Influence of Halide Ion and Lewis Acid in the Demetalation of a Spirolactam Cyclohexadienyl Ruthenium Complex

F. Christopher Pigge; John J. Coniglio; Nigam Rath

doi:10.1021/om050701a

Influence of Halide Ion and Lewis Acid in the Demetalation of a Spirolactam Cyclohexadienyl Ruthenium Complex

F. Christopher Pigge, John J. Coniglio, Nigam Rath

University of Missouri-St. Louis

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

Abstract

Demetalation of an electron-rich spirolactam-based (cyclohexadienyl)Ru(II) complex is achieved upon treatment with boron trifluoride and a source of chloride ion. The cyclohexadienyl ligand is converted to a cyclohexadienone, cyclohexenone, or cyclohexenone epoxide derivative as a function of the specific reaction conditions. Stable (cyclohexadienyl)ruthenium substrates potentially suitable for demetalation under these conditions are prepared via intramolecular spirocyclization of (η 6 -arene)Ru precursors; thus, demetalation completes a net Ru-mediated dearomatization sequence. Moreover, the functionalized spirolactam products obtained are structurally distinct from those produced via direct oxidative demetalation.

Original language	American English
Journal	Organometallics
Volume	24
DOIs	https://doi.org/10.1021/om050701a
State	Published - Sep 30 2005

Keywords

Addition reactions
Anions
Hydrocarbons
Ligands
Mixtures

Disciplines

Life Sciences
Biochemistry, Biophysics, and Structural Biology
Biochemistry

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title = "Influence of Halide Ion and Lewis Acid in the Demetalation of a Spirolactam Cyclohexadienyl Ruthenium Complex",

abstract = " Demetalation of an electron-rich spirolactam-based (cyclohexadienyl)Ru(II) complex is achieved upon treatment with boron trifluoride and a source of chloride ion. The cyclohexadienyl ligand is converted to a cyclohexadienone, cyclohexenone, or cyclohexenone epoxide derivative as a function of the specific reaction conditions. Stable (cyclohexadienyl)ruthenium substrates potentially suitable for demetalation under these conditions are prepared via intramolecular spirocyclization of (η 6 -arene)Ru precursors; thus, demetalation completes a net Ru-mediated dearomatization sequence. Moreover, the functionalized spirolactam products obtained are structurally distinct from those produced via direct oxidative demetalation. ",

keywords = "Addition reactions, Anions, Hydrocarbons, Ligands, Mixtures",

author = "Pigge, {F. Christopher} and Coniglio, {John J.} and Nigam Rath",

note = "Demetalation of an electron-rich spirolactam-based (cyclohexadienyl)Ru(II) complex is achieved upon treatment with boron trifluoride and a source of chloride ion. The cyclohexadienyl ligand is converted to a cyclohexadienone, cyclohexenone, or cyclohexenone epoxide derivative as a function of the specific reaction conditions.",

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month = sep,

day = "30",

doi = "10.1021/om050701a",

language = "American English",

volume = "24",

journal = "Organometallics",

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TY - JOUR

T1 - Influence of Halide Ion and Lewis Acid in the Demetalation of a Spirolactam Cyclohexadienyl Ruthenium Complex

AU - Pigge, F. Christopher

AU - Coniglio, John J.

AU - Rath, Nigam

N1 - Demetalation of an electron-rich spirolactam-based (cyclohexadienyl)Ru(II) complex is achieved upon treatment with boron trifluoride and a source of chloride ion. The cyclohexadienyl ligand is converted to a cyclohexadienone, cyclohexenone, or cyclohexenone epoxide derivative as a function of the specific reaction conditions.

PY - 2005/9/30

Y1 - 2005/9/30

N2 - Demetalation of an electron-rich spirolactam-based (cyclohexadienyl)Ru(II) complex is achieved upon treatment with boron trifluoride and a source of chloride ion. The cyclohexadienyl ligand is converted to a cyclohexadienone, cyclohexenone, or cyclohexenone epoxide derivative as a function of the specific reaction conditions. Stable (cyclohexadienyl)ruthenium substrates potentially suitable for demetalation under these conditions are prepared via intramolecular spirocyclization of (η 6 -arene)Ru precursors; thus, demetalation completes a net Ru-mediated dearomatization sequence. Moreover, the functionalized spirolactam products obtained are structurally distinct from those produced via direct oxidative demetalation.

AB - Demetalation of an electron-rich spirolactam-based (cyclohexadienyl)Ru(II) complex is achieved upon treatment with boron trifluoride and a source of chloride ion. The cyclohexadienyl ligand is converted to a cyclohexadienone, cyclohexenone, or cyclohexenone epoxide derivative as a function of the specific reaction conditions. Stable (cyclohexadienyl)ruthenium substrates potentially suitable for demetalation under these conditions are prepared via intramolecular spirocyclization of (η 6 -arene)Ru precursors; thus, demetalation completes a net Ru-mediated dearomatization sequence. Moreover, the functionalized spirolactam products obtained are structurally distinct from those produced via direct oxidative demetalation.

KW - Addition reactions

KW - Anions

KW - Hydrocarbons

KW - Ligands

KW - Mixtures

UR - https://doi.org/10.1021/om050701a

U2 - 10.1021/om050701a

DO - 10.1021/om050701a

M3 - Article

VL - 24

JO - Organometallics

JF - Organometallics

ER -

Influence of Halide Ion and Lewis Acid in the Demetalation of a Spirolactam Cyclohexadienyl Ruthenium Complex

Abstract

Keywords

Disciplines

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