Synthesis and structural characterization of mono-, di- and trinuclear complexes of tungsten
Three new WOX[sub 2]L[sub 3] type complexes containing W(IV) with X = Br and L = PMe[sub 2]Ph or PMePh[sub 2] ligand are reported. All complexes have been spectroscopically and structurally characterized. Full details of structure and bonding, and spectroscopic properties of these complexes are given. New, simpler, and more straightforward synthetic routes for the preparation of the chloro- and bromo-bridged dinuclear W(III) face-sharing and edge-sharing complexes have been described. The structural characterizations of W[sub 2]Cl[sub 6](PMe[sub 2]Ph)[sub 3], W[sub 2]Br[sub 6](PMe[sub 2]Ph)[sub 3], and W[sub 2]Cl[sub 6](PMe[sub 2]Ph)[sub 4] have been done by single crystal X-ray diffraction methods. Structure and bonding as well as the spectroscopic properties of these complexes are discussed. A new type of synthetic entry to the W[sub 3]S[sub 4][sup 4+] core (where W is in oxidation state IV) from mononuclear tungsten halides in a higher oxidation state has been developed by using two different reducing agents. The following trinuclear clusters have been structurally characterized by X-ray diffraction studies: [W[sub 3]S[sub 4]Br[sub 3](dmpe)[sub 3]]Br, [W[sub 3]S[sub 4]Br[sub 3](dmpe)[sub 3]]PF[sub 6], [W[sub 3]S[sub 4]Br[sub 3](depe)[sub 3]]Br[center dot]2CH[sub 3]OH, [W[sub 3]S[sub 4]Br[sub 3](depe)[sub 3]]PF[sub 6][center dot]0.5C[sub 7]H[sub 8]. Ligand substitution reaction on the W[sub 3]S[sub 4][sup 4+] core has yielded the first organometallic trinuclear cluster of tungsten, [W[sub 3]S[sub 4](CH[sub 3])[sub 3](dmpe)[sub 3]]PF[sub 6]. The synthesis of the first complex, [W[sub 3]Se[sub 4]Br[sub 3](dmpe)[sub 3]]Br, containing the W[sub 3]Se[sub 4][sup 4+] core has been described. Full details of the syntheses, structural characterizations, and properties of these trinuclear clusters are given. Comparative studies with other such compounds reported in the literature have been presented to illustrate their similar structural features and chemical properties.
- Research Organization:
- Texas A and M Univ., College Station, TX (United States)
- OSTI ID:
- 5652313
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
360602* -- Other Materials-- Structure & Phase Studies
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
BROMIDES
BROMINE COMPOUNDS
CHEMICAL PREPARATION
CHEMICAL PROPERTIES
CHLORIDES
CHLORINE COMPOUNDS
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DIFFRACTION
HALIDES
HALOGEN COMPOUNDS
REFRACTORY METAL COMPOUNDS
SCATTERING
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
TUNGSTEN BROMIDES
TUNGSTEN CHLORIDES
TUNGSTEN COMPLEXES
TUNGSTEN COMPOUNDS
X-RAY DIFFRACTION