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Title: Synthesis and characterization of tetranuclear molybdenum(II) cluster derivatives

Abstract

A series of new tetranuclear molybdenum(II) nitrile cluster derivatives is reported. Improvements in the synthetic routes to these and other derivatives is also reported. The single crystal x-ray structure of Mo/sub 4/Cl/sub 12//sup 4/minus// is modeled. New tetrameric nitrile derivatives with the stoichiometry Mo/sub 4/Cl/sub 8/(RCN)/sub 4/ (R = Pr/sup n/, Pr/sup i/, Bu/sup t/, PhCH/sub 2/) have been isolated by ligand exchange from Mo/sub 4/Cl/sub 8/(EtCN)/sub 4/ and/or direct synthesis from Mo/sub 4/Cl/sub 8/(PBu/sup n/sub 3//)/sub 4/. Mo/sub 4/Cl/sub 8/(Pr/sup n/CN)/sub 4/ was synthesized with higher yields and with simpler reaction conditions than Mo/sub 4/Cl/sub 8/(EtCN)/sub 4/. Improved synthetic routes for R/sub 4/Mo/sub 4/Cl/sub 12/ (R = Et/sub 4/N, Pr/sub 4/N) have been developed. (Et/sub 4/N)/sub 4/Mo/sub 4/Cl/sub 12/ can be directly synthesized from the phosphine tetramer, circumventing the preparation of the reactive species-Mo/sub 4/Cl/sub 8/(EtCN)/sub 4/, which is the most difficult precursor to prepare. A change in reaction solvent, from dichloromethane or dichloroethane to chlorobenzene, in the preparation of (Pr/sub 4/N)/sub 4/Mo/sub 4/Cl/sub 12/ has permitted its isolation under less rigorous conditions and in high yield. A single crystal structure determination has been done on a sample of (Ph/sub 4/P)/sub 4/Mo/sub 4/Cl/sub 12/. Although, the quality of themore » data is poor, the structure of the Mo/sub 4/Cl/sub 12/ cluster core was refined. Four complex types have been found to fit the data. 22 refs., 12 figs., 7 tabs.« less

Authors:
Publication Date:
Research Org.:
Ames Lab., IA (USA)
OSTI Identifier:
6360955
Report Number(s):
IS-T-1331
ON: DE89007621
DOE Contract Number:  
W-7405-ENG-82
Resource Type:
Technical Report
Resource Relation:
Other Information: Thesis (M.S.). Portions of this document are illegible in microfiche products
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; MOLYBDENUM COMPOUNDS; SYNTHESIS; NITRILES; BOND ANGLE; CRYSTAL STRUCTURE; DERIVATIZATION; INFRARED SPECTRA; INTERATOMIC DISTANCES; LATTICE PARAMETERS; LIGANDS; MOLECULAR STRUCTURE; MOLYBDENUM CHLORIDES; PHOSPHINES; CHEMICAL REACTIONS; CHLORIDES; CHLORINE COMPOUNDS; DISTANCE; HALIDES; HALOGEN COMPOUNDS; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; PHOSPHORUS COMPOUNDS; REFRACTORY METAL COMPOUNDS; SPECTRA; TRANSITION ELEMENT COMPOUNDS; 360602* - Other Materials- Structure & Phase Studies; 360601 - Other Materials- Preparation & Manufacture; 400201 - Chemical & Physicochemical Properties

Citation Formats

Vogel, E A.F. Synthesis and characterization of tetranuclear molybdenum(II) cluster derivatives. United States: N. p., 1987. Web.
Vogel, E A.F. Synthesis and characterization of tetranuclear molybdenum(II) cluster derivatives. United States.
Vogel, E A.F. Sun . "Synthesis and characterization of tetranuclear molybdenum(II) cluster derivatives". United States.
@article{osti_6360955,
title = {Synthesis and characterization of tetranuclear molybdenum(II) cluster derivatives},
author = {Vogel, E A.F.},
abstractNote = {A series of new tetranuclear molybdenum(II) nitrile cluster derivatives is reported. Improvements in the synthetic routes to these and other derivatives is also reported. The single crystal x-ray structure of Mo/sub 4/Cl/sub 12//sup 4/minus// is modeled. New tetrameric nitrile derivatives with the stoichiometry Mo/sub 4/Cl/sub 8/(RCN)/sub 4/ (R = Pr/sup n/, Pr/sup i/, Bu/sup t/, PhCH/sub 2/) have been isolated by ligand exchange from Mo/sub 4/Cl/sub 8/(EtCN)/sub 4/ and/or direct synthesis from Mo/sub 4/Cl/sub 8/(PBu/sup n/sub 3//)/sub 4/. Mo/sub 4/Cl/sub 8/(Pr/sup n/CN)/sub 4/ was synthesized with higher yields and with simpler reaction conditions than Mo/sub 4/Cl/sub 8/(EtCN)/sub 4/. Improved synthetic routes for R/sub 4/Mo/sub 4/Cl/sub 12/ (R = Et/sub 4/N, Pr/sub 4/N) have been developed. (Et/sub 4/N)/sub 4/Mo/sub 4/Cl/sub 12/ can be directly synthesized from the phosphine tetramer, circumventing the preparation of the reactive species-Mo/sub 4/Cl/sub 8/(EtCN)/sub 4/, which is the most difficult precursor to prepare. A change in reaction solvent, from dichloromethane or dichloroethane to chlorobenzene, in the preparation of (Pr/sub 4/N)/sub 4/Mo/sub 4/Cl/sub 12/ has permitted its isolation under less rigorous conditions and in high yield. A single crystal structure determination has been done on a sample of (Ph/sub 4/P)/sub 4/Mo/sub 4/Cl/sub 12/. Although, the quality of the data is poor, the structure of the Mo/sub 4/Cl/sub 12/ cluster core was refined. Four complex types have been found to fit the data. 22 refs., 12 figs., 7 tabs.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {1987},
month = {11}
}

Technical Report:
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