Dual Pathways in the Oxidation of an Osmium(III) Guanidine Complex. Formation of Osmium(VI) Nitrido and Osmium Nitrosyl Complex

Jing Xiang; Qian Wang; Shek-Man Yiu; Tai-Chu Lau

doi:10.1021/acs.inorgchem.6b02645

Author(s)

Jing Xiang
Qian Wang
Shek-Man Yiu
Tai-Chu Lau

Detail(s)

Original language	English
Pages (from-to)	2022-2028
Journal / Publication	Inorganic Chemistry
Volume	56
Issue number	4
Publication status	Published - 20 Feb 2017

Link(s)

DOI	DOI https://doi.org/10.1021/acs.inorgchem.6b02645 Final Published version
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Link to Scopus	https://www.scopus.com/record/display.uri?eid=2-s2.0-85013449862&origin=recordpage
Permanent Link	https://scholars.cityu.edu.hk/en/publications/publication(939dad1e-5829-42ea-b80a-668577338d86).html

Abstract

The guanidine moiety of arginine is involved in the active sites of a variety of enzymes, such as nitric oxide synthase (NOS) and NiFe hydrogenase. In this paper we aim to investigate the effects of a metal center on the oxidation of guanidine, which should provide an interesting comparison with the biological aerobic oxidation of arginine catalyzed by NOS. We studied the oxidation of an osmium(III) guanidine complex, mer-[Os(L){N(H)C(NH₂)₂}(CN)₃]⁻, (OsG, HL = 2-(2-hydroxyphenyl)benzoxazole) by m-chloroperbenzoic acid (m-CPBA), which is potentially an O atom transfer reagent, and by (NH₄)₂[Ce^IV(NO₃)₆], which is a one-electron oxidant. With m-CPBA, mer-[Os(NO)(L)(CN)₃]⁻ (mer-OsNO) is the product, while with Ce^IV, mer-[Os^VI(N)(L)(CN)₃]⁻ (mer-OsN) is formed instead. The crystal structures of mer-OsNO and mer-OsN were determined by X-ray crystallography. The mechanisms for the oxidation of OsG by m-CPBA and Ce^IV are proposed.

Citation Format(s)

[ RIS ] [ BibTeX ]

Dual Pathways in the Oxidation of an Osmium(III) Guanidine Complex. Formation of Osmium(VI) Nitrido and Osmium Nitrosyl Complex. / Xiang, Jing; Wang, Qian; Yiu, Shek-Man et al.

In: Inorganic Chemistry, Vol. 56, No. 4, 20.02.2017, p. 2022-2028.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62) › 21_Publication in refereed journal › peer-review

Xiang, J, Wang, Q, Yiu, S-M & Lau, T-C 2017, 'Dual Pathways in the Oxidation of an Osmium(III) Guanidine Complex. Formation of Osmium(VI) Nitrido and Osmium Nitrosyl Complex', Inorganic Chemistry, vol. 56, no. 4, pp. 2022-2028. https://doi.org/10.1021/acs.inorgchem.6b02645

Xiang, J., Wang, Q., Yiu, S-M., & Lau, T-C. (2017). Dual Pathways in the Oxidation of an Osmium(III) Guanidine Complex. Formation of Osmium(VI) Nitrido and Osmium Nitrosyl Complex. Inorganic Chemistry, 56(4), 2022-2028. https://doi.org/10.1021/acs.inorgchem.6b02645

Xiang J, Wang Q, Yiu S-M, Lau T-C. Dual Pathways in the Oxidation of an Osmium(III) Guanidine Complex. Formation of Osmium(VI) Nitrido and Osmium Nitrosyl Complex. Inorganic Chemistry. 2017 Feb 20;56(4):2022-2028. doi: 10.1021/acs.inorgchem.6b02645

Xiang, Jing ; Wang, Qian ; Yiu, Shek-Man et al. / Dual Pathways in the Oxidation of an Osmium(III) Guanidine Complex. Formation of Osmium(VI) Nitrido and Osmium Nitrosyl Complex. In: Inorganic Chemistry. 2017 ; Vol. 56, No. 4. pp. 2022-2028.