Relationship Between Reversible Oxygenation and Catalytic Properties of Amino Acid Cobalt Complexes†

doi:10.7503/cjcu20150578

Abstract

Abstract:

The relationship between oxygenation properties and corresponding catalytic performance of 13 natural amino acid-cobalt(Ⅱ) complexes were identified. The results indicate that for those complexes with reversible oxygenation properties, the shorter the time spent for completing a reversible oxygenation cycle is, the better their reversible oxygenation and the worse the property of their catalysis are. As a contrast, longer cycle time for completing a reversible oxygenation cycle attest to worse performance of reversible oxygenation but better property of catalysis. In particular, the results of glutamic cobalt(Ⅱ) complexes confirms that when the ratio of Co(Ⅱ) and ligand is 1:3, the reversible oxygenation property is good, while the catalytic reaction yields a low conversion rate of cyclohexene. On the other hand, the complex with Co(Ⅱ):ligand 1:1 led to a high conversion rate of cyclohexene. With the help of the preliminary structural study and theoretical calculation, we suppose that the difference between reversible oxygenation property and catalytic property are mainly due to the coordinating ability of amino acid ligands. The strong coordinating ability of amino acid ligands is favorably to the high spin to low spin transform for reversibly absorbing O₂. While the less favorably for vinyl replacement exhibited poor catalytic properties, and vice versa.

Key words: Cobalt(Ⅱ) complex, Amino acid, Oxygenation, Cyclohexene, Catalytic property

CLC Number:

O643
O657.6

TrendMD:

WEI Yana, ZHANG Xincun, LI Hui, XU Qian, YUE Fan, WANG Jide. Relationship Between Reversible Oxygenation and Catalytic Properties of Amino Acid Cobalt Complexes^†[J]. Chem. J. Chinese Universities, 2016, 37(2): 354.

Figures/Tables 7

Fig.1 UV-Vis spectra of Co(Ⅱ)-His(A) and Co(Ⅱ)-Glu(B) complexes a. His or Glu; b. Co(Ⅱ); c. Co(Ⅱ)-His or Co(Ⅱ)-Glu in N2; d: Co(Ⅱ)-His or Co(Ⅱ)-Glu in O2.cL=1.0×10-3 mol/L, L=His, Glu; cCo=5.0×10-4 mol/L.

Fig.2 Reversible oxygenation property and dynamics results of Co(Ⅱ)-His(A) and Co(Ⅱ)-Glu(B) complexes The insets of (A) and (B) show the first cycle of oxygenation and deoxygenation of the complexes.

Fig.3 Relationship between catalytic performance and oxygenation property of amino acid cobalt(Ⅱ) complexes

Fig.4 Effect of composition of catalysts on the oxidation conversion of cyclohexene Reaction conditions: solvent-free, amount of cyclohexene: 1 mL,reaction temperature: 70 ℃, reaction time: 24 h.

Fig.5 Formation of the solid-state Co(Ⅱ)-Glu complexes characterized by UV-Vis a. Glu; b. Co(Ⅱ); c. Co-Glu in N2; d. Co-Glu in O2.

Fig.6 XRD patterns of glutamate cobalt(Ⅱ) complexes a. Simulated pattern; b. synthesized complexes.

Fig.7 Theoretical structural evolution of activating dioxygen by the Co(Ⅱ)-Glu complex with coordinating of ethylene

