Kinetic Studies of Ligand Substitution for Carbon Monoxide on Dodecacarbonyltetrairidium, Ir4(CO)12

Dave Sonnenberger; Jim D. Atwood

doi:10.1021/ic50224a021

Kinetic Studies of Ligand Substitution for Carbon Monoxide on Dodecacarbonyltetrairidium, Ir₄(CO)₁₂

Dave Sonnenberger
, Jim D. Atwood

Chemistry

SUNY Buffalo

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

44 Scopus citations

Abstract

The kinetics of ligand substitution for CO on Ir₄(CO)₁₂ have been investigated for the ligands P(C₄H₉)₃, P(C₆H₅)₃, P(OC₆H₅)₃, and As(C6H5)3 between 30 and 125 °C. The rates show a dependence on the nature and concentration of the entering ligand with the rate law rate = (k₁ + k₂[L])[Ir₄(CO)_l2], For reasonably nucleophilic ligands [P(C₄H₉)₃, P(OC₆H₅)₃, and P(C₆H₅)₃] the second-order term contributes more than 95% of the total rate. The k2 term involves nucleophilic attack at an iridium center, and the k₁ term involves CO dissociation. The product of the substitution reaction depends on the ligand and on the reaction conditions. Many of the possible intermediates are identified by infrared spectroscopy. The mechanism of ligand substitution is discussed.

Original language	English
Pages (from-to)	3243-3246
Number of pages	4
Journal	Inorganic Chemistry
Volume	20
Issue number	10
DOIs	https://doi.org/10.1021/ic50224a021
State	Published - Oct 1981

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title = "Kinetic Studies of Ligand Substitution for Carbon Monoxide on Dodecacarbonyltetrairidium, Ir4(CO)12",

abstract = "The kinetics of ligand substitution for CO on Ir4(CO)12 have been investigated for the ligands P(C4H9)3, P(C6H5)3, P(OC6H5)3, and As(C6H5)3 between 30 and 125 °C. The rates show a dependence on the nature and concentration of the entering ligand with the rate law rate = (k1 + k2[L])[Ir4(CO)l2], For reasonably nucleophilic ligands [P(C4H9)3, P(OC6H5)3, and P(C6H5)3] the second-order term contributes more than 95\% of the total rate. The k2 term involves nucleophilic attack at an iridium center, and the k1 term involves CO dissociation. The product of the substitution reaction depends on the ligand and on the reaction conditions. Many of the possible intermediates are identified by infrared spectroscopy. The mechanism of ligand substitution is discussed.",

author = "Dave Sonnenberger and Atwood, \{Jim D.\}",

year = "1981",

month = oct,

doi = "10.1021/ic50224a021",

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volume = "20",

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journal = "Inorganic Chemistry",

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T1 - Kinetic Studies of Ligand Substitution for Carbon Monoxide on Dodecacarbonyltetrairidium, Ir4(CO)12

AU - Sonnenberger, Dave

AU - Atwood, Jim D.

PY - 1981/10

Y1 - 1981/10

N2 - The kinetics of ligand substitution for CO on Ir4(CO)12 have been investigated for the ligands P(C4H9)3, P(C6H5)3, P(OC6H5)3, and As(C6H5)3 between 30 and 125 °C. The rates show a dependence on the nature and concentration of the entering ligand with the rate law rate = (k1 + k2[L])[Ir4(CO)l2], For reasonably nucleophilic ligands [P(C4H9)3, P(OC6H5)3, and P(C6H5)3] the second-order term contributes more than 95% of the total rate. The k2 term involves nucleophilic attack at an iridium center, and the k1 term involves CO dissociation. The product of the substitution reaction depends on the ligand and on the reaction conditions. Many of the possible intermediates are identified by infrared spectroscopy. The mechanism of ligand substitution is discussed.

AB - The kinetics of ligand substitution for CO on Ir4(CO)12 have been investigated for the ligands P(C4H9)3, P(C6H5)3, P(OC6H5)3, and As(C6H5)3 between 30 and 125 °C. The rates show a dependence on the nature and concentration of the entering ligand with the rate law rate = (k1 + k2[L])[Ir4(CO)l2], For reasonably nucleophilic ligands [P(C4H9)3, P(OC6H5)3, and P(C6H5)3] the second-order term contributes more than 95% of the total rate. The k2 term involves nucleophilic attack at an iridium center, and the k1 term involves CO dissociation. The product of the substitution reaction depends on the ligand and on the reaction conditions. Many of the possible intermediates are identified by infrared spectroscopy. The mechanism of ligand substitution is discussed.

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U2 - 10.1021/ic50224a021

DO - 10.1021/ic50224a021

M3 - Article

AN - SCOPUS:4243478894

SN - 0020-1669

VL - 20

SP - 3243

EP - 3246

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 10

ER -

Kinetic Studies of Ligand Substitution for Carbon Monoxide on Dodecacarbonyltetrairidium, Ir₄(CO)₁₂

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