Stabilization of [Ru(bpy)2(CO)(η1-CO2)] and unprecedented reversible oxide transfer reactions from CO32- to [Ru(bpy)2(CO)2]2+ and from [Ru(bpy)2(CO)(η1-CO2)] to CO2

Hiroshi Nakajima; Kiyoshi Tsuge; Kiyotsuna Toyohara; Koji Tanaka

doi:10.1016/S0022-328X(98)00774-8

Stabilization of [Ru(bpy)₂(CO)(η¹-CO₂)] and unprecedented reversible oxide transfer reactions from CO₃^2- to [Ru(bpy)₂(CO)₂]²⁺ and from [Ru(bpy)₂(CO)(η¹-CO₂)] to CO₂

Hiroshi Nakajima, Kiyoshi Tsuge, Kiyotsuna Toyohara, Koji Tanaka^*

^*Corresponding author for this work

Department of Chemistry

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

12 Scopus citations

Abstract

Unusual thermal stability of [Ru(bpy)₂(CO)(η¹-CO₂)] (1) as a metal-η¹-CO₂ complex was examined both in solid state and in solution. Compound 1 dissolves in CH₃CN containing LiCF₃SO₃. Interaction between Li⁺ and the η¹-CO₂ group enhances an electron flow from Ru to the CO₂ ligand and greatly contributes to the stabilization of the Ru-η¹-CO₂ bond. The reaction of [Ru(bpy)₂(CO)₂](PF₆)₂ with [Crown·K]₂CO₃ in dry CH₃CN selectively produced 1 through the 1:1 adduct with the RuC(O)-OCO₂ moiety. Stoichimetric formation of 1 from the 1:1 adduct is also assisted by [Crown·K]⁺ as a Lewis acid. Similarly, the reaction of [Ru(bpy)₂(CO)₂](PF₆)₂ with (Me₄N)₂CO₃ in DMSO gave the 1:1 adduct in the initial stage, which gradually changed to a metalloanhydride complex, [Ru(bpy)₂(CO)((CO)₂O)] due to the absence of Lewis acids to stabilize 1, since an addition of LiCF₃SO₃ to the solution gave [Ru(bpy)₂(CO)(η¹-CO₂)] quantitatively.

Original language	English
Pages (from-to)	61-69
Number of pages	9
Journal	Journal of Organometallic Chemistry
Volume	569
Issue number	1-2
DOIs	https://doi.org/10.1016/S0022-328X(98)00774-8
State	Published - 1998/10/30

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/S0022-328X(98)00774-8

Cite this

@article{cc311cd41b014ccc84acdf824767686f,

title = "Stabilization of [Ru(bpy)2(CO)(η1-CO2)] and unprecedented reversible oxide transfer reactions from CO32- to [Ru(bpy)2(CO)2]2+ and from [Ru(bpy)2(CO)(η1-CO2)] to CO2",

abstract = "Unusual thermal stability of [Ru(bpy)2(CO)(η1-CO2)] (1) as a metal-η1-CO2 complex was examined both in solid state and in solution. Compound 1 dissolves in CH3CN containing LiCF3SO3. Interaction between Li+ and the η1-CO2 group enhances an electron flow from Ru to the CO2 ligand and greatly contributes to the stabilization of the Ru-η1-CO2 bond. The reaction of [Ru(bpy)2(CO)2](PF6)2 with [Crown·K]2CO3 in dry CH3CN selectively produced 1 through the 1:1 adduct with the RuC(O)-OCO2 moiety. Stoichimetric formation of 1 from the 1:1 adduct is also assisted by [Crown·K]+ as a Lewis acid. Similarly, the reaction of [Ru(bpy)2(CO)2](PF6)2 with (Me4N)2CO3 in DMSO gave the 1:1 adduct in the initial stage, which gradually changed to a metalloanhydride complex, [Ru(bpy)2(CO)((CO)2O)] due to the absence of Lewis acids to stabilize 1, since an addition of LiCF3SO3 to the solution gave [Ru(bpy)2(CO)(η1-CO2)] quantitatively.",

