Oxidative addition of rhodium complexes containing a dithioimidodiphosphinate ligand: Facile reductive elimination of methyl iodide from a tetranuclear rhodium sulfido cluster

Wai Man Cheung; Wai Hang Chiu; Herman H.Y. Sung; Ian D. Williams; Wa Hung Leung

doi:10.1002/ejic.201402080

Oxidative addition of rhodium complexes containing a dithioimidodiphosphinate ligand: Facile reductive elimination of methyl iodide from a tetranuclear rhodium sulfido cluster

Wai Man Cheung
, Wai Hang Chiu
, Herman H.Y. Sung
, Ian D. Williams
, Wa Hung Leung

Construction and Quality Management

Research output: Contribution to journal › Article › peer-review

4 Citations (Scopus)

Abstract

Rhodium complexes containing the dithioimidodiphosphinate ligand [N(iPr₂PS)₂]^- have been synthesized and their oxidative addition of methyl iodide investigated. Treatment of [Rh(PPh ₃)₃Cl] with K[N(iPr₂PS)₂] afforded [Rh{N(iPr₂PS)₂}(PPh₃)₂] (1). Recrystallization of 1 from hexane in the presence of adventitious oxygen yielded the peroxo complex [Rh{N(iPr₂PS)₂}(PPh ₃)₂(η²-O₂)] (2). Oxidative addition of methyl iodide to 1 gave [Rh(Me)(I){N(iPr₂PS) ₂}(PPh₃)₂] (3), which reacted with K[N(iPr ₂PS)₂] to afford [Rh(Me){N(iPr₂PS) ₂}₂] (4). Treatment of K[N(iPr₂PS)₂] with [Rh(coe)₂Cl]₂ (coe = cyclooctene) yielded the tetranuclear sulfido cluster [Rh₄(μ₃-S) ₂{iPr₂PNP(S)iPr₂}₂{N(iPr ₂PS)₂}₂] (5) containing two four-coordinate Rh^I and two five-coordinate Rh^III centers. Oxidative addition of methyl iodide to 5 gave the monomethyl compound [Rh ₄(μ₃-S)₂(Me)(μ-I){iPr₂PNP(S) iPr₂}₂{N(iPr₂PS)₂}₂] (6). In benzene solution, 6 underwent spontaneous reductive elimination of methyl iodide to give 5. The crystal structures of complexes 2-6 have been determined.

Original language	English
Pages (from-to)	2961-2968
Number of pages	8
Journal	European Journal of Inorganic Chemistry
Issue number	18
DOIs	https://doi.org/10.1002/ejic.201402080
Publication status	Published - Jun 2014

Keywords

Cluster compounds
Oxidation
Reduction
Rhodium
S ligands

Access to Document

10.1002/ejic.201402080

Cite this

@article{6a04d9fbb19a484788cff957d4ab710c,

title = "Oxidative addition of rhodium complexes containing a dithioimidodiphosphinate ligand: Facile reductive elimination of methyl iodide from a tetranuclear rhodium sulfido cluster",

abstract = "Rhodium complexes containing the dithioimidodiphosphinate ligand [N(iPr2PS)2]- have been synthesized and their oxidative addition of methyl iodide investigated. Treatment of [Rh(PPh 3)3Cl] with K[N(iPr2PS)2] afforded [Rh\{N(iPr2PS)2\}(PPh3)2] (1). Recrystallization of 1 from hexane in the presence of adventitious oxygen yielded the peroxo complex [Rh\{N(iPr2PS)2\}(PPh 3)2(η2-O2)] (2). Oxidative addition of methyl iodide to 1 gave [Rh(Me)(I)\{N(iPr2PS) 2\}(PPh3)2] (3), which reacted with K[N(iPr 2PS)2] to afford [Rh(Me)\{N(iPr2PS) 2\}2] (4). Treatment of K[N(iPr2PS)2] with [Rh(coe)2Cl]2 (coe = cyclooctene) yielded the tetranuclear sulfido cluster [Rh4(μ3-S) 2\{iPr2PNP(S)iPr2\}2\{N(iPr 2PS)2\}2] (5) containing two four-coordinate RhI and two five-coordinate RhIII centers. Oxidative addition of methyl iodide to 5 gave the monomethyl compound [Rh 4(μ3-S)2(Me)(μ-I)\{iPr2PNP(S) iPr2\}2\{N(iPr2PS)2\}2] (6). In benzene solution, 6 underwent spontaneous reductive elimination of methyl iodide to give 5. The crystal structures of complexes 2-6 have been determined.",

