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

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^*

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

18 Citations (Scopus)

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.

Original language	English
Pages (from-to)	2022-2028
Journal	Inorganic Chemistry
Volume	56
Issue number	4
DOIs	https://doi.org/10.1021/acs.inorgchem.6b02645
Publication status	Published - 20 Feb 2017

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

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[CeIV(NO3)6], which is a one-electron oxidant. With m-CPBA, mer-[Os(NO)(L)(CN)3]− (mer-OsNO) is the product, while with CeIV, mer-[OsVI(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 CeIV are proposed.",

author = "Jing Xiang and Qian Wang and Shek-Man Yiu and Tai-Chu Lau",

year = "2017",

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doi = "10.1021/acs.inorgchem.6b02645",

language = "English",

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TY - JOUR

T1 - Dual Pathways in the Oxidation of an Osmium(III) Guanidine Complex. Formation of Osmium(VI) Nitrido and Osmium Nitrosyl Complex

AU - Xiang, Jing

AU - Wang, Qian

AU - Yiu, Shek-Man

AU - Lau, Tai-Chu

PY - 2017/2/20

Y1 - 2017/2/20

N2 - 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[CeIV(NO3)6], which is a one-electron oxidant. With m-CPBA, mer-[Os(NO)(L)(CN)3]− (mer-OsNO) is the product, while with CeIV, mer-[OsVI(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 CeIV are proposed.

AB - 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[CeIV(NO3)6], which is a one-electron oxidant. With m-CPBA, mer-[Os(NO)(L)(CN)3]− (mer-OsNO) is the product, while with CeIV, mer-[OsVI(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 CeIV are proposed.

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U2 - 10.1021/acs.inorgchem.6b02645

DO - 10.1021/acs.inorgchem.6b02645

M3 - RGC 21 - Publication in refereed journal

SN - 0020-1669

VL - 56

SP - 2022

EP - 2028

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 4

ER -

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

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