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 00:00:00 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), Vol. 32:18; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

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