Amine-oxide-mediated oxidative methanolysis of metal-metal bonds in [MM'(CO)10] (M = Mn, Re; M' = Re) and [Os3(CO)12]: Crystal structure of fac-[Re{OC(O)OMe}(CO)3(η2-dppf)]

Yaw Kai Yan; Wendy Koh; Chenghua Jiang; Weng Kee Leong; T. S.Andy Hor

doi:10.1016/S0277-5387(00)00296-5

Amine-oxide-mediated oxidative methanolysis of metal-metal bonds in [MM'(CO)₁₀] (M = Mn, Re; M' = Re) and [Os₃(CO)₁₂]: Crystal structure of fac-[Re{OC(O)OMe}(CO)₃(η²-dppf)]

Yaw Kai Yan^*, Wendy Koh, Chenghua Jiang, Weng Kee Leong, T. S.Andy Hor

^*Corresponding author for this work

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

12 Citations (Scopus)

Abstract

The reaction of 1,1'-bis(diphenylphosphino)ferrocene (dppf) with a mixture of [MnRe(CO)₁₀], MeOH and Me₃NO afforded the complexes fac-[MnH(CO)₃(η²-dppf)] and [Re₂(μ-OMe)₂(μ-dppf) (CO)₆]. In the one-pot reaction of [Re₂(CO)₁₀] with Me₃NO, MeOH and dppf, the major mononuclear Re species isolated was the CO₂-inserted complex fac-[Re{OC(O)OMe}(CO)₃(η²-dppf)], the crystal structure of which was determined. The coordination sphere of the rhenium atom is roughly octahedral, consisting of an oxygen atom from the methyl carbonate ligand, two phosphorus atoms from a chelating dppf ligand, and three carbon atoms from a facial arrangement of three terminally bonded carbonyls. Analogous Me₃NO-mediated methoxylation reactions involving [Os₃(CO)₁₂] were also investigated. With a [Me₃NO]:[Os₃(CO)₁₂] ratio of 2:1, the major product is [Os₃(CO)₁₀(μ-H)(μ-Ome)]. With three molar equivalents of Me₃NO, significant quantities of [Os₃(CO)₁₀(μ-OMe)₂] are also obtained. (C) 2000 Elsevier Science Ltd.

Original language	English
Pages (from-to)	641-647
Number of pages	7
Journal	Polyhedron
Volume	19
Issue number	6
DOIs	https://doi.org/10.1016/S0277-5387(00)00296-5
Publication status	Published - Mar 30 2000
Externally published	Yes

ASJC Scopus Subject Areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

Keywords

Amine oxide
Carbonyl
Methanolysis
Methylcarbonate
Osmium
Rhenium

Access to Document

10.1016/S0277-5387(00)00296-5

Cite this

@article{c6a6caa234884aa89a9ec7fd441cd22e,

title = "Amine-oxide-mediated oxidative methanolysis of metal-metal bonds in [MM'(CO)10] (M = Mn, Re; M' = Re) and [Os3(CO)12]: Crystal structure of fac-[Re{OC(O)OMe}(CO)3(η2-dppf)]",

abstract = "The reaction of 1,1'-bis(diphenylphosphino)ferrocene (dppf) with a mixture of [MnRe(CO)10], MeOH and Me3NO afforded the complexes fac-[MnH(CO)3(η2-dppf)] and [Re2(μ-OMe)2(μ-dppf) (CO)6]. In the one-pot reaction of [Re2(CO)10] with Me3NO, MeOH and dppf, the major mononuclear Re species isolated was the CO2-inserted complex fac-[Re{OC(O)OMe}(CO)3(η2-dppf)], the crystal structure of which was determined. The coordination sphere of the rhenium atom is roughly octahedral, consisting of an oxygen atom from the methyl carbonate ligand, two phosphorus atoms from a chelating dppf ligand, and three carbon atoms from a facial arrangement of three terminally bonded carbonyls. Analogous Me3NO-mediated methoxylation reactions involving [Os3(CO)12] were also investigated. With a [Me3NO]:[Os3(CO)12] ratio of 2:1, the major product is [Os3(CO)10(μ-H)(μ-Ome)]. With three molar equivalents of Me3NO, significant quantities of [Os3(CO)10(μ-OMe)2] are also obtained. (C) 2000 Elsevier Science Ltd.",

keywords = "Amine oxide, Carbonyl, Methanolysis, Methylcarbonate, Osmium, Rhenium",

author = "Yan, {Yaw Kai} and Wendy Koh and Chenghua Jiang and Leong, {Weng Kee} and Hor, {T. S.Andy}",

year = "2000",

month = mar,

day = "30",

doi = "10.1016/S0277-5387(00)00296-5",

language = "English",

volume = "19",

pages = "641--647",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier Limited",

number = "6",

}

TY - JOUR

T1 - Amine-oxide-mediated oxidative methanolysis of metal-metal bonds in [MM'(CO)10] (M = Mn, Re; M' = Re) and [Os3(CO)12]

T2 - Crystal structure of fac-[Re{OC(O)OMe}(CO)3(η2-dppf)]

AU - Yan, Yaw Kai

AU - Koh, Wendy

AU - Jiang, Chenghua

AU - Leong, Weng Kee

AU - Hor, T. S.Andy

PY - 2000/3/30

Y1 - 2000/3/30

N2 - The reaction of 1,1'-bis(diphenylphosphino)ferrocene (dppf) with a mixture of [MnRe(CO)10], MeOH and Me3NO afforded the complexes fac-[MnH(CO)3(η2-dppf)] and [Re2(μ-OMe)2(μ-dppf) (CO)6]. In the one-pot reaction of [Re2(CO)10] with Me3NO, MeOH and dppf, the major mononuclear Re species isolated was the CO2-inserted complex fac-[Re{OC(O)OMe}(CO)3(η2-dppf)], the crystal structure of which was determined. The coordination sphere of the rhenium atom is roughly octahedral, consisting of an oxygen atom from the methyl carbonate ligand, two phosphorus atoms from a chelating dppf ligand, and three carbon atoms from a facial arrangement of three terminally bonded carbonyls. Analogous Me3NO-mediated methoxylation reactions involving [Os3(CO)12] were also investigated. With a [Me3NO]:[Os3(CO)12] ratio of 2:1, the major product is [Os3(CO)10(μ-H)(μ-Ome)]. With three molar equivalents of Me3NO, significant quantities of [Os3(CO)10(μ-OMe)2] are also obtained. (C) 2000 Elsevier Science Ltd.

AB - The reaction of 1,1'-bis(diphenylphosphino)ferrocene (dppf) with a mixture of [MnRe(CO)10], MeOH and Me3NO afforded the complexes fac-[MnH(CO)3(η2-dppf)] and [Re2(μ-OMe)2(μ-dppf) (CO)6]. In the one-pot reaction of [Re2(CO)10] with Me3NO, MeOH and dppf, the major mononuclear Re species isolated was the CO2-inserted complex fac-[Re{OC(O)OMe}(CO)3(η2-dppf)], the crystal structure of which was determined. The coordination sphere of the rhenium atom is roughly octahedral, consisting of an oxygen atom from the methyl carbonate ligand, two phosphorus atoms from a chelating dppf ligand, and three carbon atoms from a facial arrangement of three terminally bonded carbonyls. Analogous Me3NO-mediated methoxylation reactions involving [Os3(CO)12] were also investigated. With a [Me3NO]:[Os3(CO)12] ratio of 2:1, the major product is [Os3(CO)10(μ-H)(μ-Ome)]. With three molar equivalents of Me3NO, significant quantities of [Os3(CO)10(μ-OMe)2] are also obtained. (C) 2000 Elsevier Science Ltd.

KW - Amine oxide

KW - Carbonyl

KW - Methanolysis

KW - Methylcarbonate

KW - Osmium

KW - Rhenium

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U2 - 10.1016/S0277-5387(00)00296-5

DO - 10.1016/S0277-5387(00)00296-5

M3 - Article

AN - SCOPUS:0034731981

SN - 0277-5387

VL - 19

SP - 641

EP - 647

JO - Polyhedron

JF - Polyhedron

IS - 6

ER -