箭推法视角下对卤素含氧酸根歧化反应的思考

doi:10.3866/PKU.DXHX201807013

Abstract

Abstract:

The article uses the disproportionation of chlorate and hypobromite as examples to analyze the application of arrow-pushing in the disproportionation of halogen oxoanions. Based on the experimental results, we have discussed the rationality of each possible mechanism we proposed based on electronic structure methods. All these efforts are put to demonstrate the way to introduce basic organic-style arrow-pushing into inorganic field.

Key words: Halogen oxoanion, Disproportionation, Inorganic reaction, Mechanism

MSC2000:

Tianyi YANG,Qing ZENG,Gan WANG,Yidan MIAO. Application of Arrow-Pushing in the Disproportionation of Halogen Oxoanions[J].University Chemistry, 2019, 34(3): 68-76.

Figures/Tables 16

References 14

1	Ghosh A. ; Berg S. J. Chem. Educ. 2011, 88, 1663. doi: 10.1021/ed200166z
2	Basolo, F.; Pearson, R. G. Mechanism of Inorganic Reactions; John Willy & Sons: New York, 1958.
3	Ghosh, A.; Berg, S. Arrow Pushing in Inorganic Chemistry; John Willy & Sons: Hoboken, 2014.
4	Earnshaw, A.; Greenwood, N. N. Chemistry of the Elements, 2nd ed.; Elsevier: New York, 1997; pp 856.
5	北京师范大学无机化学教研室; 华中师范大学无机化学教研室; 南京师范大学无机化学教研室. 无机化学(下册), 第4版北京: 高等教育出版社, 2003.
6	Speight, J. G. Lange's Handbook of Chemistry, 16th ed.; The McGraw-Hill Companies: United States of America, 2005.
7	Beckwith R. C. ; Margerum D. W. Inorg. Chem. 1997, 36, 3754. doi: 10.1021/ic970155g
8	Shilov E. A. J. Am. Chem. Soc. 1938, 60, 490.
9	Engel P. ; Oplatka A. ; Perlmutter-Hayman B. J. Am. Chem. Soc. 1954, 76, 2010. doi: 10.1021/ja01636a092
10	Hamano A. ; Nakamori I. Kenkyu Hokoku-Sasebo Kogyo Koto Senmon Gakko 1990, 27, 9.
11	Lewin M. ; Avrahami M. J. Am. Chem. Soc. 1955, 77, 4491. doi: 10.1021/ja01622a014
12	Velghe N. ; Claeys A. Talanta 1972, 19, 1555. doi: 10.1016/0039-9140(72)80228-5
13	Horvath A. ; Nagypal I. ; Peintler G. ; Epstein I. ; Kustin K. The Journal of Physical Chemistry A 2003, 107, 6966. doi: 10.1021/jp027411h
14	Sebők-Nagy K. ; Körtvélyesi T. International Journal of Chemical Kinetics 2004, 36, 596. doi: 10.1002/kin.v36:11

原子	电荷
Cl	0.444229
O(1)	−0.314229
O(2)	−0.325256
O(3)	−0.360169
K	0.556524

机理	活化能/(kJ∙mol⁻¹)			过渡态
机理	第一步	第二步步步	第三步	第一步	第二步	第三步
离子型机理(图7)	186.0	118.9	70.1
自由基机理(图8)	515.5

原子	电荷
Br	−0.32447
O	−0.67553

pH	介质/缓冲溶液^a	10³k₁/(mol⁻¹∙L∙s⁻¹)	参考文献
7.5	硼酸盐	2.4^b	[10]
7.9	总浓度0.4 mol∙L⁻¹的硼酸盐	1.3	[11]
8.5	硼酸盐	1.6^c	[10]
8.84	硼酸盐	0.83^c	[9]
9.5	硼酸盐	1.1^c	[10]
10.0	硼酸盐	0.025^b	[10]
12	NaOH	0.00036^b	[10]
12.8	NaOH	0.00026^c	[12]

机理	活化能/(kJ∙mol⁻¹)		过渡态
机理	第一步	第二步	第一步	第二步
离子型机理(图5、6)	71.2	77.1
协同机理(图7)	166.0	94.3

Application of Arrow-Pushing in the Disproportionation of Halogen Oxoanions

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