keywords = "Cluster compounds, Oxidation, Reduction, Rhodium, S ligands",

author = "Cheung, \{Wai Man\} and Chiu, \{Wai Hang\} and Sung, \{Herman H.Y.\} and Williams, \{Ian D.\} and Leung, \{Wa Hung\}",

year = "2014",

month = jun,

doi = "10.1002/ejic.201402080",

language = "English",

pages = "2961--2968",

number = "18",

}

Oxidative addition of rhodium complexes containing a dithioimidodiphosphinate ligand: Facile reductive elimination of methyl iodide from a tetranuclear rhodium sulfido cluster. / Cheung, Wai Man; Chiu, Wai Hang; Sung, Herman H.Y. et al.
In: European Journal of Inorganic Chemistry, No. 18, 06.2014, p. 2961-2968.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Oxidative addition of rhodium complexes containing a dithioimidodiphosphinate ligand

T2 - Facile reductive elimination of methyl iodide from a tetranuclear rhodium sulfido cluster

AU - Cheung, Wai Man

AU - Chiu, Wai Hang

AU - Sung, Herman H.Y.

AU - Williams, Ian D.

AU - Leung, Wa Hung

PY - 2014/6

Y1 - 2014/6

N2 - Rhodium complexes containing the dithioimidodiphosphinate ligand [N(iPr2PS)2]- have been synthesized and their oxidative addition of methyl iodide investigated. Treatment of [Rh(PPh 3)3Cl] with K[N(iPr2PS)2] afforded [Rh{N(iPr2PS)2}(PPh3)2] (1). Recrystallization of 1 from hexane in the presence of adventitious oxygen yielded the peroxo complex [Rh{N(iPr2PS)2}(PPh 3)2(η2-O2)] (2). Oxidative addition of methyl iodide to 1 gave [Rh(Me)(I){N(iPr2PS) 2}(PPh3)2] (3), which reacted with K[N(iPr 2PS)2] to afford [Rh(Me){N(iPr2PS) 2}2] (4). Treatment of K[N(iPr2PS)2] with [Rh(coe)2Cl]2 (coe = cyclooctene) yielded the tetranuclear sulfido cluster [Rh4(μ3-S) 2{iPr2PNP(S)iPr2}2{N(iPr 2PS)2}2] (5) containing two four-coordinate RhI and two five-coordinate RhIII centers. Oxidative addition of methyl iodide to 5 gave the monomethyl compound [Rh 4(μ3-S)2(Me)(μ-I){iPr2PNP(S) iPr2}2{N(iPr2PS)2}2] (6). In benzene solution, 6 underwent spontaneous reductive elimination of methyl iodide to give 5. The crystal structures of complexes 2-6 have been determined.

AB - Rhodium complexes containing the dithioimidodiphosphinate ligand [N(iPr2PS)2]- have been synthesized and their oxidative addition of methyl iodide investigated. Treatment of [Rh(PPh 3)3Cl] with K[N(iPr2PS)2] afforded [Rh{N(iPr2PS)2}(PPh3)2] (1). Recrystallization of 1 from hexane in the presence of adventitious oxygen yielded the peroxo complex [Rh{N(iPr2PS)2}(PPh 3)2(η2-O2)] (2). Oxidative addition of methyl iodide to 1 gave [Rh(Me)(I){N(iPr2PS) 2}(PPh3)2] (3), which reacted with K[N(iPr 2PS)2] to afford [Rh(Me){N(iPr2PS) 2}2] (4). Treatment of K[N(iPr2PS)2] with [Rh(coe)2Cl]2 (coe = cyclooctene) yielded the tetranuclear sulfido cluster [Rh4(μ3-S) 2{iPr2PNP(S)iPr2}2{N(iPr 2PS)2}2] (5) containing two four-coordinate RhI and two five-coordinate RhIII centers. Oxidative addition of methyl iodide to 5 gave the monomethyl compound [Rh 4(μ3-S)2(Me)(μ-I){iPr2PNP(S) iPr2}2{N(iPr2PS)2}2] (6). In benzene solution, 6 underwent spontaneous reductive elimination of methyl iodide to give 5. The crystal structures of complexes 2-6 have been determined.

KW - Cluster compounds

KW - Oxidation

KW - Reduction

KW - Rhodium

KW - S ligands

UR - https://www.scopus.com/pages/publications/84903193110

U2 - 10.1002/ejic.201402080

DO - 10.1002/ejic.201402080

M3 - Article

AN - SCOPUS:84903193110

SN - 1434-1948

SP - 2961

EP - 2968

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 18

ER -

Oxidative addition of rhodium complexes containing a dithioimidodiphosphinate ligand: Facile reductive elimination of methyl iodide from a tetranuclear rhodium sulfido cluster

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Cite this