References 16

[1]	Cho J., Jeon S., Solomon E. I., Wonwoo N., Nature, 2011, 478, 502—505
[2]	Christoph A. R., Hubert W., Lutz H. G., Angew. Chem., 2015, 127(16), 4962—4966
[3]	Cramer C. J., Tolman W. B., Acc. Chem. Res., 2007, 40, 601—608
[4]	Kunishita A., Ertem M. Z., Okubo Y., Tano T., Sugimoto H., Ohkubo K., Fujieda N., Fukuzumi S., Cramer C., Itoh S., Inorg. Chem., 2012, 51, 9465—9580
[5]	Harris W. R., McLendon G., Martell A. E., J. Am. Chem. Soc., 1976, 98(26), 8378—8381
[6]	Chen D. D., Zhang T., Ren L. P., J. Anal. Sci., 2006, 22(5), 600—604
	(陈丹丹, 张涛, 任丽萍. 分析科学学报, 2006, 22(5), 600—604 )
[7]	Burk D., Hearon J., Caroline L., Schade A. L., J. Biol. Chem., 1946, 165(2), 723—724
[8]	Zhang X. C., Yue F., Huang Y., Cheng X., Wen H. M., Hu D., Wang J. D., Chem. J. Chinese Universities, 2012, 33(7), 1370—1375
	(张新村, 岳凡, 黄艳, 程翔, 文红梅, 胡地, 王吉德. 高等学校化学学报, 2012, 33(7), 1370—1375)
[9]	Wen H. M., Zhang X., Li H., Yue F., Wang J. D., Chem. J. Chinese Universities, 2013, 34(10), 2262—2269
	(文红梅, 张旭, 李辉, 岳凡, 王吉德. 高等学校化学学报, 2013, 34(10), 2262—2269)
[10]	Yue F., Song N., Huang Y., Wang J. D., Xie Z F., Lei H. Q., Zhang X. C., Fu P., Tao R. P., Chen X., Shi M. S., Inorg. Chim. Acta, 2013, 398, 141—146
[11]	Fu P., Fu J. H., Li J. F., Yue F., Zhang X. L., Wang J. D., Chinese J. Inorg. Chem., 2012, 28(7), 1360—1364
	(付佩, 符继红, 李俊芳, 岳凡, 张旭龙, 王吉德. 无机化学学报, 2012, 28(7), 1360—1364)
[12]	Zhang X.C., Reversible Oxygenation of Amino Acid-cobalt(Ⅱ) Complexes and Their Basic Structural Unit for Uptaking Dioxygen Reversibly, Xinjiang University, Urumqi, 2012
	(张新村. 氨基酸钴(Ⅱ)配合物可逆氧合性能及其可逆氧合结构单元的研究, 乌鲁木齐: 新疆大学, 2012)
[13]	Fu J. H., Li J. F., Fu P., Yue F., Zhang X. L., Wang J. D., Chem. J. Chinese Universities, 2011, 32(7), 1483—1487
	(符继红, 李俊芳, 付佩, 岳凡, 张旭龙, 王吉德. 高等学校化学学报, 2011, 32(7), 1483—1487)
[14]	Zhang Y. G., Saha M. K., Bernal I., Cryst. Eng. Comm., 2003, 5(5), 34—37
[15]	Frisch M.J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Montgomery J. A. Jr., Vreven T., Kudin K. N., Burant J. C., Millam J. M., Iyengar S. S., Tomasi J., Barone V., Mennucci B., Cossi M., Scalmani G., Rega N., Petersson G. A., Nakatsuji H., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Klene M., Li X., Knox J. E., Hratchian H. P., Cross J. B., Bakken V., Adamo C., Jaramillo J., Gomperts R., Stratmann R. E., Yazyev O., Austin A. J., Cammi R., Pomelli C., Ochterski J. W., Ayala P. Y., Morokuma K., Voth G. A., Salvador P., Dannenberg J. J., Zakrzewski V. G., Dapprich S., Daniels A. D., Strain M. C., Farkas O., Malick D. K., Rabuck A. D., Raghavachari K., Foresman J. B., Ortiz J. V., Cui Q., Baboul A. G., Clifford S., Cioslowski J., Stefanov B. B., Liu G., Liashenko A., Piskorz P., Komaromi I., Martin R. L., Fox D. J., Keith T., Al-Laham M. A., Peng C.Y., Nanayakkara A., Challacombe M., Gill P. M. W., Johnson B., Chen W., Wong M. W., Gonzalez C., Pople J. A., Gaussian 03, Revision E.01, Gaussian Inc., Wallingford, CT, 2004
[16]	Reinaud O. M., Yap G. P. A., Rheingold A. L., Theopold K. H., Angew. Chem., 1995, 34(18), 2051—2052.