Oxidative addition of carboxylic acids to trans-carbonylhalogenobis-(tertiary phosphine)iridium(I) complexes

Doorn, J. A. Van; Masters, Christopher; Woude, C. Van Der

doi:10.1039/dt9780001213

Cited by 11 publications

(3 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…where KP is the equilibrium constant for the equilibrium IrH(CO)P3 IrH(CO)P2 + P (7) k*t ka is the observed apparent first-order rate constant, [Ir] = [IrH(CO)P3], and £CH2ci2 is the bimolecular rate constant for reaction of 1 with CH2C12. The integrated form of this rate law corresponds to the experimental observation and predicts that the slope of a plot of ka vs. 1 / [P] will equal IV.…”

Section: Resultsmentioning

confidence: 99%

Preparation and interconversion of two isomeric iridium trihydrides

Harrod¹,

YORKE²

1981

Inorg. Chem.

View full text Add to dashboard Cite

Section: Resultsmentioning

confidence: 99%

Preparation and interconversion of two isomeric iridium trihydrides

Harrod¹,

YORKE²

1981

Inorg. Chem.

View full text Add to dashboard Cite

“…Subsequent insertion of one of the CC bonds into the Ir–H bond would account for the formation of 1 (Scheme ). In this context, it is worth mentioning that the oxidative addition of carboxylic acids to iridium(I) complexes is a well-documented process …”

Section: Results and Disscusionmentioning

confidence: 99%

ONO Dianionic Pincer-Type Ligand Precursors for the Synthesis of σ,π-Cyclooctenyl Iridium(III) Complexes: Formation Mechanism and Coordination Chemistry

et al. 2013

View full text Add to dashboard Cite

The σ,π-cyclooctenyl iridium (III) pincer compounds [Ir(κ 3-pydc-X)(1-κ-4,5-η-C 8 H 13)] (X = H (1), Cl, Br) have been prepared from [Ir(µ-OMe)(cod)] 2 and the corresponding 4substituted pyridine-2,6-dicarboxylic acids (H 2 pydc-X) or, alternatively, from their lithium salts (X = H) and [Ir(cod)(CH 3 CN) 2 ]PF 6. Deuterium labeling studies in combination with theoretical calculations have shown that formation of 1 involves a metal-mediated proton transfer in the reactive intermediate [Ir(κ 2-Hpydc)(cod)], through the solvent stabilized hydrido complex [IrH(κ 3-pydc)(cod)(CH 3 OH)], followed by olefin insertion. The formation of this hydrido intermediate results from the solvent-assisted proton transfer through a hydrogen-bonding network forming an eight-membered metallacycle. In contrast, reaction of [Ir(µ-OMe)(cod)] 2 with iminodiacetic acid derivatives, RN(CH 2 COOH) 2 , gave the stable iridium(I) mononuclear [Ir{κ 2-MeN(CH 2 COOH)(CH 2 COO)}(cod)] (R = Me) complex having a free carboxymethyl group, and the tetranuclear complex [Ir 4 {κ 4-PhN(CH 2 COO) 2 } 2 (cod) 4 ] (R = Ph) with doubly deprotonated ligands. The molecular structure of the related cyclooctene complex [Ir 4 {κ 4-PhN(CH 2 COO) 2 } 2 (coe) 8 ] has been determined by X-ray analysis. Reaction of 1 with monodentate N-and P-donor ligands gave the compounds [Ir(κ 3pydc)(1-κ-4,5-η-C 8 H 13)(L)] (L = py, BnNH 2 , PPh 3 and PMe 3). Reaction of 1 with the shortbite bis(diphenylphosphino)methane (dppm) afforded the mononuclear 1-dppm, with an uncoordinated P-donor atom, or the dinuclear 1 2-dppm complex as a function of the molar ratio used. Similarly, the dinuclear complexes 1 2-dppe and 1 2-dppp have been prepared using 1,2-bis(diphenylphosphino)ethane (dppe) and 1,3-bis(diphenylphosphino)propane (dppp) as bridging ligands. The diphosphine-bridged dinuclear assemblies have been obtained as two diastereoisomers in a 1:1 ratio due to the chirality of the mononuclear building block. The single crystal X-ray structures of 1-py and 1-dppm are reported.

show abstract

“…These 1 H and 31 P{ 1 H} NMR spectra show that two phosphine ligands of complex 5 are located in mutually cis position and by the P-H(hydride) coupling constants ( 2 J P1H = 16. (4) Ir (1) 20.2 Hz) of 1 H NMR measurement, hydride and two phosphine ligands are located in mutually cis position [18].…”

Section: Reaction Of Complex 2 With Acetic Acidmentioning

confidence: 99%