H/D exchange reactions of an iridium dithiol complex

Journal Article · Wed May 26 04:00:00 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), Journal Name: Inorganic Chemistry; (United States) Vol. 32:11; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

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