Formation and Reactivity of Ir(III) Hydroxycarbonyl Complexes

Paul I P Elliott, Claire E. Haslam, Sharon E. Spey, Anthony Haynes

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

Kinetic studies show that the reaction of [TpIr(CO)2] (1, Tp = hydrotris(pyrazolyl)borate) with water to give [TpIr(CO2H)(CO)H] (2) is second order (k = 1.65 × 10-4 dm3 mol -1 s-1, 25°C, MeCN) with activation parameters ΔH = 46±2 kJ mol-1 and ΔS = -162±5 J K-1 mol-1. A kinetic isotope effect of kH2O/kD2O = 1.40 at 20°C indicates that O-H/D bond cleavage is involved in the rate-determining step. Despite being more electron rich than 1, [Tp*Ir(CO)2] (1*, Tp* = hydrotris(3,5-dimethylpyrazolyl)borate) reacts rapidly with adventitious water to give [Tp*Ir(CO2H)(CO)H] (2*). A proposed mechanism consistent with the relative reactivity of 1 and 1* involves initial protonation of Ir(I) followed by nucleophilic attack on a carbonyl ligand. An X-ray crystal structure of 2* shows dimer formation via pairwise H-bonding interactions of hydroxycarbonyl ligands (r(O⋯O) 2.65 Å). Complex 2* is thermally stable but (like 2) is amphoteric, undergoing dehydroxylation with acid to give [Tp*Ir(CO)2H]+ (3*) and decarboxylation with OH- to give [Tp*Ir(CO) H2] (4*). Complex 2 undergoes thermal decarboxylation above ca. 50 °C to give [TpIr(CO)H2] (4) in a first-order process with activation parameters ΔH = 115±4 kJ mol -1 and ΔS = 60±10 J K-1 mol-1.

Original languageEnglish
Pages (from-to)6269-6275
Number of pages7
JournalInorganic Chemistry
Volume45
Issue number16
DOIs
Publication statusPublished - 7 Aug 2006
Externally publishedYes

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decarboxylation
borates
reactivity
Chemical activation
activation
Ligands
Borates
ligands
Kinetics
Water
Protonation
kinetics
Isotopes
Dimers
isotope effect
water
attack
cleavage
Crystal structure
dimers

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Elliott, Paul I P ; Haslam, Claire E. ; Spey, Sharon E. ; Haynes, Anthony. / Formation and Reactivity of Ir(III) Hydroxycarbonyl Complexes. In: Inorganic Chemistry. 2006 ; Vol. 45, No. 16. pp. 6269-6275.
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title = "Formation and Reactivity of Ir(III) Hydroxycarbonyl Complexes",
abstract = "Kinetic studies show that the reaction of [TpIr(CO)2] (1, Tp = hydrotris(pyrazolyl)borate) with water to give [TpIr(CO2H)(CO)H] (2) is second order (k = 1.65 × 10-4 dm3 mol -1 s-1, 25°C, MeCN) with activation parameters ΔH‡ = 46±2 kJ mol-1 and ΔS ‡ = -162±5 J K-1 mol-1. A kinetic isotope effect of kH2O/kD2O = 1.40 at 20°C indicates that O-H/D bond cleavage is involved in the rate-determining step. Despite being more electron rich than 1, [Tp*Ir(CO)2] (1*, Tp* = hydrotris(3,5-dimethylpyrazolyl)borate) reacts rapidly with adventitious water to give [Tp*Ir(CO2H)(CO)H] (2*). A proposed mechanism consistent with the relative reactivity of 1 and 1* involves initial protonation of Ir(I) followed by nucleophilic attack on a carbonyl ligand. An X-ray crystal structure of 2* shows dimer formation via pairwise H-bonding interactions of hydroxycarbonyl ligands (r(O⋯O) 2.65 {\AA}). Complex 2* is thermally stable but (like 2) is amphoteric, undergoing dehydroxylation with acid to give [Tp*Ir(CO)2H]+ (3*) and decarboxylation with OH- to give [Tp*Ir(CO) H2] (4*). Complex 2 undergoes thermal decarboxylation above ca. 50 °C to give [TpIr(CO)H2] (4) in a first-order process with activation parameters ΔH‡ = 115±4 kJ mol -1 and ΔS‡ = 60±10 J K-1 mol-1.",
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Formation and Reactivity of Ir(III) Hydroxycarbonyl Complexes. / Elliott, Paul I P; Haslam, Claire E.; Spey, Sharon E.; Haynes, Anthony.

