Preparation and reactivity of the heterobimetallic ReIr face-shared bioctahedral compounds Cp*Ir(μ-Cl)3Re(CO)3 and Cp*Ir(μ-SC6H4Me-4)3Re(CO) 3: X-ray diffraction structures and redox behavior

Xiaoping Wang; Casey Hammons; Michael G. Richmond

doi:10.1016/j.poly.2009.04.023

Preparation and reactivity of the heterobimetallic ReIr face-shared bioctahedral compounds CpIr(μ-Cl)₃Re(CO)₃ and CpIr(μ-SC₆H₄Me-4)₃Re(CO)₃: X-ray diffraction structures and redox behavior

Xiaoping Wang, Casey Hammons, Michael G. Richmond

Single Crystal Diffraction

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

2 Scopus citations

Abstract

Thermolysis of the dinuclear compound [Cp*IrCl₂]₂ (1) with ClRe(CO)₅ (2) leads to the formation of the confacial bioctahedral compound Cp*Ir(μ-Cl)₃Re(CO)₃ (3) in high yield. Whereas the substitution of the chloride ligands in 3 is observed on treatment with excess p-methylbenzenethiol to furnish the sulfido-bridged compound Cp*Ir(μ-SC₆H₄Me-4)₃Re(CO)₃ (4), 3 undergoes fragmentation upon reaction with tertiary phosphines [PPh₃ and P(OMe)₃] to furnish the mononuclear compounds Cp*IrCl₂P and fac-ClRe(CO)₃P₂. Both 3 and 4 have been isolated and fully characterized in solution by IR and ¹H NMR spectroscopies, and their solid-state structures have been established by X-ray crystallography. The redox properties of 3 and 4 have been explored by cyclic voltammetry, and the results are discussed relative to extended Hückel MO calculations.

Original language	English
Pages (from-to)	2294-2300
Number of pages	7
Journal	Polyhedron
Volume	28
Issue number	11
DOIs	https://doi.org/10.1016/j.poly.2009.04.023
State	Published - Jul 6 2009

Funding

Generous and continued financial support from the Robert A. Welch Foundation (Grant B-1093-MGR) is much appreciated.

Keywords

Halide-bridged compounds
Heterobimetallic compounds
Rhenium-iridium compounds
Sulfido-bridged compounds
X-ray crystallography

Access to Document

10.1016/j.poly.2009.04.023

Cite this

@article{7b3bf59fdaa3459281e904e3fcbed552,

title = "Preparation and reactivity of the heterobimetallic ReIr face-shared bioctahedral compounds Cp*Ir(μ-Cl)3Re(CO)3 and Cp*Ir(μ-SC6H4Me-4)3Re(CO) 3: X-ray diffraction structures and redox behavior",

abstract = "Thermolysis of the dinuclear compound [Cp*IrCl2]2 (1) with ClRe(CO)5 (2) leads to the formation of the confacial bioctahedral compound Cp*Ir(μ-Cl)3Re(CO)3 (3) in high yield. Whereas the substitution of the chloride ligands in 3 is observed on treatment with excess p-methylbenzenethiol to furnish the sulfido-bridged compound Cp*Ir(μ-SC6H4Me-4)3Re(CO) 3 (4), 3 undergoes fragmentation upon reaction with tertiary phosphines [PPh3 and P(OMe)3] to furnish the mononuclear compounds Cp*IrCl2P and fac-ClRe(CO)3P2. Both 3 and 4 have been isolated and fully characterized in solution by IR and 1H NMR spectroscopies, and their solid-state structures have been established by X-ray crystallography. The redox properties of 3 and 4 have been explored by cyclic voltammetry, and the results are discussed relative to extended H{\"u}ckel MO calculations.",

keywords = "Halide-bridged compounds, Heterobimetallic compounds, Rhenium-iridium compounds, Sulfido-bridged compounds, X-ray crystallography",

author = "Xiaoping Wang and Casey Hammons and Richmond, {Michael G.}",

year = "2009",

month = jul,

day = "6",

doi = "10.1016/j.poly.2009.04.023",

language = "English",

volume = "28",

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journal = "Polyhedron",

issn = "0277-5387",

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}

Preparation and reactivity of the heterobimetallic ReIr face-shared bioctahedral compounds Cp*Ir(μ-Cl)₃Re(CO)₃ and Cp*Ir(μ-SC₆H₄Me-4)₃Re(CO)₃: X-ray diffraction structures and redox behavior. / Wang, Xiaoping; Hammons, Casey; Richmond, Michael G.
In: Polyhedron, Vol. 28, No. 11, 06.07.2009, p. 2294-2300.

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

TY - JOUR

T1 - Preparation and reactivity of the heterobimetallic ReIr face-shared bioctahedral compounds Cp*Ir(μ-Cl)3Re(CO)3 and Cp*Ir(μ-SC6H4Me-4)3Re(CO) 3

T2 - X-ray diffraction structures and redox behavior

AU - Wang, Xiaoping

AU - Hammons, Casey

AU - Richmond, Michael G.

PY - 2009/7/6

Y1 - 2009/7/6

N2 - Thermolysis of the dinuclear compound [Cp*IrCl2]2 (1) with ClRe(CO)5 (2) leads to the formation of the confacial bioctahedral compound Cp*Ir(μ-Cl)3Re(CO)3 (3) in high yield. Whereas the substitution of the chloride ligands in 3 is observed on treatment with excess p-methylbenzenethiol to furnish the sulfido-bridged compound Cp*Ir(μ-SC6H4Me-4)3Re(CO) 3 (4), 3 undergoes fragmentation upon reaction with tertiary phosphines [PPh3 and P(OMe)3] to furnish the mononuclear compounds Cp*IrCl2P and fac-ClRe(CO)3P2. Both 3 and 4 have been isolated and fully characterized in solution by IR and 1H NMR spectroscopies, and their solid-state structures have been established by X-ray crystallography. The redox properties of 3 and 4 have been explored by cyclic voltammetry, and the results are discussed relative to extended Hückel MO calculations.

AB - Thermolysis of the dinuclear compound [Cp*IrCl2]2 (1) with ClRe(CO)5 (2) leads to the formation of the confacial bioctahedral compound Cp*Ir(μ-Cl)3Re(CO)3 (3) in high yield. Whereas the substitution of the chloride ligands in 3 is observed on treatment with excess p-methylbenzenethiol to furnish the sulfido-bridged compound Cp*Ir(μ-SC6H4Me-4)3Re(CO) 3 (4), 3 undergoes fragmentation upon reaction with tertiary phosphines [PPh3 and P(OMe)3] to furnish the mononuclear compounds Cp*IrCl2P and fac-ClRe(CO)3P2. Both 3 and 4 have been isolated and fully characterized in solution by IR and 1H NMR spectroscopies, and their solid-state structures have been established by X-ray crystallography. The redox properties of 3 and 4 have been explored by cyclic voltammetry, and the results are discussed relative to extended Hückel MO calculations.

KW - Halide-bridged compounds

KW - Heterobimetallic compounds

KW - Rhenium-iridium compounds

KW - Sulfido-bridged compounds

KW - X-ray crystallography

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