H/D exchange reactions of an iridium dithiol complex

Journal Article · Wed May 26 00:00:00 EDT 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00063a006· OSTI ID:5784319

Jessop, P G; Morris, R H ^[1]

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1. Univ. of Toronto, Ontario (Canada)

The complex [Ir(H)[sub 2](HS(CH[sub 2])[sub 3]SH)(PCy[sub 3])[sub 2]]BF[sub 4] (1) which contains an unprecedented chelating dithiol ligand was prepared by the action of 1,3-propanedithiol and HBF[sub 4][center dot]Et[sub 2]O on IrH[sub 5](PCy[sub 3])[sub 2]. The acidic thiol protons of 1 (pK[sub a][approx]9) exchange much more rapidly than the hydride ligands with deuterium from MeOD. This allows a unique opportunity to measure by [sup 1]H NMR the rate constant for intramolecular H/D transfer, [Ir(H)(DSR)][sup +][r reversible] [Ir(D)(HSR)][sup +], a process which likely proceeds via an unobserved [Ir([eta][sup 2]-HD)(SR)][sup +] complex. The reaction of 1 with D[sub 2] deuterates both the thiol and hydride hydrogens; this and the observation of similar stable dihydrogen complexes support the proposal of an [eta][sup 2]-HD intermediate.

• OSTI ID: 5784319
• Journal Information: Inorganic Chemistry; (United States), Vol. 32:11; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
IRIDIUM COMPLEXES
ISOTOPIC EXCHANGE
ABSORPTION SPECTROSCOPY
CHELATES
CHELATING AGENTS
CHEMICAL REACTION KINETICS
DEUTERIUM COMPOUNDS
HYDRIDES
NUCLEAR MAGNETIC RESONANCE
REACTION INTERMEDIATES
THIOLS
COMPLEXES
HYDROGEN COMPOUNDS
KINETICS
MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
REACTION KINETICS
RESONANCE
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
400202* - Isotope Effects
Isotope Exchange
& Isotope Separation