Crystal Growth & Design
Communication
Table 1. Single-Pot Hydrocarboxylation of Cn Alkanes into
Cn+1 Carboxylic Acids Catalyzed by 1
REFERENCES
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a
(1) For recent state-of-the-art books on the topic, see: (a) Batten,
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total
yield
b
c
entry
1
alkane
carboxylic acid product (yield, %)
(%)
n-C5H12 2-methylpentanoic (16.8), 2-ethylbutanoic (7.6),
25.1
hexanoic (0.7)
2
3
4
5
n-C6H14 2-methylhexanoic (7.8), 2-ethylpentanoic (8.3),
16.6
heptanoic (0.5)
n-C7H16 2-methylheptanoic (6.5), 2-ethylhexanoic (5.6), 2- 15.0
propylpentanoic (2.7), octanoic (0.4)
n-C8H18 2-methyloctanoic (5.0), 2-ethylheptanoic (5.1), 2- 14.8
propylhexanoic (4.4), nonanoic (0.3)
n-C9H20 2-methylnonanoic (3.1), 2-ethyloctanoic (2.5), 2-
9.2
propylheptanoic (2.3), 2-butylhexanoic (1.1),
decanoic (0.2)
́
2366. (f) Fromm, K. M.; Sague, J. L.; Mirolo, L. Macromol. Symp.
d
6
7
8
9
C5H10
C6H12
C7H14
C8H16
cyclopentanecarboxylic (39.3), one/ol (4.3)
43.6
30.2
27.4
26.2
2010, 291−292, 75. (g) Perry, J. J. IV; Perman, J. A.; Zaworotko, M. J.
Chem. Soc. Rev. 2009, 38, 1400. (h) Tranchemontagne, D. J.;
Mendoza-Cortes, J. L.; O’Keeffe, M.; Yaghi, O. M. Chem. Soc. Rev.
2009, 38, 1257. (i) Qiu, S.; Zhu, G. Coord. Chem. Rev. 2009, 253,
2891.
d
cyclohexanecarboxylic (28.1), one/ol (2.1)
d
cycloheptanecarboxylic (20.9), one/ol (6.5)
d
cyclooctanecarboxylic (13.7), one/ol (12.5)
a
Reaction conditions: alkane (1.0 mmol), p(CO) = 20 atm (1 atm =
0.266 mmol); compound 1 (4.0 μmol); K2S2O8 (1.5 mmol). H2O
(2.0 mL)/MeCN (4.0 mL); 60 °C, 4 h, 13.0 mL autoclave. Moles of
(3) (a) Banerjee, D.; Parise, J. B. Cryst. Growth Des. 2011, 11, 44704.
(b) Fromm, K. M. Coord. Chem. Rev. 2008, 252, 856.
(4) See the CambridgeStructuralDatabase (CSD, version 5.32, Aug.
2011): Allen, F. H. Acta Crystallogr. 2002, B58, 380.
(5) (a) Karabach, Y. Y.; Guedes da Silva, M. F. C.; Kopylovich,
b
c
product/100 moles of alkane. Yield of all products. The following
regioselectivity parameters C(1)/C(2)/C(3)/C(n) (normalized for
the relative number of H atoms at different positions of linear alkane
chains) were obtained: 1:36:33 (n-C5H12), 1:23:25 (n-C6H14),
1:24:21:20 (n-C7H16), 1:25:25:22 (n-C8H18), and 1:23:19:17:16
́
M. N.; Gil-Hernandez, B.; Sanchiz, J.; Kirillov, A. M.; Pombeiro, A. J. L.
Inorg. Chem. 2010, 49, 11096. (b) Karabach, Y. Y.; Kirillov, A. M.;
Haukka, M.; Kopylovich, M. N.; Pombeiro, A. J. L. J. Inorg. Biochem.
2008, 102, 1190. (c) Karabach, Y. Y.; Kirillov, A. M.; Haukka, M.;
Sanchiz, J.; Kopylovich, M. N.; Pombeiro, A. J. L. Cryst. Growth Des.
2008, 8, 4100.
d
(n-C9H20). one/ol = overall yield of cyclic ketones and alcohols
(products of oxidation).
respectively. Besides, compound 1 has been applied as an
efficient and versatile catalyst precursor for the mild single-pot
hydrocarboxylation of inert Cn alkanes into the corresponding
Cn+1 carboxylic acids, thus extending the limited application of
copper−organic networks in oxidation catalysis. Further
research toward the exploration of the aqueous medium self-
assembly protocol as a convenient synthetic tool for the design
of new functional heterometallic coordination polymers is
currently in progress.
(6) (a) Kirillov, A. M.; Coelho, J. A. S.; Kirillova, M. V.; Guedes da Silva,
M. F. C.; Nesterov, D. S.; Gruenwald, K. R.; Haukka, M.; Pombeiro,
A. J. L. Inorg. Chem. 2010, 49, 6390. (b) Kirillov, A. M.; Karabach, Y. Y.;
Haukka, M.; Guedes da Silva, M. F. C.; Sanchiz, J.; Kopylovich, M. N.;
Pombeiro, A. J. L. Inorg. Chem. 2008, 47, 162. (c) Karabach, Y. Y.;
Kirillov, A. M.; Guedes da Silva, M. F. C.; Kopylovich, M. N.; Pombeiro,
A. J. L. Cryst. Growth Des. 2006, 6, 2200.
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Guedes da Silva, M. F. C.; Pombeiro, A. J. L. Eur. J. Inorg. Chem. 2008,
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ASSOCIATED CONTENT
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S
* Supporting Information
Materials and methods, refinement details for X-ray analysis,
procedure for alkane hydrocarboxylation studies, supporting
references, additional structural representations (Figures S1−
S4), results of thermal analysis (Figure S5, Table S1), additional
catalytic tests (Figure S2, Table S2), and crystallographic file in
CIF format for 1. This material is available free of charge via the
AUTHOR INFORMATION
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Corresponding Author
(A.J.L.P.). Phone: +351 218419207/37. Fax: +351 218464455.
Notes
(10) Synthesis and analytical data of 1: To an aqueous solution
(10.0 mL) of Cu(NO3)2·2.5H2O (1.00 mmol) were added triethanolamine
(1.00 mmol, 130 μL) and an excess of Mg(OH)2 (0.5 g, 8.65 mmol) in
this order, and with continuous stirring in air at room temperature
(rt, ∼25 °C). Pyromellitic acid (0.50 mmol, 127 mg) was dissolved in
an aqueous solution (2.0 mL) of LiOH (2.0 mmol, 46 mg) and then
added to the reaction mixture. This was stirred for 1 day and filtered
off; the filtrate was left in a beaker to evaporate in air at rt. Pale blue
crystals (including those of X-ray quality) were formed in 1−2 weeks
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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This work was supported by the Foundation for Science and
Technology (FCT) (Projects PTDC/QUI-QUI/121526/2010,
PTDC/QUI-QUI/102150/2008, and PEst-OE/QUI/UI0100/
2011), Portugal, as well as its “Science 2007” program.
1073
dx.doi.org/10.1021/cg201459k | Cryst. Growth Des. 2012, 12, 1069−1074