In: Inorganic Chemistry, Vol. 45, No. 16, 07.08.2006, p. 6269-6275.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Formation and Reactivity of Ir(III) Hydroxycarbonyl Complexes

AU - Elliott, Paul I P

AU - Haslam, Claire E.

AU - Spey, Sharon E.

AU - Haynes, Anthony

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N2 - Kinetic studies show that the reaction of [TpIr(CO)2] (1, Tp = hydrotris(pyrazolyl)borate) with water to give [TpIr(CO2H)(CO)H] (2) is second order (k = 1.65 × 10-4 dm3 mol -1 s-1, 25°C, MeCN) with activation parameters ΔH‡ = 46±2 kJ mol-1 and ΔS ‡ = -162±5 J K-1 mol-1. A kinetic isotope effect of kH2O/kD2O = 1.40 at 20°C indicates that O-H/D bond cleavage is involved in the rate-determining step. Despite being more electron rich than 1, [Tp*Ir(CO)2] (1*, Tp* = hydrotris(3,5-dimethylpyrazolyl)borate) reacts rapidly with adventitious water to give [Tp*Ir(CO2H)(CO)H] (2*). A proposed mechanism consistent with the relative reactivity of 1 and 1* involves initial protonation of Ir(I) followed by nucleophilic attack on a carbonyl ligand. An X-ray crystal structure of 2* shows dimer formation via pairwise H-bonding interactions of hydroxycarbonyl ligands (r(O⋯O) 2.65 Å). Complex 2* is thermally stable but (like 2) is amphoteric, undergoing dehydroxylation with acid to give [Tp*Ir(CO)2H]+ (3*) and decarboxylation with OH- to give [Tp*Ir(CO) H2] (4*). Complex 2 undergoes thermal decarboxylation above ca. 50 °C to give [TpIr(CO)H2] (4) in a first-order process with activation parameters ΔH‡ = 115±4 kJ mol -1 and ΔS‡ = 60±10 J K-1 mol-1.

AB - Kinetic studies show that the reaction of [TpIr(CO)2] (1, Tp = hydrotris(pyrazolyl)borate) with water to give [TpIr(CO2H)(CO)H] (2) is second order (k = 1.65 × 10-4 dm3 mol -1 s-1, 25°C, MeCN) with activation parameters ΔH‡ = 46±2 kJ mol-1 and ΔS ‡ = -162±5 J K-1 mol-1. A kinetic isotope effect of kH2O/kD2O = 1.40 at 20°C indicates that O-H/D bond cleavage is involved in the rate-determining step. Despite being more electron rich than 1, [Tp*Ir(CO)2] (1*, Tp* = hydrotris(3,5-dimethylpyrazolyl)borate) reacts rapidly with adventitious water to give [Tp*Ir(CO2H)(CO)H] (2*). A proposed mechanism consistent with the relative reactivity of 1 and 1* involves initial protonation of Ir(I) followed by nucleophilic attack on a carbonyl ligand. An X-ray crystal structure of 2* shows dimer formation via pairwise H-bonding interactions of hydroxycarbonyl ligands (r(O⋯O) 2.65 Å). Complex 2* is thermally stable but (like 2) is amphoteric, undergoing dehydroxylation with acid to give [Tp*Ir(CO)2H]+ (3*) and decarboxylation with OH- to give [Tp*Ir(CO) H2] (4*). Complex 2 undergoes thermal decarboxylation above ca. 50 °C to give [TpIr(CO)H2] (4) in a first-order process with activation parameters ΔH‡ = 115±4 kJ mol -1 and ΔS‡ = 60±10 J K-1 mol-1.

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JF - Inorganic Chemistry

SN - 0020-1669

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