisting of large
{Ag(dppb)+}6 macrocycles. These macrocycles exhibit three
different conformations of the dppb ligands. The Ag atoms
are tetracoordinated by three P and one C atoms. This
structure shares similar properties with the {Ag2(dpph)3(O2-
CCF3)3}n and {[Au2(dppb)3](Au(CN)2)}n 2-D polymers re-
cently reported by Brandys and Puddephatt.23,24 The distorted
hexagonal {Ag(dppb)+}6 macrocycles in 5 exhibit three sets
of closest-neighbor Ag‚‚‚Ag distances (8.95, 9.90, and 10.00
Å). The interior of this 42-membered ring exhibits long
Ag‚‚‚Ag diagonal distances varying from 16 to 20 Å and
contains two MeCN molecules of crystallization (Figure 5)
and two BF4- counterions.
Figure 6.
dmb-Containing Materials. 11-18 were prepared in the
same manner as the t-BuNC-containing polymers. Crystals
suitable for X-ray analysis were obtained for 12b (Figure
6). The data reveal an unprecedented 1-D structure of a
mixed-ligand chain (Chart 4), best described as a polymer
of Ag2(dppm)2 dimers that are doubly bridged by dmb
ligands. d(Ag...Ag) values between the tetrahedral Ag atoms
are 4.028(1) and 9.609(1) Å for the dppm and dmb bridged
(20) Aurivillius, K.; Wendel, K. Acta Crystallogr., Sect. B.: Struct.
Crystallogr. Cryst. Chem. 1976, 32, 2941.
(21) The crystals for 7 and 8 appear identical under the microscope.
(22) Brandys, M.-C.; Puddephatt, R. J. Chem. Commun. 2001, 1508.
(23) Brandys, M.-C.; Puddephatt, R. J. J. Am. Chem. Soc. 2002, 124, 3946.
(24) Brandys, M.-C.; Puddephatt, R. J. J. Am. Chem. Soc. 2001, 123, 4839.
2+
Inorganic Chemistry, Vol. 43, No. 10, 2004 3133

Fournier et al.
Table 4. TGA Data for the Polymers 3, 4, 6, 7, 9-11, 12a, and
13-18a
wt loss 1
wt loss 2
residue
(metal alone)
(loss of isocyanides)b
(loss of diphos)b
temp
(°C)
expt theor
(%) (%)
temp
(°C)
expt theor expt theor
(%) (%)
(%)
(%)
3
4
6
7
9
171-229 22
144-176 21
180-220 23
150-200 20
162-224 21
150-190 21
150-330 36
23
21
22
21
21
21
38
25
36
23
35
23
35
23
305-445 68
300-420 65
310-420 66
290-385 67
297-458 70
288-424 66
330-400 55
280-400 63
340-442 54
300-415 64
350-420 58
270-410 61
333-455 56
300-395 64
68
65
69
65
70
66
53
61
56
63
57
64
57
64
10
14
11
13
9
13
9
15
10
13
8
9
14
9
14
8
13
9
14
8
14
8
13
8
10
11
12a 170-220 22
13
14
15
16
17
18
178-340 36
176-231 23
195-340 34
190-210 26
180-249 36
173-226 24
13
8
12
Figure 7. TGA trace for the polymer {[Ag(dpph)(dmb)]BF4}n (18).
13
Chart 4
a The uncertainty is estimated to be ∼2-3% because of a small drift in
the baseline. No data were acquired for 1, 2a, 2b, 5, 7, 8, and 12b. b For
+
the {M(diphos)(CN-t-Bu)2
}
(M ) Cu, Ag) and {Ag(diphos)(dmb)+}n
n
polymers (3, 4, 6, 7, 9, 10, 12a, 14, 16, and 18), the weight loss events
associated with the loss of BF4 overlaps with the weight loss associated
-
+
with the diphosphine ligands (weight loss 2). For the {Cu(diphos)(dmb)2
}
n
polymers (11, 13, 15, 17), the weight loss event associated with the loss of
BF4- overlaps with the weight loss associated with the dmb ligands (weight
loss 1). The data are presented as such.
