Synthesis and characterization of heterometallic carbonyl clusters containing ruthenium and a highly coordinated oxo, acetamidato, or sulfido ligand

Thesis/Dissertation · Wed Jan 01 04:00:00 EST 1992

OSTI ID:5517742

Voss, E J

This thesis describes investigations of carbonyl clusters containing a highly coordinated oxo, acetamidato, or sulfido ligand supported on a low oxidation mixed-metal framework. These heterometallic complexes contain a triangle of ruthenium atoms and result from the reaction of an electron rich three-metal oxo or sulfido cluster with a lightly stabilized electrophilic cluster building reagent. Chapter One details the formation of the five-metal oxo cluster [Fe[sub 2]Ru[sub 3](CO)[sub 14]([mu][sub 4]-O)][sup 2[minus]] from reaction of the oxo cluster [Fe[sub 3](CO)[sub 9]([mu][sub 3]-O)][sup 2[minus]] with Ru[sub 3](CO)[sub 10](NCCH[sub 3])[sub 2]. The attempted synthesis of the ruthenium oxo cluster [Ru[sub 3](CO)[sub 9]([mu][sub 3]-O)][sup 2[minus]] is presented in Chapter Two. This cluster was not isolated, but evidence of its existence is shown by its reaction with the lightly stabilized manganese and rhenium reagents [M(CO)[sub 3](NCCH[sub 3])[sub 3]][sup +] (M = Mn or Re). The resulting butterfly clusters [MRu[sub 3](CO)[sub 12]([eta][sup 2]-[mu][sub 3]-NC([mu]-O)CH[sub 3])][sup [minus]] (M = Mn or Re), contain a bridging acetamidato ligand, which appears to form from the [mu][sub 3]-O of the ruthenium cluster and an acetonitrile ligand from the metal center. The chemistry of the ruthenium sulfido cluster [Ru[sub 3](CO)[sub 9]([mu][sub 3]-S)][sup 2[minus]] is described in Chapter Three. The single crystal X-ray structure determination of the protonated butterfly oxo cluster HFe[sub 3]Mn(CO)[sub 10](dmpm)([mu][sub 4]-O) is presented in the Appendix. The structure of this molecule is compared to the parent cluster [Fe[sub 3]Mn(CO)[sub 12]([mu][sub 4]O)][sup [minus]] from which it is derived. The new species described were characterized by infrared, [sup 1]H, [sup 13]C and [sup 17]O nuclear magnetic resonance spectroscopy, fast atom bombardment mass spectrometry, and single crystal X-ray structure determinations.

• Research Organization: Northeastern Univ., Boston, MA (United States)
• OSTI ID: 5517742
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400100 -- Analytical & Separations Chemistry
400200* -- Inorganic
Organic
& Physical Chemistry
CARBONYL RADICALS
CHEMICAL PREPARATION
CHEMICAL REACTION YIELD
COHERENT SCATTERING
COORDINATION VALENCES
CRYSTAL STRUCTURE
DIFFRACTION
ELEMENTS
LIGANDS
MAGNETIC RESONANCE
MANGANESE
MASS SPECTRA
METALS
NUCLEAR MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
RADICALS
REFRACTORY METAL COMPOUNDS
RESONANCE
RHENIUM
RUTHENIUM COMPOUNDS
SCATTERING
SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
TRANSITION ELEMENTS
VALENCE
X-RAY DIFFRACTION
YIELDS