Chiral osmium complexes with sterically bulky schiff-base ligands. Crystal structures of Os(IV) derivatives and the reactivity and catalytic cyclopropanation of alkenes with EDA

Jing Zhang, Jiang Lin Liang, Xian Ru Sun, Hai Bing Zhou, Nian Yong Zhu, Zhong Yuan Zhou, Philip Wai Hong Chan, Chi Ming Che

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Abstract

The syntheses and reactivities of sterically encumbered trans-dioxoosmium(VI) complexes containing Schiff-base ligands bis(3,5-di-tert-butylsalicylidene)-1,2-cydohexane-diamine (H2Bu- salch) and bis(3,5-dibromosalicylidene)-1,2-cyclohexane-diamine (H 2Br-salch) are described. Reactions of [OsVI(Bu-salch) O2] (1a) and [OsVI(Br-salch)O2] (1b) with PPh3, p-X-arylamines (X = NO2, CN), N2H 4·H2O, Ph2NNH2, SOCl 2, CF3CO2H, Br2, and I2 under reducing conditions gave [OsII(Br-salch)(OPPh3) 2] (2), [OsVI(Br-salch)(p-X-C6H 4NH)2] (3), [μ-O{OsIV(Bu-salch)(p-NO 2C6H4-NH)}2] (4), [Os II(Br-salch)(N2)(H2O)] (5), [Os IV(Bu-salch)(OH)(Cl)] (6), [OsIV(Bu-salch)(OH) 2] (7), [OsIV(Bu-salch)-Cl2] (8), [Os IV(Bu-salch)(CF3CO2)2] (9), [Os IV(Bu-salch)Br2] (10), and [OsIV(Bu-salch) I2] (11), respectively. X-ray crystal structure determinations of [OsIV(Br-salch)(p-NO2C6H4NH) 2] (3a), [OsIV(Br-salch)(p-CNC6H 4NH)2] (3b), 6, 8, 9, and 11 reveal the Os-N(amido) distances to be 1.965(4)-1.995(1) Å for the bis(amido) complexes, Os-Cl distances of 2.333(8)-2.3495(1) Å for 6 and 8, Os-O(CF3CO 2) distances of 2.025(6)-2.041(6) Å for 9, and Os-I distances of 2.6884(6)-2.6970(6) Å for 11. Upon UV irradiation, (1S,2S)-(1a) reacted with aryl-substituted alkenes to give the corresponding epoxides in moderate yields, albeit with no enantioselectivity. The (1R,2R)-6 catalyzed cyclopropanation of a series of substituted styrenes exhibited moderate to good enantioselectivity (up to 79% ee) and moderate trans selectivity.

Original languageEnglish
Pages (from-to)3942-3954
Number of pages13
JournalInorganic Chemistry
Volume44
Issue number11
DOIs
Publication statusPublished - 30 May 2005
Externally publishedYes

Cite this

Zhang, Jing ; Liang, Jiang Lin ; Sun, Xian Ru ; Zhou, Hai Bing ; Zhu, Nian Yong ; Zhou, Zhong Yuan ; Chan, Philip Wai Hong ; Che, Chi Ming. / Chiral osmium complexes with sterically bulky schiff-base ligands. Crystal structures of Os(IV) derivatives and the reactivity and catalytic cyclopropanation of alkenes with EDA. In: Inorganic Chemistry. 2005 ; Vol. 44, No. 11. pp. 3942-3954.
@article{f9d297db61d4492d9ba3df311fe9ca6a,
title = "Chiral osmium complexes with sterically bulky schiff-base ligands. Crystal structures of Os(IV) derivatives and the reactivity and catalytic cyclopropanation of alkenes with EDA",
abstract = "The syntheses and reactivities of sterically encumbered trans-dioxoosmium(VI) complexes containing Schiff-base ligands bis(3,5-di-tert-butylsalicylidene)-1,2-cydohexane-diamine (H2Bu- salch) and bis(3,5-dibromosalicylidene)-1,2-cyclohexane-diamine (H 2Br-salch) are described. Reactions of [OsVI(Bu-salch) O2] (1a) and [OsVI(Br-salch)O2] (1b) with PPh3, p-X-arylamines (X = NO2, CN), N2H 4·H2O, Ph2NNH2, SOCl 2, CF3CO2H, Br2, and I2 under reducing conditions gave [OsII(Br-salch)(OPPh3) 2] (2), [OsVI(Br-salch)(p-X-C6H 4NH)2] (3), [μ-O{OsIV(Bu-salch)(p-NO 2C6H4-NH)}2] (4), [Os II(Br-salch)(N2)(H2O)] (5), [Os IV(Bu-salch)(OH)(Cl)] (6), [OsIV(Bu-salch)(OH) 2] (7), [OsIV(Bu-salch)-Cl2] (8), [Os IV(Bu-salch)(CF3CO2)2] (9), [Os IV(Bu-salch)Br2] (10), and [OsIV(Bu-salch) I2] (11), respectively. X-ray crystal structure determinations of [OsIV(Br-salch)(p-NO2C6H4NH) 2] (3a), [OsIV(Br-salch)(p-CNC6H 4NH)2] (3b), 6, 8, 9, and 11 reveal the Os-N(amido) distances to be 1.965(4)-1.995(1) {\AA} for the bis(amido) complexes, Os-Cl distances of 2.333(8)-2.3495(1) {\AA} for 6 and 8, Os-O(CF3CO 2) distances of 2.025(6)-2.041(6) {\AA} for 9, and Os-I distances of 2.6884(6)-2.6970(6) {\AA} for 11. Upon UV irradiation, (1S,2S)-(1a) reacted with aryl-substituted alkenes to give the corresponding epoxides in moderate yields, albeit with no enantioselectivity. The (1R,2R)-6 catalyzed cyclopropanation of a series of substituted styrenes exhibited moderate to good enantioselectivity (up to 79{\%} ee) and moderate trans selectivity.",
author = "Jing Zhang and Liang, {Jiang Lin} and Sun, {Xian Ru} and Zhou, {Hai Bing} and Zhu, {Nian Yong} and Zhou, {Zhong Yuan} and Chan, {Philip Wai Hong} and Che, {Chi Ming}",
year = "2005",
month = "5",
day = "30",
doi = "10.1021/ic0481935",
language = "English",
volume = "44",
pages = "3942--3954",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "11",

}

Chiral osmium complexes with sterically bulky schiff-base ligands. Crystal structures of Os(IV) derivatives and the reactivity and catalytic cyclopropanation of alkenes with EDA. / Zhang, Jing; Liang, Jiang Lin; Sun, Xian Ru; Zhou, Hai Bing; Zhu, Nian Yong; Zhou, Zhong Yuan; Chan, Philip Wai Hong; Che, Chi Ming.

In: Inorganic Chemistry, Vol. 44, No. 11, 30.05.2005, p. 3942-3954.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Chiral osmium complexes with sterically bulky schiff-base ligands. Crystal structures of Os(IV) derivatives and the reactivity and catalytic cyclopropanation of alkenes with EDA

AU - Zhang, Jing

AU - Liang, Jiang Lin

AU - Sun, Xian Ru

AU - Zhou, Hai Bing

AU - Zhu, Nian Yong

AU - Zhou, Zhong Yuan

AU - Chan, Philip Wai Hong

AU - Che, Chi Ming

PY - 2005/5/30

Y1 - 2005/5/30

N2 - The syntheses and reactivities of sterically encumbered trans-dioxoosmium(VI) complexes containing Schiff-base ligands bis(3,5-di-tert-butylsalicylidene)-1,2-cydohexane-diamine (H2Bu- salch) and bis(3,5-dibromosalicylidene)-1,2-cyclohexane-diamine (H 2Br-salch) are described. Reactions of [OsVI(Bu-salch) O2] (1a) and [OsVI(Br-salch)O2] (1b) with PPh3, p-X-arylamines (X = NO2, CN), N2H 4·H2O, Ph2NNH2, SOCl 2, CF3CO2H, Br2, and I2 under reducing conditions gave [OsII(Br-salch)(OPPh3) 2] (2), [OsVI(Br-salch)(p-X-C6H 4NH)2] (3), [μ-O{OsIV(Bu-salch)(p-NO 2C6H4-NH)}2] (4), [Os II(Br-salch)(N2)(H2O)] (5), [Os IV(Bu-salch)(OH)(Cl)] (6), [OsIV(Bu-salch)(OH) 2] (7), [OsIV(Bu-salch)-Cl2] (8), [Os IV(Bu-salch)(CF3CO2)2] (9), [Os IV(Bu-salch)Br2] (10), and [OsIV(Bu-salch) I2] (11), respectively. X-ray crystal structure determinations of [OsIV(Br-salch)(p-NO2C6H4NH) 2] (3a), [OsIV(Br-salch)(p-CNC6H 4NH)2] (3b), 6, 8, 9, and 11 reveal the Os-N(amido) distances to be 1.965(4)-1.995(1) Å for the bis(amido) complexes, Os-Cl distances of 2.333(8)-2.3495(1) Å for 6 and 8, Os-O(CF3CO 2) distances of 2.025(6)-2.041(6) Å for 9, and Os-I distances of 2.6884(6)-2.6970(6) Å for 11. Upon UV irradiation, (1S,2S)-(1a) reacted with aryl-substituted alkenes to give the corresponding epoxides in moderate yields, albeit with no enantioselectivity. The (1R,2R)-6 catalyzed cyclopropanation of a series of substituted styrenes exhibited moderate to good enantioselectivity (up to 79% ee) and moderate trans selectivity.

AB - The syntheses and reactivities of sterically encumbered trans-dioxoosmium(VI) complexes containing Schiff-base ligands bis(3,5-di-tert-butylsalicylidene)-1,2-cydohexane-diamine (H2Bu- salch) and bis(3,5-dibromosalicylidene)-1,2-cyclohexane-diamine (H 2Br-salch) are described. Reactions of [OsVI(Bu-salch) O2] (1a) and [OsVI(Br-salch)O2] (1b) with PPh3, p-X-arylamines (X = NO2, CN), N2H 4·H2O, Ph2NNH2, SOCl 2, CF3CO2H, Br2, and I2 under reducing conditions gave [OsII(Br-salch)(OPPh3) 2] (2), [OsVI(Br-salch)(p-X-C6H 4NH)2] (3), [μ-O{OsIV(Bu-salch)(p-NO 2C6H4-NH)}2] (4), [Os II(Br-salch)(N2)(H2O)] (5), [Os IV(Bu-salch)(OH)(Cl)] (6), [OsIV(Bu-salch)(OH) 2] (7), [OsIV(Bu-salch)-Cl2] (8), [Os IV(Bu-salch)(CF3CO2)2] (9), [Os IV(Bu-salch)Br2] (10), and [OsIV(Bu-salch) I2] (11), respectively. X-ray crystal structure determinations of [OsIV(Br-salch)(p-NO2C6H4NH) 2] (3a), [OsIV(Br-salch)(p-CNC6H 4NH)2] (3b), 6, 8, 9, and 11 reveal the Os-N(amido) distances to be 1.965(4)-1.995(1) Å for the bis(amido) complexes, Os-Cl distances of 2.333(8)-2.3495(1) Å for 6 and 8, Os-O(CF3CO 2) distances of 2.025(6)-2.041(6) Å for 9, and Os-I distances of 2.6884(6)-2.6970(6) Å for 11. Upon UV irradiation, (1S,2S)-(1a) reacted with aryl-substituted alkenes to give the corresponding epoxides in moderate yields, albeit with no enantioselectivity. The (1R,2R)-6 catalyzed cyclopropanation of a series of substituted styrenes exhibited moderate to good enantioselectivity (up to 79% ee) and moderate trans selectivity.

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U2 - 10.1021/ic0481935

DO - 10.1021/ic0481935

M3 - Article

AN - SCOPUS:20444482485

VL - 44

SP - 3942

EP - 3954

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 11

ER -