Bond-Forming Reactions to a Coordinated Hydroxo Group: Reaction of trans-Ir(CO)(OH)(P(p-tolyl)3)2 with Mel, EtI, HCI, CH3C(0)CI, and H2

Jeffrey S. Thompson; Sherri L. Randall; Jim D. Atwood

doi:10.1021/om00057a023

Bond-Forming Reactions to a Coordinated Hydroxo Group: Reaction of trans-Ir(CO)(OH)(P(p-tolyl)₃)₂ with Mel, EtI, HCI, CH₃C(0)CI, and H₂

Jeffrey S. Thompson
, Sherri L. Randall
, Jim D. Atwood

Chemistry

SUNY Buffalo

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

36 Scopus citations

Abstract

Reactions of trans-Ir(CO)(OH)(P(p-tolyl)₃)₂ with Mel, EtI, HC1, and CH₃C(O)C1 lead to the formation of bonds between the hydroxide and the adding group. For Mel and EtI addition, where the alcohols are formed, the reactions occur by oxidative addition followed by reductive elimination to form the carbon-oxygen bond. Reaction with HC1 proceeds very rapidly by protonation of the hydroxide to eliminate H₂0. The reaction of trans-Ir(CO)(OH)(P(p-tolyl)₃)₂ with acetyl chloride gives a mixture of products from initial attack of acetyl chloride on the hydroxide to produce acetic acid. Subsequent oxidative addition of the acid produces an acetate complex. Reaction of £rans-Ir(CO)(OH)(P(p-tolyl)₃)₂ with H₂ produces the trihydride H₃Ir(CO)(P(p-tolyl)₃)₂ and H₂O. This reaction is partially reversible; treatment of the trihydride with H₂O produces the hydroxy complex. The reactions reported here are among the first that exhibit bond formation to a metal-bound hydroxo group.

Original language	English
Pages (from-to)	3906-3910
Number of pages	5
Journal	Organometallics
Volume	10
Issue number	11
DOIs	https://doi.org/10.1021/om00057a023
State	Published - Oct 1 1991

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title = "Bond-Forming Reactions to a Coordinated Hydroxo Group: Reaction of trans-Ir(CO)(OH)(P(p-tolyl)3)2 with Mel, EtI, HCI, CH3C(0)CI, and H2",

abstract = "Reactions of trans-Ir(CO)(OH)(P(p-tolyl)3)2 with Mel, EtI, HC1, and CH3C(O)C1 lead to the formation of bonds between the hydroxide and the adding group. For Mel and EtI addition, where the alcohols are formed, the reactions occur by oxidative addition followed by reductive elimination to form the carbon-oxygen bond. Reaction with HC1 proceeds very rapidly by protonation of the hydroxide to eliminate H20. The reaction of trans-Ir(CO)(OH)(P(p-tolyl)3)2 with acetyl chloride gives a mixture of products from initial attack of acetyl chloride on the hydroxide to produce acetic acid. Subsequent oxidative addition of the acid produces an acetate complex. Reaction of £rans-Ir(CO)(OH)(P(p-tolyl)3)2 with H2 produces the trihydride H3Ir(CO)(P(p-tolyl)3)2 and H2O. This reaction is partially reversible; treatment of the trihydride with H2O produces the hydroxy complex. The reactions reported here are among the first that exhibit bond formation to a metal-bound hydroxo group.",

author = "Thompson, \{Jeffrey S.\} and Randall, \{Sherri L.\} and Atwood, \{Jim D.\}",

year = "1991",

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doi = "10.1021/om00057a023",

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T1 - Bond-Forming Reactions to a Coordinated Hydroxo Group

T2 - Reaction of trans-Ir(CO)(OH)(P(p-tolyl)3)2 with Mel, EtI, HCI, CH3C(0)CI, and H2

AU - Thompson, Jeffrey S.

AU - Randall, Sherri L.

AU - Atwood, Jim D.

PY - 1991/10/1

Y1 - 1991/10/1

N2 - Reactions of trans-Ir(CO)(OH)(P(p-tolyl)3)2 with Mel, EtI, HC1, and CH3C(O)C1 lead to the formation of bonds between the hydroxide and the adding group. For Mel and EtI addition, where the alcohols are formed, the reactions occur by oxidative addition followed by reductive elimination to form the carbon-oxygen bond. Reaction with HC1 proceeds very rapidly by protonation of the hydroxide to eliminate H20. The reaction of trans-Ir(CO)(OH)(P(p-tolyl)3)2 with acetyl chloride gives a mixture of products from initial attack of acetyl chloride on the hydroxide to produce acetic acid. Subsequent oxidative addition of the acid produces an acetate complex. Reaction of £rans-Ir(CO)(OH)(P(p-tolyl)3)2 with H2 produces the trihydride H3Ir(CO)(P(p-tolyl)3)2 and H2O. This reaction is partially reversible; treatment of the trihydride with H2O produces the hydroxy complex. The reactions reported here are among the first that exhibit bond formation to a metal-bound hydroxo group.

AB - Reactions of trans-Ir(CO)(OH)(P(p-tolyl)3)2 with Mel, EtI, HC1, and CH3C(O)C1 lead to the formation of bonds between the hydroxide and the adding group. For Mel and EtI addition, where the alcohols are formed, the reactions occur by oxidative addition followed by reductive elimination to form the carbon-oxygen bond. Reaction with HC1 proceeds very rapidly by protonation of the hydroxide to eliminate H20. The reaction of trans-Ir(CO)(OH)(P(p-tolyl)3)2 with acetyl chloride gives a mixture of products from initial attack of acetyl chloride on the hydroxide to produce acetic acid. Subsequent oxidative addition of the acid produces an acetate complex. Reaction of £rans-Ir(CO)(OH)(P(p-tolyl)3)2 with H2 produces the trihydride H3Ir(CO)(P(p-tolyl)3)2 and H2O. This reaction is partially reversible; treatment of the trihydride with H2O produces the hydroxy complex. The reactions reported here are among the first that exhibit bond formation to a metal-bound hydroxo group.

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U2 - 10.1021/om00057a023

DO - 10.1021/om00057a023

M3 - Article

AN - SCOPUS:0000569770

SN - 0276-7333

VL - 10

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EP - 3910

JO - Organometallics

JF - Organometallics

IS - 11

ER -

Bond-Forming Reactions to a Coordinated Hydroxo Group: Reaction of trans-Ir(CO)(OH)(P(p-tolyl)₃)₂ with Mel, EtI, HCI, CH₃C(0)CI, and H₂

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