author = "Hiroshi Nakajima and Kiyoshi Tsuge and Kiyotsuna Toyohara and Koji Tanaka",

year = "1998",

month = oct,

day = "30",

doi = "10.1016/S0022-328X(98)00774-8",

language = "英語",

volume = "569",

pages = "61--69",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "1-2",

}

Stabilization of [Ru(bpy)₂(CO)(η¹-CO₂)] and unprecedented reversible oxide transfer reactions from CO₃^2- to [Ru(bpy)₂(CO)₂]²⁺ and from [Ru(bpy)₂(CO)(η¹-CO₂)] to CO₂. / Nakajima, Hiroshi; Tsuge, Kiyoshi; Toyohara, Kiyotsuna et al.
In: Journal of Organometallic Chemistry, Vol. 569, No. 1-2, 30.10.1998, p. 61-69.

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

TY - JOUR

T1 - Stabilization of [Ru(bpy)2(CO)(η1-CO2)] and unprecedented reversible oxide transfer reactions from CO32- to [Ru(bpy)2(CO)2]2+ and from [Ru(bpy)2(CO)(η1-CO2)] to CO2

AU - Nakajima, Hiroshi

AU - Tsuge, Kiyoshi

AU - Toyohara, Kiyotsuna

AU - Tanaka, Koji

PY - 1998/10/30

Y1 - 1998/10/30

N2 - Unusual thermal stability of [Ru(bpy)2(CO)(η1-CO2)] (1) as a metal-η1-CO2 complex was examined both in solid state and in solution. Compound 1 dissolves in CH3CN containing LiCF3SO3. Interaction between Li+ and the η1-CO2 group enhances an electron flow from Ru to the CO2 ligand and greatly contributes to the stabilization of the Ru-η1-CO2 bond. The reaction of [Ru(bpy)2(CO)2](PF6)2 with [Crown·K]2CO3 in dry CH3CN selectively produced 1 through the 1:1 adduct with the RuC(O)-OCO2 moiety. Stoichimetric formation of 1 from the 1:1 adduct is also assisted by [Crown·K]+ as a Lewis acid. Similarly, the reaction of [Ru(bpy)2(CO)2](PF6)2 with (Me4N)2CO3 in DMSO gave the 1:1 adduct in the initial stage, which gradually changed to a metalloanhydride complex, [Ru(bpy)2(CO)((CO)2O)] due to the absence of Lewis acids to stabilize 1, since an addition of LiCF3SO3 to the solution gave [Ru(bpy)2(CO)(η1-CO2)] quantitatively.

AB - Unusual thermal stability of [Ru(bpy)2(CO)(η1-CO2)] (1) as a metal-η1-CO2 complex was examined both in solid state and in solution. Compound 1 dissolves in CH3CN containing LiCF3SO3. Interaction between Li+ and the η1-CO2 group enhances an electron flow from Ru to the CO2 ligand and greatly contributes to the stabilization of the Ru-η1-CO2 bond. The reaction of [Ru(bpy)2(CO)2](PF6)2 with [Crown·K]2CO3 in dry CH3CN selectively produced 1 through the 1:1 adduct with the RuC(O)-OCO2 moiety. Stoichimetric formation of 1 from the 1:1 adduct is also assisted by [Crown·K]+ as a Lewis acid. Similarly, the reaction of [Ru(bpy)2(CO)2](PF6)2 with (Me4N)2CO3 in DMSO gave the 1:1 adduct in the initial stage, which gradually changed to a metalloanhydride complex, [Ru(bpy)2(CO)((CO)2O)] due to the absence of Lewis acids to stabilize 1, since an addition of LiCF3SO3 to the solution gave [Ru(bpy)2(CO)(η1-CO2)] quantitatively.

UR - http://www.scopus.com/inward/record.url?scp=0002358237&partnerID=8YFLogxK

U2 - 10.1016/S0022-328X(98)00774-8

DO - 10.1016/S0022-328X(98)00774-8

M3 - 学術論文

AN - SCOPUS:0002358237

SN - 0022-328X

VL - 569

SP - 61

EP - 69

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1-2