units, respectively. The dmb ligand adopts the rarely
encountered “Z-shape” (gauche conformation)25 to avoid the
inter-Ag2(dppm)22+ unit Ph...Ph steric interactions that would
otherwise be obtained in the anti conformation. Ring stress
is observed, as the PAgP (136.5), PAgC (103.5 (aver-
age)), and CAgC (99.0°) angles deviate from the ideal
tetrahedral angle, and the AgC bond lengths differ (2.25 and
2.33 Å; Table 3). The Ag2C4P2 ring does not exhibit the
typical S8 crown structure, but rather the 4 P atoms describe
a plane where one Ag and one C atom lie above and below
the plane, describing a local Ci symmetry.
Physical Properties. The colorless polymers are soluble
or weakly soluble in common organic solvents (such as
acetonitrile, methanol, dichloromethane, and chloroform).
The materials prove to be thermally stable to at least 150
°C (TGA) and photochemically stable to sun light (over
several months as no change in color or spectroscopic profile
was observed). The TGA traces exhibit two thermal events.
They occur between 150 and 340 °C (see Figure 7, as an
example, and Table 4), the lower of the two being the loss
of the isocyanide and the higher being the loss of the
diphosphine ligands. The loss of the counterion is spread
over a greater temperature range and overlaps with the ligand
losses (see foonote of Table 4). The loss of the isocyanide
occurs in a narrower temperature window as observed by
the first derivative of the TGA traces. In general, the loss of
the t-BuNC group occurs at a slightly lower temperature than
in the corresponding dmb polymer.
Figure 8. Comparison of the solid-state emission spectra of 6, 11, 15, 7,
12a, and 16 at room temperature. The intensity has not been normalized so
that the bands could be distinguished.
soluble in common solvents (as listed above) and form brittle
films when the solvent is evaporated. Conversely, the Cu
polymers are somewhat less soluble but can form stand-alone
films from spin-coating or simple solution evaporation.
Polymers 15-17 swell in most solvents during attempts to
dissolve them (which prevented us from obtaining reliable
solution 1H NMR spectra) or are simply insoluble. In DMF,
{Cu(diphos)(dmb)BF4}n polymers produce either highly
viscous solutions or a polymer film on the solution surface
(Supporting Information). The XRD patterns indicate that
the Ag materials are more crystalline than those of Cu. This
15 and 17 exhibit Tg (glass transition; DSC) at 47 (∆Cp
) 0.55) and 39 °C (∆Cp ) 0.45 J/(g.deg)), respectively. No
Tg was observed from -20 to 150 °C for any of the other
materials. The Ag-containing materials are generally more
+
property is well-known for the {M(dmb)2 }n polymers,4b,d
where for M ) Ag and Cu shorter (n ∼ 8)2c and longer chains
(25) Harvey, P. D. Coord. Chem. ReV. 2002, 233-234, 289.
3134 Inorganic Chemistry, Vol. 43, No. 10, 2004
(n ∼ 300) are observed.4e In addition, the {[Ag(diphos)-

Oligomers and Polymers of Copper(I) and SilWer(I)
Table 5. Solid-State Spectroscopic and Emission Lifetimes for 3, 4, 6, 7, 9-11, 12a, and 13-18a
{[Cu(diphos)(CN-t-Bu)2]BF4}n
{[Ag(diphos)(CN-t-Bu)2]BF4}n
polymer
morphology
λ
max (nm)
τe (µs)
polymer
morphology
λ
max (nm)
τe (µs)
3
6
9
SC
SC
SC
475
483
485
22 ( 5
31 ( 5
12 ( 3
4
7
10
C
C
C
481
491
486
14 ( 3
55 ( 4
56 ( 4
{[Cu(diphos)(dmb)]BF4}n
{[Ag(diphos)(dmb)]BF4}n
11
13
15
17
A
A
A
A
495
490
492
485
42 ( 7
12a
14
16
C
C
C
C
499
487
483
487
27 ( 3
15 ( 5
24 ( 5
18 ( 3
26 ( 5
48 ( 4
6 ( 1
18
a C ) crystalline, SC ) semicrystalline, A ) amorphous, at 293 K.
(dmb)]BF4}n (10, 14, 16, and 18) polymers exhibit weak
ν(NC) IR peaks at ∼2130 cm-1 (in the solid state) consistent
with uncoordinated RNC groups (i.e. end-of-chain), sug-
gesting that these materials may be oligomers. This feature
is consistent with the highly crystalline morphology.
and PPh2 groups. The similarity in photophysical properties
between the Cu- and Ag-containing materials is not surpris-
ing or, at least, is not unprecedented.4b,28 The interpretation
of this result is not simple since the structures of many of
the investigated materials are not known.29
Luminescence. The luminescence properties of 3, 4, 6,
7, 9-11, 12a, and 13-18 in the solid state were investigated
at 293 K (Figure 8 and Table 5). The solids emit with λmax
in the 491 ( 8 nm window and with emission lifetimes of
6 < τe < 56 µs, which is indicative of phosphorescence.
These λmax’s and τe’s are typical of Cu-P- and Ag-P-
containing chromophores.26 On the basis of recent spectro-
scopic findings and theorical DFT calculations on the related
compoundsM(CN-t-Bu)4+(M)Cu,Ag)4b and[Cu2(dppm)2(O2-
CMe)]+,27 the excited-state responsible for the luminescence
is assigned to a metal-to-ligand charge transfer (MLCT),
where the ligand manifold is both the π-system of the CNR
Acknowledgment. This research was supported by the
Natural Sciences and Engineering Research Council of
Canada (NSERC). P.D.H. thanks Dr. Daniel Fortin for
fruitful discussion on the X-ray data interpretation.
Supporting Information Available: XRD patterns for 3, 4, 6,
7, 9, 10, 12a, 13, 14, and 16-18, a picture showing vials of 15
and 17 in DMF, and X-ray crystallographic files for 1, 2b, 5, 7, 8,
and 12b in CIF format. This material is available free of charge
via the Internet at http://pubs.acs.org.
IC034806M
(26) (a) Che, C.-M.; Yip, H.-K.; Li, D.; Peng, S.-M.; Lee, G.-H.; Wang,
Y.-M.; Liu, S.-T. J. Chem. Soc., Chem. Commun. 1991, 1615. (b)
Che, C.-M.; Yip, H.-K.; Yam, V. W. W.; Cheung, P.-Y.; Lai, T.-F.;
Shieh, S.-J.; Peng, S.-M. J. Chem. Soc., Dalton Trans. 1992, 427. (c)
Li, D.; Che, C.-M.; Kwong, H.-L.; Yam, V. W. W. J. Chem. Soc.,
Dalton Trans. 1992, 3325. (d) Yip, H.-K.; Lin, H.-M.; Cheung, K.-
K.; Che, C.-M.; Wang, Y. Inorg. Chem. 1994, 33, 1644. (e) Yip, H.-
K.; Lin, H.-M.; Wang, Y.; Che, C.-M. J. Chem. Soc., Dalton Trans.
1993, 2939. (f) Wang, C.-F.; Peng, S.-M.; Chan, C.-K.; Che, C.-M.
Polyhedron 1996, 15, 1853.
(28) The presence of an exciton phenomenon is possible. Previous works4b
showed that the λmax’s of emission for the polymer salts {[Ag-
(dmb)2]Y}n (Y ) BF4-, PF6-, NO3-, CH3CO2-) and {[Cu(dmb)2]-
BF4}n were counterion dependent, despite the fact that no interaction
with the chromophore was apparent (but small structural perturbations
were observed), and changed with experimental conditions (i.e.
temperature and physical state). As a consequence the λmax’s of
emission become unpredictable.
(29) The photophysical properties for the polymers in solution are not
investigated as strong RNC ligand dissociation occurs for the Ag
materials.
(27) Harvey, P. D.; Drouin, M.; Zhang, T. Inorg. Chem. 1997, 36, 4998.
Inorganic Chemistry, Vol. 43, No. 10, 2004 3135