Structure and Reactivity of a Seven-Coordinate Ruthenium Iodosylbenzene Complex

Yunling Pan; Miaomiao Zhou; Rui Wang; Dan Song; Shek-Man Yiu; Jianhui Xie; Kai-Chung Lau; Tai-Chu Lau; Yingying Liu

doi:10.1021/acs.inorgchem.3c00417

Structure and Reactivity of a Seven-Coordinate Ruthenium Iodosylbenzene Complex

Yunling Pan, Miaomiao Zhou, Rui Wang, Dan Song, Shek-Man Yiu, Jianhui Xie, Kai-Chung Lau^*, Tai-Chu Lau^*, Yingying Liu^*

^*Corresponding author for this work

Department of Chemistry

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

3 Citations (Scopus)

Abstract

Seven-coordinate (CN7) ruthenium-oxo species have attracted much attention as highly reactive intermediates in both organic and water oxidation. Apart from metal-oxo, other metal-oxidant adducts, such as metal-iodosylarenes, have also recently emerged as active oxidants. We reported herein the first example of a CN7 Ru-iodosylbenzene complex, [Ru^IV(bdpm)-(pic)₂(O)I(Cl)Ph]⁺ (H₂bdpm = [2,2'-bipyridine]-6,6'-diylbis-(diphenylmethanol); pic = 4-picoline). The X-ray crystal structure of this complex shows that it adopts a distorted pentagonal bipyramidal geometry with Ru-O(I) and O-I distances of 2.0451(39) and 1.9946(40) Å, respectively. This complex is highly reactive, and it readily undergoes O-atom transfer (OAT) and C-H bond activation reactions with various organic substrates. This work should provide insights for the development of new highly reactive oxidizing agents based on CN7 geometry.

Original language	English
Pages (from-to)	7772-7778
Journal	Inorganic Chemistry
Volume	62
Issue number	20
Online published	5 May 2023
DOIs	https://doi.org/10.1021/acs.inorgchem.3c00417
Publication status	Published - 22 May 2023

Research Keywords

OXYGEN-ATOM TRANSFER
IRON-OXO COMPLEXES
PORPHYRIN COMPLEXES
OXIDATION REACTIONS
WATER
IODOSYLARENE
BOND
INTERMEDIATE
EPOXIDATION
ACTIVATION

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title = "Structure and Reactivity of a Seven-Coordinate Ruthenium Iodosylbenzene Complex",

abstract = "Seven-coordinate (CN7) ruthenium-oxo species have attracted much attention as highly reactive intermediates in both organic and water oxidation. Apart from metal-oxo, other metal-oxidant adducts, such as metal-iodosylarenes, have also recently emerged as active oxidants. We reported herein the first example of a CN7 Ru-iodosylbenzene complex, [RuIV(bdpm)-(pic)2(O)I(Cl)Ph]+ (H2bdpm = [2,2'-bipyridine]-6,6'-diylbis-(diphenylmethanol); pic = 4-picoline). The X-ray crystal structure of this complex shows that it adopts a distorted pentagonal bipyramidal geometry with Ru-O(I) and O-I distances of 2.0451(39) and 1.9946(40) {\AA}, respectively. This complex is highly reactive, and it readily undergoes O-atom transfer (OAT) and C-H bond activation reactions with various organic substrates. This work should provide insights for the development of new highly reactive oxidizing agents based on CN7 geometry.",

keywords = "OXYGEN-ATOM TRANSFER, IRON-OXO COMPLEXES, PORPHYRIN COMPLEXES, OXIDATION REACTIONS, WATER, IODOSYLARENE, BOND, INTERMEDIATE, EPOXIDATION, ACTIVATION",

author = "Yunling Pan and Miaomiao Zhou and Rui Wang and Dan Song and Shek-Man Yiu and Jianhui Xie and Kai-Chung Lau and Tai-Chu Lau and Yingying Liu",

year = "2023",

month = may,

day = "22",

doi = "10.1021/acs.inorgchem.3c00417",

language = "English",

volume = "62",

pages = "7772--7778",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "20",

}

TY - JOUR

T1 - Structure and Reactivity of a Seven-Coordinate Ruthenium Iodosylbenzene Complex

AU - Pan, Yunling

AU - Zhou, Miaomiao

AU - Wang, Rui

AU - Song, Dan

AU - Yiu, Shek-Man

AU - Xie, Jianhui

AU - Lau, Kai-Chung

AU - Lau, Tai-Chu

AU - Liu, Yingying

PY - 2023/5/22

Y1 - 2023/5/22

N2 - Seven-coordinate (CN7) ruthenium-oxo species have attracted much attention as highly reactive intermediates in both organic and water oxidation. Apart from metal-oxo, other metal-oxidant adducts, such as metal-iodosylarenes, have also recently emerged as active oxidants. We reported herein the first example of a CN7 Ru-iodosylbenzene complex, [RuIV(bdpm)-(pic)2(O)I(Cl)Ph]+ (H2bdpm = [2,2'-bipyridine]-6,6'-diylbis-(diphenylmethanol); pic = 4-picoline). The X-ray crystal structure of this complex shows that it adopts a distorted pentagonal bipyramidal geometry with Ru-O(I) and O-I distances of 2.0451(39) and 1.9946(40) Å, respectively. This complex is highly reactive, and it readily undergoes O-atom transfer (OAT) and C-H bond activation reactions with various organic substrates. This work should provide insights for the development of new highly reactive oxidizing agents based on CN7 geometry.

AB - Seven-coordinate (CN7) ruthenium-oxo species have attracted much attention as highly reactive intermediates in both organic and water oxidation. Apart from metal-oxo, other metal-oxidant adducts, such as metal-iodosylarenes, have also recently emerged as active oxidants. We reported herein the first example of a CN7 Ru-iodosylbenzene complex, [RuIV(bdpm)-(pic)2(O)I(Cl)Ph]+ (H2bdpm = [2,2'-bipyridine]-6,6'-diylbis-(diphenylmethanol); pic = 4-picoline). The X-ray crystal structure of this complex shows that it adopts a distorted pentagonal bipyramidal geometry with Ru-O(I) and O-I distances of 2.0451(39) and 1.9946(40) Å, respectively. This complex is highly reactive, and it readily undergoes O-atom transfer (OAT) and C-H bond activation reactions with various organic substrates. This work should provide insights for the development of new highly reactive oxidizing agents based on CN7 geometry.

KW - OXYGEN-ATOM TRANSFER

KW - IRON-OXO COMPLEXES

KW - PORPHYRIN COMPLEXES

KW - OXIDATION REACTIONS

KW - WATER

KW - IODOSYLARENE

KW - BOND

KW - INTERMEDIATE

KW - EPOXIDATION

KW - ACTIVATION

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U2 - 10.1021/acs.inorgchem.3c00417

DO - 10.1021/acs.inorgchem.3c00417

M3 - RGC 21 - Publication in refereed journal

SN - 0020-1669

VL - 62

SP - 7772

EP - 7778

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 20

ER -

Structure and Reactivity of a Seven-Coordinate Ruthenium Iodosylbenzene Complex

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