Influence of halide ligands on the energetics of the reversible loss of hydrogen from the Iridium nonclassical polyhydride complexes IrXH[sub 2](H[sub 2])(PPr[sup i][sub 3])[sub 2] (X = Cl, Br, I)

Journal Article · Wed Sep 01 04:00:00 EDT 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00070a002· OSTI ID:7071579

Le-Husebo, T; Jensen, C M ^[1]

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1. Univ. of Hawaii, Honolulu (United States)

Recently there has been a great deal of interest in nonclassical polyhydride complexes. Early studies of these complexes were primarily concerned with the determination of the dihydrogen versus hydride character of the metal-bound hydrogen. More recent studies have focused on the influence of the ligand environmental on the metal-dihydrogen interaction. Crabtree and Kubas have shown that the activation of dihydrogen ligands increase with increasing basicity of ancillary phosphine ligands. The authors have demonstrated a threshold to the steric sensitivity of the energetics of the reversible binding of H[sub 2] by the complexes IrClH[sub 2](PR[sub 3])[sub 2](R = Pr[sup i] (1a), Cy (1b), Bu[sup t] (1c)). These results also suggest that the presence of the chloride ligand in 1a is responsible for the arrested activation of dihydrogen in IrClH[sub 2](H[sub 2])(PPr[sup i][sub 3])[sub 2] (2) relative to IrH[sub 5](PPr[sup i][sub 3])[sub 2](X = Br (3), I (4)) and compared their hydrogen binding behavior to that previously observed for IrClH[sub 2](PPr[sup i][sub 3])[sub 2] (1a).

• OSTI ID: 7071579
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 32:18; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CHEMICAL PREPARATION
CHEMICAL REACTIONS
ELEMENTS
HALOGEN COMPOUNDS
HYDRIDES
HYDROGEN
HYDROGEN COMPOUNDS
IRIDIUM COMPOUNDS
IRIDIUM HYDRIDES
LIGANDS
NONMETALS
PHOSPHINES
PHOSPHORUS COMPOUNDS
REFRACTORY METAL COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS