Carbonylation of trans-Ir(CO)Cl(TPPTS)2 and reactivity of [Ir(CO)2(TPPTS)3]Cl (TPPTS = P(m-C6H4SO3Na)3) in DMSO and water

Paul J. Roman; Jim D. Atwood

doi:10.1021/om970351v

Carbonylation of trans-Ir(CO)Cl(TPPTS)₂ and reactivity of [Ir(CO)₂(TPPTS)₃]Cl (TPPTS = P(m-C₆H₄SO₃Na)₃) in DMSO and water

Paul J. Roman
, Jim D. Atwood

Chemistry

University at Buffalo

SUNY Buffalo

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

5 Scopus citations

Abstract

Reaction of CO with trans-Ir(CO)(Cl)(TPPTS)₂ in DMSO and H₂O give [Ir(CO)₃(TPPTS)₂]-Cl (H₂O and DMSO) and Ir(CO)₂(Cl)(TPPTS)₂ (DMSO only). In both solvents the carbonylation is reversed by passing N2 through the solution. In water, further reactions occur slowly, including water-gas-shift reactions and formation of Ir(CO)₂(TPPTS)₃⁺. This trisphosphine complex was independently prepared to examine its reactions. In DMSO, reaction with CO readily forms Ir(CO)₃(TPPTS)₂⁺; no reaction with CO is observed in water. Reaction of Ir(CO)₂(TPPTS)₃⁺ with H₂ occurs through TPPTS dissociation giving Ir(CO)₂-(H)₂(TPPTS)₂⁺ initially before reaction with free TPPTS gives Ir(CO)(H)₂(TPPTS)₃⁺ as the final product. Hydrogen bonding from water to the sulfonated phosphine ligands provides a reasonable explanation for the differing ligand substitution behavior in DMSO and H₂O.

Original language	English
Pages (from-to)	5536-5540
Number of pages	5
Journal	Organometallics
Volume	16
Issue number	25
DOIs	https://doi.org/10.1021/om970351v
State	Published - Dec 9 1997

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@article{9b5be5de70a54f5184f0ed7599144fc0,

title = "Carbonylation of trans-Ir(CO)Cl(TPPTS)2 and reactivity of [Ir(CO)2(TPPTS)3]Cl (TPPTS = P(m-C6H4SO3Na)3) in DMSO and water",

abstract = "Reaction of CO with trans-Ir(CO)(Cl)(TPPTS)2 in DMSO and H2O give [Ir(CO)3(TPPTS)2]-Cl (H2O and DMSO) and Ir(CO)2(Cl)(TPPTS)2 (DMSO only). In both solvents the carbonylation is reversed by passing N2 through the solution. In water, further reactions occur slowly, including water-gas-shift reactions and formation of Ir(CO)2(TPPTS)3+. This trisphosphine complex was independently prepared to examine its reactions. In DMSO, reaction with CO readily forms Ir(CO)3(TPPTS)2+; no reaction with CO is observed in water. Reaction of Ir(CO)2(TPPTS)3+ with H2 occurs through TPPTS dissociation giving Ir(CO)2-(H)2(TPPTS)2+ initially before reaction with free TPPTS gives Ir(CO)(H)2(TPPTS)3+ as the final product. Hydrogen bonding from water to the sulfonated phosphine ligands provides a reasonable explanation for the differing ligand substitution behavior in DMSO and H2O.",

author = "Roman, \{Paul J.\} and Atwood, \{Jim D.\}",

year = "1997",

month = dec,

day = "9",

doi = "10.1021/om970351v",

language = "English",

volume = "16",

pages = "5536--5540",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "25",

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TY - JOUR

T1 - Carbonylation of trans-Ir(CO)Cl(TPPTS)2 and reactivity of [Ir(CO)2(TPPTS)3]Cl (TPPTS = P(m-C6H4SO3Na)3) in DMSO and water

AU - Roman, Paul J.

AU - Atwood, Jim D.

PY - 1997/12/9

Y1 - 1997/12/9

N2 - Reaction of CO with trans-Ir(CO)(Cl)(TPPTS)2 in DMSO and H2O give [Ir(CO)3(TPPTS)2]-Cl (H2O and DMSO) and Ir(CO)2(Cl)(TPPTS)2 (DMSO only). In both solvents the carbonylation is reversed by passing N2 through the solution. In water, further reactions occur slowly, including water-gas-shift reactions and formation of Ir(CO)2(TPPTS)3+. This trisphosphine complex was independently prepared to examine its reactions. In DMSO, reaction with CO readily forms Ir(CO)3(TPPTS)2+; no reaction with CO is observed in water. Reaction of Ir(CO)2(TPPTS)3+ with H2 occurs through TPPTS dissociation giving Ir(CO)2-(H)2(TPPTS)2+ initially before reaction with free TPPTS gives Ir(CO)(H)2(TPPTS)3+ as the final product. Hydrogen bonding from water to the sulfonated phosphine ligands provides a reasonable explanation for the differing ligand substitution behavior in DMSO and H2O.

AB - Reaction of CO with trans-Ir(CO)(Cl)(TPPTS)2 in DMSO and H2O give [Ir(CO)3(TPPTS)2]-Cl (H2O and DMSO) and Ir(CO)2(Cl)(TPPTS)2 (DMSO only). In both solvents the carbonylation is reversed by passing N2 through the solution. In water, further reactions occur slowly, including water-gas-shift reactions and formation of Ir(CO)2(TPPTS)3+. This trisphosphine complex was independently prepared to examine its reactions. In DMSO, reaction with CO readily forms Ir(CO)3(TPPTS)2+; no reaction with CO is observed in water. Reaction of Ir(CO)2(TPPTS)3+ with H2 occurs through TPPTS dissociation giving Ir(CO)2-(H)2(TPPTS)2+ initially before reaction with free TPPTS gives Ir(CO)(H)2(TPPTS)3+ as the final product. Hydrogen bonding from water to the sulfonated phosphine ligands provides a reasonable explanation for the differing ligand substitution behavior in DMSO and H2O.

UR - https://www.scopus.com/pages/publications/0038698556

U2 - 10.1021/om970351v

DO - 10.1021/om970351v

M3 - Article

SN - 0276-7333

VL - 16

SP - 5536

EP - 5540

JO - Organometallics

JF - Organometallics

IS - 25

ER -

Carbonylation of trans-Ir(CO)Cl(TPPTS)₂ and reactivity of [Ir(CO)₂(TPPTS)₃]Cl (TPPTS = P(m-C₆H₄SO₃Na)₃) in DMSO and water

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