Syntheses of the seven-metal carbide cluster [PPN][sub 2][Os[sub 3]Ni[sub 4]C(CO)[sub 15]] and of [PPN][sub 2][Os[sub 3]Ni[sub 3]C(CO)[sub 13]]
- Northwestern Univ., Evanston, IL (United States)
Clusters containing Ni, Pd, and Pt often have fewer electrons for their geometries than predicted by traditional electron-counting rules such as the polyhedral skeletal electron pair theory (PSEPT). For example, [Pt[sub 3](CO)[sub 6]] has only 44 electrons, although PSEPT predicts that it should be a 48-electron cluster. Extended Hueckel calculations on the 48-electron cluster Fe[sub 3](CO)[sub 12] show that 9 predominantly s and p metal orbitals and 3 d orbitals interact with the 12 CO ligands to give 24 filled cluster orbitals. In [Pt[sub 3](CO)[sub 6]][sup 2[minus]] only 22 cluster orbitals are filled, because two high-lying e[double prime] orbitals do not interact with CO ligands to form bonding orbitals. Similarly, in heterometallic clusters, the replacement of an M(CO)[sub 3] fragment with an isolobal PtL[sub 2] fragment may result in a decrease in the number of electrons required for a closed-shell configuration, but many heterometallic Pt clusters, for example Pt[sub 2]Os[sub 4](CO)[sub 12](COD)[sub 2] (COD = 1,5-cyclooctadiene), obey traditional electron-counting rules such as PSEPT. The ketenylidene clusters [PPN][sub 2][M[sub 3](CO)[sub 9]CCO] react through redox condensation to form a variety of mixed-metal carbide clusters. The authors report here the redox condensation of [PPN][sub 2][Os[sub 3](CO)[sub 9]CCO] and Ni(CO)[sub 4] to form the seven-metal, 100-electron carbide cluster [PPN][sub 2][Os[sub 3]Ni[sub 4]C(CO)[sub 15]].
- DOE Contract Number:
- FG02-86ER13640
- OSTI ID:
- 7180853
- Journal Information:
- Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 31:12; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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Characteristic vibrational frequencies and normal modes of the CCO ligand in trinuclear ketenylidene clusters
Related Subjects
400201* -- Chemical & Physicochemical Properties
BOND ANGLE
BOND LENGTHS
CARBONYLS
CHEMICAL PREPARATION
COHERENT SCATTERING
COMPLEXES
DIFFRACTION
DIMENSIONS
ELECTRONIC STRUCTURE
LENGTH
MOLECULAR STRUCTURE
NICKEL COMPLEXES
NMR SPECTRA
OSMIUM COMPLEXES
SCATTERING
SPECTRA
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION