172
S. Gu et al. / Inorganic Chemistry Communications 21 (2012) 168–172
H), 8.96 (d, J=8.8 Hz, 2H), 8.50 (s, 2H), 8.59 (d, J=8.0 Hz, 2H), 8.41–8.39 (m, 4 H), in reduction reactions and click chemistry. On the advantage of using well-defined
2
8
.14 (b, 4 H), 7.90–7.87 (m, 2 H), 7.05 (s, 2 H) ppm. 1 C NMR (100 MHz, d
3
catalytic systems, Dalton Trans. 39 (2010) 7595–7606.
6
-DMSO):
δ150.7, 145.5, 144.6, 144.3, 141.9, 137.9, 137.3, 129.9, 129.5, 128.8, 126.5, 124.0,
20.7, 114.4, 59.7 ppm.
20] Synthesis of [Cu (2) ](PF
mL of acetonitrile was treated with Ag
ature. After 10 h, Ag O completely disappeared, an excess of copper powers or
[26] A.A.D. Tulloch, A.A. Danopoulos, S. Kleinhenz, M.E. Light, M.B. Hursthouse,
G. Eastham, Structural diversity in pyridine-N-functionalized carbene
copper(I) complexes, Organometallics 20 (2001) 2027–2031.
[27] A. Biffis, C. Tubaro, E. Scattolin, M. Basato, G. Papini, C. Santini, E. Alvarez, S.
Conejero, Trinuclear copper(I) complexes with triscarbene ligands: catalysis of C–
N and C–C coupling reactions, Dalton Trans. (2009) 7223–7229.
1
[
4
2
)
6 4
(3): A solution of H
2 6 2
(2)(PF ) (783 mg, 1 mmol ) in
5
2
O (24 mg, 0.10 mmol) at room temper-
2
CuI (764 mg,4 mmol) was added. After it was stirred for 12 h at room tempera-
ture, the solution was filtered. The filtrate was then concentrated to ca. 2 mL. Ad-
[28] X.L. Hu, I. Castro-Rodriguez, K. Meyer, Copper complexes of nitrogen-anchored tri-
podal N-heterocyclic carbene ligands, J. Am. Chem. Soc. 125 (2003) 12237–12245.
[29] P.L. Arnold, A.C. Scarisbrick, A.J. Blake, C. Wilson, Chelating alkoxy-N-heterocyclic
carbene complexes of silver and copper, Chem. Commun. (2001) 2340–2341.
[30] X. Hu, I. Castro-Rodriguez, K. Meyer, A bis-carbenealkenyl copper(I) complex
from a tripodal tris-carbene ligand, Organometallics 22 (2003) 3016–3018.
[31] V.V. Rostovtsev, L.G. Green, V.V. Fokin, K.B. Sharpless, A stepwise huisgen cycload-
dition process: copper(I)-catalyzed regioselective “ligation” of azides and termi-
nal alkynes, Angew. Chem. Int. Ed. 41 (2002) 2596–2599.
[32] S.Q. Bai, L.L. Koh, T.S.A. Hor, Structures of copper complexes of the hybrid SNS li-
gand of bis(2-(benzylthio)ethyl)amine and facile catalytic formation of 1-benzyl-
4-phenyl-1H-1,2,3-triazole through click reaction, Inorg. Chem. 48 (2009)
1207–1213.
dition of Et
collected and washed with Et
Anal. Calcd for C62 40Cu
4
4
2
O (20 mL) to the filtrate afforded a brown solid. The precipitate was
O to obtain the orange solid. Yield: 712 mg, 75%.
24.2H O: C, 49.29; H, 2.95; N, 13.69.Found: C,
8.93; H, 3.13; N, 13.76. H NMR (400 MHz, DMSO-d ): δ 9.30 (d, J=8.0 Hz,
H), 8.50 (d, J=8.4 Hz, 4H), 8.47 (d, J=8.8 Hz, 4H), 8.38 (s, 4H), 8.35 (d,
2
H
4
P
4
N
16
F
2
1
6
J=8.4 Hz, 4H), 8.17 (d, J=9.6 Hz, 4H), 7.97 (d, J=4.8 Hz, 4H), 7.8 3(s, 4H),
.63–7. 60 (m, 4H), 6.16 (s, 4H); 13C NMR (100 MHz, DMSO-d
): δ 182.5 (Cu-
C), 149.9, 149.7, 143.2, 142.8, 152.5, 139.2, 129.3, 128.3, 127.4, 126.9, 125.9,
24.8, 120.9, 120.6, 65.2; IR(KBr): λ = 3124 (w),1586 (m), 1516 (m), 1435
7
6
1
-
1
(m), 1399 (m), 1155 (w), 1103 (m), 833 (s) ,734 (w), 560 (s) cm ; ESI-MS
+ 2+
m/z (%): [M-PF
6
]
1697.61, [M-2PF
6
]
776.12.
[
21] Crystallographic data for 3: C70H52Cu4F24N20P4, T=298(2) K, Mr=2007.36,
monoclinic, C2/c, a=23.723(2)Å, b=14.8546(13) Å, c=25.104(2) Å, α=90°
β=107.917(2)° γ=90° V=8417.5(13) Å3, Z=4, Dcalcd=1.584 Mg/m3,
[33] S. Diez-Gonzalez, A. Correa, L. Cavallo, S.P. Nolan, (NHC)copper(I)-catalyzed 3+2
cycloaddition of azides and mono- or disubstituted alkynes, Chem. Eur. J. 12
(2006) 7558–7564.
21353 reflections collected, 7420 reflections unique (Rint=0.1270), goodness-
of-fit on F2=0.927, R1, wR2 [(I >2σ(I)]: 0.0858, 0.2113.
[34] General procedure for the copper catalyzed three-component click reaction:
[
[
[
[
22] V.J. Catalano, L.B. Munro, C.E. Strasser, A.F. Samin, Modulation of metal–metal
separations in a series of Ag(I) and intensely blue photoluminescent Cu(I) NHC-
bridged triangular clusters, Inorg. Chem. 50 (2011) 8465–8476.
23] C. Chen, H. Qiu, W. Chen, Trinuclear copper(I) complex of 1,3-bis(2-pyridinylmethyl)
imidazolylidene as a carbene-transfer reagent for the preparation of catalytically active
nickel(II) and palladium(II) complexes, J. Organomet. Chem. 696 (2012) 4166–4172.
24] C.E. Ellul, G. Reed, M.F. Mahon, S.I. Pascu, M.K. Whittlesey, Tripodal N-heterocyclic
carbene complexes of palladium and copper: syntheses, characterization, and
catalytic activity, Organometallics 29 (2010) 4097–4104.
Complex 3 (0.0075 mmol, 14 mg), alkyl halide (1.0 mmol), a mixture of CH3-
CN/H
added to a 10 mL Schlenk with a magnetic stirrer bar, and the mixture were
stirred at RT over a required duration. H O (2 mL) and CH Cl (8 mL) were
added to the resultant mixture, and the organic layer was separated from the
aqueous phase. The organic extract was dried over MgSO , and filtered. It was
2 3
O (2 mL, volume ratio 1:1), alkyne (1.2 mmol), NaN (1.2 mmol) were
2
2
2
4
then concentrated in vacuum and purified by column chromatography (silica
gel, petroleum ether/ethyl acetate 2:1).
25] S. Diez-Gonzalez, E.C. Escudero-Adan, J. Benet-Buchholz, E.D. Stevens, A.M.Z. Slawin,
S.P. Nolan, (NHC)CuX complexes: synthesis, characterization and catalytic activities