Synthesis and solution structure of heterobimetallic rhenium-iridium polyhydride complexes

Journal Article · Wed May 12 00:00:00 EDT 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00062a040· OSTI ID:6298599

Michos, D; Luo, Xiaoliang; Crabtree, R H ^[1]

---

1. Yale Univ., New Haven, CT (United States)

The reaction of [IrH[sub 2](Me[sub 2]CO)[sub 2](PPh[sub 3])[sub 2]]SbF[sub 6] with ReH[sub 7](PPh[sub 3])[sub 2] or ReH[sub 7](dppf) (dppf = 1,1[prime]-bis(diphenylphosphino)ferrocene) is extremely rapid and leads to the quantitative formation of the heterobimetallic polyhydride complexes [L[sub 2]H[sub 3]Re([mu]-H)[sub 3]IrH(PPh[sub 3])[sub 2]]SbF[sub 6] (L = PPh[sub 3] (1), 1/2 dppf (2)), which have been characterized by IR and variable-temperature [sup 1]H and [sup 31]P NMR spectroscopy. The spectroscopic data for compounds 1 and 2 suggest that they contain three bridging and four terminal hydride ligands. The coordination polyhedron about rhenium is a dodecahedron, and that about iridium is an octahedron; the two polyhedra are fused by sharing a face containing the three bridging hydride ligands, which is an equilateral (E) triangular face of the dodecahedron and a triangular face of the octahedron. Compounds 1 and 2 are most likely formed by a formal dinuclear H[sub 2] elimination mechanism, which involves initial displacement of the labile acetone ligands from [IrH[sub 2](Me[sub 2]CO)[sub 2](PPh[sub 3])[sub 2]]SbF[sub 6] by the hydride ligands of ReH[sub 7]L[sub 2] to give a transient hydride-bridged dinuclear [eta][sup 2]-H[sub 2] species which subsequently undergoes facile H[sub 2] elimination. The geometric factors favoring or disfavoring M([mu]-H)[sub n]M[prime] (n = 3--5) bridging systems are discussed.

• OSTI ID: 6298599
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 32:10; 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
ABSORPTION SPECTROSCOPY
ANTIMONY COMPOUNDS
ANTIMONY FLUORIDES
CHEMICAL PREPARATION
COMPLEXES
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
HYDRIDES
HYDROGEN COMPOUNDS
IRIDIUM COMPLEXES
IRIDIUM COMPOUNDS
IRIDIUM HYDRIDES
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
MOLECULAR STRUCTURE
NUCLEAR MAGNETIC RESONANCE
NUCLEI
ODD-EVEN NUCLEI
PHOSPHINES
PHOSPHORUS 31
PHOSPHORUS COMPOUNDS
PHOSPHORUS ISOTOPES
REFRACTORY METAL COMPOUNDS
RESONANCE
RHENIUM COMPLEXES
RHENIUM COMPOUNDS
RHENIUM HYDRIDES
SPECTROSCOPY
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS