Preparation of Acylpentacarbonylchromate Salts and Alkoxycarbene Pentacarbonyl Complexes of Chromium Employing the Pentacarbonylchromate Dianion ([Cr(CO)5]2-)

M. F. Semmelhack; G. R. Lee

doi:10.1021/om00152a002

Preparation of Acylpentacarbonylchromate Salts and Alkoxycarbene Pentacarbonyl Complexes of Chromium Employing the Pentacarbonylchromate Dianion ([Cr(CO)₅]^2-)

M. F. Semmelhack, G. R. Lee

Chemistry

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64 Scopus citations

Abstract

The in situ generated lithium and sodium salts of [Cr(CO)₅]^2-(3) react rapidly and cleanly with a variety of aryl and alkyl acid chlorides at -78 °C in THF to provide solutions of the corresponding acylpenta-carbonylchromate salts M′[RC(0)Cr(C0)₅] (M′[l], M′ = Li, Na). Subsequent O-methylation of 1 produces Fischer-type alkoxycarbene complexes in yields competitive with established methodologies. This two-step procedure has enabled the preparation of arylmethoxycarbene complexes such as (CO)₅Cr=C(OMe)-{2,5·(OAc)2C₆H₃} (2g) which are otherwise inaccessible by the standard Fischer synthesis. Alkoxycarbene complexes of molybdenum and tungsten may be prepared analogously from [Mo(CO)₅]^2- and [W(CO)₅]^2-.

Original language	English (US)
Pages (from-to)	1839-1844
Number of pages	6
Journal	Organometallics
Volume	6
Issue number	9
DOIs	https://doi.org/10.1021/om00152a002
State	Published - Sep 1 1987

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Preparation of Acylpentacarbonylchromate Salts and Alkoxycarbene Pentacarbonyl Complexes of Chromium Employing the Pentacarbonylchromate Dianion ([Cr(CO)5]2-)",

abstract = "The in situ generated lithium and sodium salts of [Cr(CO)5]2-(3) react rapidly and cleanly with a variety of aryl and alkyl acid chlorides at -78 °C in THF to provide solutions of the corresponding acylpenta-carbonylchromate salts M′[RC(0)Cr(C0)5] (M′[l], M′ = Li, Na). Subsequent O-methylation of 1 produces Fischer-type alkoxycarbene complexes in yields competitive with established methodologies. This two-step procedure has enabled the preparation of arylmethoxycarbene complexes such as (CO)5Cr=C(OMe)-{2,5·(OAc)2C6H3} (2g) which are otherwise inaccessible by the standard Fischer synthesis. Alkoxycarbene complexes of molybdenum and tungsten may be prepared analogously from [Mo(CO)5]2- and [W(CO)5]2-.",

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AU - Lee, G. R.

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N2 - The in situ generated lithium and sodium salts of [Cr(CO)5]2-(3) react rapidly and cleanly with a variety of aryl and alkyl acid chlorides at -78 °C in THF to provide solutions of the corresponding acylpenta-carbonylchromate salts M′[RC(0)Cr(C0)5] (M′[l], M′ = Li, Na). Subsequent O-methylation of 1 produces Fischer-type alkoxycarbene complexes in yields competitive with established methodologies. This two-step procedure has enabled the preparation of arylmethoxycarbene complexes such as (CO)5Cr=C(OMe)-{2,5·(OAc)2C6H3} (2g) which are otherwise inaccessible by the standard Fischer synthesis. Alkoxycarbene complexes of molybdenum and tungsten may be prepared analogously from [Mo(CO)5]2- and [W(CO)5]2-.

AB - The in situ generated lithium and sodium salts of [Cr(CO)5]2-(3) react rapidly and cleanly with a variety of aryl and alkyl acid chlorides at -78 °C in THF to provide solutions of the corresponding acylpenta-carbonylchromate salts M′[RC(0)Cr(C0)5] (M′[l], M′ = Li, Na). Subsequent O-methylation of 1 produces Fischer-type alkoxycarbene complexes in yields competitive with established methodologies. This two-step procedure has enabled the preparation of arylmethoxycarbene complexes such as (CO)5Cr=C(OMe)-{2,5·(OAc)2C6H3} (2g) which are otherwise inaccessible by the standard Fischer synthesis. Alkoxycarbene complexes of molybdenum and tungsten may be prepared analogously from [Mo(CO)5]2- and [W(CO)5]2-.

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Preparation of Acylpentacarbonylchromate Salts and Alkoxycarbene Pentacarbonyl Complexes of Chromium Employing the Pentacarbonylchromate Dianion ([Cr(CO)₅]^2-)

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