Oxidation of the Carbonylbis(1,2-bis(diphenylphosphino)ethane)iridium(I) Cation. Preparation and Characterization of a Series of Iridium(III) Carbonyl Dications

Michael A. Lilga; James A. Ibers

doi:10.1021/ic00190a021

Oxidation of the Carbonylbis(1,2-bis(diphenylphosphino)ethane)iridium(I) Cation. Preparation and Characterization of a Series of Iridium(III) Carbonyl Dications

Michael A. Lilga, James A. Ibers

Chemistry

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Abstract

Oxidation of Ir(CO)(dppe)₂⁺ with halogens affords cw-IrX(CO)(dppe)₂²⁺ (X = Cl, Br) while oxidation with HBF₄affords cis-IrH(CO)(dppe)₂²⁺. The species trans-IrX(CO)(dppe)₂²⁺ (X = Cl, Br) are prepared by the oxidation of Ir(CO)(dppe)₂⁺ with nitrosonium ion in the presence of Cl^- or Br^-. The complex transs-IrH(CO)(dppe)₂²⁺ is most convenientlyprepared by protonation of [Ir(dppe)₂]BF₄ with HBF₄-Et₂O to afford the intermediate IrH(dppe)₂²⁺, followedby CO addition. In contrast, both cis-and trans-IrCl(CO)(dppe)₂²⁺ species are formed by the electrochemical oxidation of Ir(CO)(dppe)₂⁺ in chloride media. The trans isomer is reduced at a more negative potential and is thus thermodynamically the more stable. Reversible deprotonation of cis-[IrH(CO)(dppe)₂][BF₄]₂ by chloride implies that the acidity of this compound is of the order of that of HC1, unusually strong for a third-row transition-metal hydrido complex.

Original language	English (US)
Pages (from-to)	3538-3543
Number of pages	6
Journal	Inorganic chemistry
Volume	23
Issue number	22
DOIs	https://doi.org/10.1021/ic00190a021
State	Published - Jan 1984

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Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Oxidation of the Carbonylbis(1,2-bis(diphenylphosphino)ethane)iridium(I) Cation. Preparation and Characterization of a Series of Iridium(III) Carbonyl Dications",

abstract = "Oxidation of Ir(CO)(dppe)2+ with halogens affords cw-IrX(CO)(dppe)22+ (X = Cl, Br) while oxidation with HBF4affords cis-IrH(CO)(dppe)22+. The species trans-IrX(CO)(dppe)22+ (X = Cl, Br) are prepared by the oxidation of Ir(CO)(dppe)2+ with nitrosonium ion in the presence of Cl- or Br-. The complex transs-IrH(CO)(dppe)22+ is most convenientlyprepared by protonation of [Ir(dppe)2]BF4 with HBF4-Et2O to afford the intermediate IrH(dppe)22+, followedby CO addition. In contrast, both cis-and trans-IrCl(CO)(dppe)22+ species are formed by the electrochemical oxidation of Ir(CO)(dppe)2+ in chloride media. The trans isomer is reduced at a more negative potential and is thus thermodynamically the more stable. Reversible deprotonation of cis-[IrH(CO)(dppe)2][BF4]2 by chloride implies that the acidity of this compound is of the order of that of HC1, unusually strong for a third-row transition-metal hydrido complex.",

author = "Lilga, {Michael A.} and Ibers, {James A.}",

year = "1984",

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doi = "10.1021/ic00190a021",

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AU - Ibers, James A.

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N2 - Oxidation of Ir(CO)(dppe)2+ with halogens affords cw-IrX(CO)(dppe)22+ (X = Cl, Br) while oxidation with HBF4affords cis-IrH(CO)(dppe)22+. The species trans-IrX(CO)(dppe)22+ (X = Cl, Br) are prepared by the oxidation of Ir(CO)(dppe)2+ with nitrosonium ion in the presence of Cl- or Br-. The complex transs-IrH(CO)(dppe)22+ is most convenientlyprepared by protonation of [Ir(dppe)2]BF4 with HBF4-Et2O to afford the intermediate IrH(dppe)22+, followedby CO addition. In contrast, both cis-and trans-IrCl(CO)(dppe)22+ species are formed by the electrochemical oxidation of Ir(CO)(dppe)2+ in chloride media. The trans isomer is reduced at a more negative potential and is thus thermodynamically the more stable. Reversible deprotonation of cis-[IrH(CO)(dppe)2][BF4]2 by chloride implies that the acidity of this compound is of the order of that of HC1, unusually strong for a third-row transition-metal hydrido complex.

AB - Oxidation of Ir(CO)(dppe)2+ with halogens affords cw-IrX(CO)(dppe)22+ (X = Cl, Br) while oxidation with HBF4affords cis-IrH(CO)(dppe)22+. The species trans-IrX(CO)(dppe)22+ (X = Cl, Br) are prepared by the oxidation of Ir(CO)(dppe)2+ with nitrosonium ion in the presence of Cl- or Br-. The complex transs-IrH(CO)(dppe)22+ is most convenientlyprepared by protonation of [Ir(dppe)2]BF4 with HBF4-Et2O to afford the intermediate IrH(dppe)22+, followedby CO addition. In contrast, both cis-and trans-IrCl(CO)(dppe)22+ species are formed by the electrochemical oxidation of Ir(CO)(dppe)2+ in chloride media. The trans isomer is reduced at a more negative potential and is thus thermodynamically the more stable. Reversible deprotonation of cis-[IrH(CO)(dppe)2][BF4]2 by chloride implies that the acidity of this compound is of the order of that of HC1, unusually strong for a third-row transition-metal hydrido complex.

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Oxidation of the Carbonylbis(1,2-bis(diphenylphosphino)ethane)iridium(I) Cation. Preparation and Characterization of a Series of Iridium(III) Carbonyl Dications

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