Synthesis and crystal structure of (PPh sub 4 ) sub 2 (Ir sub 4 (CO) sub 10 (CH sub 2 COOMe) sub 2 ) and (PPh sub 4 )(Ir sub 4 (CO) sub 11 (CH sub 2 COOMe)). First examples of iridium clusters bearing an alkyl-like ligand
- Dipt. di Chimica Inorganica e Metallorganica and CNR Center, Milano (Italy)
- Ist. di Chimica Strutturistica Inorganica and CNR Center, Milano (Italy)
The reaction of Na(Ir(CO){sub 4}) ((Na)1) with given amounts of BrCH{sub 2}COOMe in THF, followed by treatment with PPh{sub 4}Cl, gave high yields of the two novel clusters (PPh{sub 4}){sub 2}(Ir{sub 4}(CO){sub 10}(CH{sub 2}COOOMe){sub 2}) ((PPh{sub 4}){sub 2}2) and (PPh{sub 4})(Ir(CO){sub 11}(CH{sub 2}COOMe)) ((PPh{sub 4})3). The reaction takes place in two steps; the first compound formed is 2, which then reacts, in a slower reaction, with excess BrCH{sub 2}COOMe to afford 3. To the best of the authors' knowledge, 2 and 3 are among the first examples of clusters bearing an alkyl or alkyl-like substitutent. X-ray diffraction analysis of the clusters was carried out on crystals obtained by using PPh{sub 4}{sup +} as a countercation. Compound (PPh{sub 4}){sub 2}2 is triclinic. Both anions contain a tetrahedron of iridium atoms with three bridging CO ligands around a triangular basal face of the metal tetrahedron of iridium atoms with three bridging CO ligands around a triangular basal face of the metal tetrahedron, the alkyl-like substituents being axially bonded to the iridium atoms of this face. The reactivity of the sodium salt of (Ir(CO){sub 4}){sup {minus}} with BrCH{sub 2}COOMe was quite different from that, already reported by the authors, of the same anion with PPN{sup +} (PPN{sup +} = (PPh{sub 3}){sub 2}N{sup +}) as a countercation. This latter reaction forms only mononuclear species. The possible role of Na{sup +} in the formation of the clusters is discussed.
- OSTI ID:
- 6070188
- Journal Information:
- Organometallics; (United States), Vol. 10:1; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
IRIDIUM COMPLEXES
CHEMICAL PREPARATION
CRYSTAL STRUCTURE
BOND ANGLE
BOND LENGTHS
CARBONYLS
LIGANDS
ORGANIC PHOSPHORUS COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOSPHORUS NITRIDES
REAGENTS
X-RAY DIFFRACTION
COHERENT SCATTERING
COMPLEXES
DIFFRACTION
DIMENSIONS
LENGTH
NITRIDES
NITROGEN COMPOUNDS
ORGANIC COMPOUNDS
PHOSPHORUS COMPOUNDS
PNICTIDES
SCATTERING
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties