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Title: Synthesis and characterization of compounds containing discrete tetranuclear clusters and extended arrays of molybdenum atoms

Abstract

Improved synthetic pathways to the Mo/sub 4/Cl/sub 8/L/sub 4/ cluster compounds were elucidated which provide a facile entrance to the synthesis of new four metal atom clusters. The new tetranuclear clusters, with the stoichiometry R/sub 4/Mo/sub 4/Cl/sub 12/ (R = Et/sub 4/N, Pr/sub 4/N, O/sub 4/P), were prepared by the reaction of tealkylammonium or tetraphenylphosphonium chlorides with the rectangular tetrameric cluster Mo/sub 4/Cl/sub 8/L/sub 4/. One electron oxidation of Mo/sub 4/Cl/sub 12//sup 4 -/ by I/sub 2/ or dichlorophenyliodine yielded the Mo/sub 4/Cl/sub 12//sup 3 -/ cluster anion, which was shown to exist as two geometric isomers, both of which are fragments of the larger hexanuclear cluster anion Mo/sub 6/Cl/sub 14//sup 2 -/. The metal atoms in (Et/sub 4/N)/sub 3/Mo/sub 4/Cl/sub 12/ form an opened tetrahedron or butterfly. In (O/sub 4/P)/sub 3/Mo/sub 4/Cl/sub 12/, (Pr/sub 4/N)/sub 3/-Mo/sub 4/Cl/sub 12/, and (O/sub 4/As)/sub 2/(Et/sub 4/N)Mo/sub 4/Cl/sub 12/ the metal atoms form a planar rhomboidal cluster unit. Bond distances in both cluster units are indicative of strong metal-metal bonding. Magnetic susceptibility and electron paramagnetic resonance studies of (O/sub 4/P)/sub 3/Mo/sub 4/Cl/sub 12/ are consistent with the assignment of one unpaired electron, delocalized over the cluster unit. The ternary molybdenum oxide, Sn/sub 0.9/Mo/submore » 4/O/sub 6/, was synthesized by high temperature reactions in sealed molybdenum tubes. The structure of this compound is dominated by metal-metal bonded octahedral clusters which are fused on trans edges to form infinite chains through the lattice. Four such clusters are interconnected to form a tetragonal tunnel occupied by Sn. Resistivity studies show the compound is metallic. The compound exhibits weak, temperature independent paramagnetism.« less

Authors:
Publication Date:
Research Org.:
Iowa State Univ. of Science and Technology, Ames (USA)
OSTI Identifier:
5502090
DOE Contract Number:  
W-7405-ENG-82
Resource Type:
Thesis/Dissertation
Resource Relation:
Other Information: Thesis (Ph. D.)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ARSENIC OXIDES; SYNTHESIS; MOLYBDENUM COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; PHOSPHORUS OXIDES; PRASEODYMIUM NITRIDES; TIN OXIDES; CHEMICAL BONDS; ARSENIC COMPOUNDS; CHALCOGENIDES; NITRIDES; NITROGEN COMPOUNDS; ORGANIC COMPOUNDS; OXIDES; OXYGEN COMPOUNDS; PHOSPHORUS COMPOUNDS; PNICTIDES; PRASEODYMIUM COMPOUNDS; RARE EARTH COMPOUNDS; REFRACTORY METAL COMPOUNDS; TIN COMPOUNDS; TRANSITION ELEMENT COMPOUNDS; 400201* - Chemical & Physicochemical Properties; 400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)

Citation Formats

Aufdembrink, B A. Synthesis and characterization of compounds containing discrete tetranuclear clusters and extended arrays of molybdenum atoms. United States: N. p., 1985. Web.
Aufdembrink, B A. Synthesis and characterization of compounds containing discrete tetranuclear clusters and extended arrays of molybdenum atoms. United States.
Aufdembrink, B A. Tue . "Synthesis and characterization of compounds containing discrete tetranuclear clusters and extended arrays of molybdenum atoms". United States.
@article{osti_5502090,
title = {Synthesis and characterization of compounds containing discrete tetranuclear clusters and extended arrays of molybdenum atoms},
author = {Aufdembrink, B A},
abstractNote = {Improved synthetic pathways to the Mo/sub 4/Cl/sub 8/L/sub 4/ cluster compounds were elucidated which provide a facile entrance to the synthesis of new four metal atom clusters. The new tetranuclear clusters, with the stoichiometry R/sub 4/Mo/sub 4/Cl/sub 12/ (R = Et/sub 4/N, Pr/sub 4/N, O/sub 4/P), were prepared by the reaction of tealkylammonium or tetraphenylphosphonium chlorides with the rectangular tetrameric cluster Mo/sub 4/Cl/sub 8/L/sub 4/. One electron oxidation of Mo/sub 4/Cl/sub 12//sup 4 -/ by I/sub 2/ or dichlorophenyliodine yielded the Mo/sub 4/Cl/sub 12//sup 3 -/ cluster anion, which was shown to exist as two geometric isomers, both of which are fragments of the larger hexanuclear cluster anion Mo/sub 6/Cl/sub 14//sup 2 -/. The metal atoms in (Et/sub 4/N)/sub 3/Mo/sub 4/Cl/sub 12/ form an opened tetrahedron or butterfly. In (O/sub 4/P)/sub 3/Mo/sub 4/Cl/sub 12/, (Pr/sub 4/N)/sub 3/-Mo/sub 4/Cl/sub 12/, and (O/sub 4/As)/sub 2/(Et/sub 4/N)Mo/sub 4/Cl/sub 12/ the metal atoms form a planar rhomboidal cluster unit. Bond distances in both cluster units are indicative of strong metal-metal bonding. Magnetic susceptibility and electron paramagnetic resonance studies of (O/sub 4/P)/sub 3/Mo/sub 4/Cl/sub 12/ are consistent with the assignment of one unpaired electron, delocalized over the cluster unit. The ternary molybdenum oxide, Sn/sub 0.9/Mo/sub 4/O/sub 6/, was synthesized by high temperature reactions in sealed molybdenum tubes. The structure of this compound is dominated by metal-metal bonded octahedral clusters which are fused on trans edges to form infinite chains through the lattice. Four such clusters are interconnected to form a tetragonal tunnel occupied by Sn. Resistivity studies show the compound is metallic. The compound exhibits weak, temperature independent paramagnetism.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {1985},
month = {1}
}

Thesis/Dissertation:
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