Coordinative Dimerization of Aminosilanes. Model MNDO and Ab Initio Molecular Orbital Calculations

The possibility of formation of cyclodisilazanes by the coordinative dimerization of aminosilanes has been investigated by MNDO and ab initio (3–21G(*)) methods. It has been shown that this process is mainly controlled by the silicon centers through their charges and acceptor orbitals. One chlorine (Br,I) at silicon makes available a low energy acceptor orbital which afford a reasonable low barrier to dimerization. One fluorine at silicon raises the energy of the proper symmetry acceptor orbital to such a level that no dimerization can be detected by MNDO. More fluorine substituents enhance the electrostatic attractive interactions which coupled with some lowered acceptor orbitals make feasible the formation of 2,2,2,4,4,4 hexafluorodisilazanes.

[1]  Warren J. Hehre,et al.  Practical strategies for electronic structure calculations , 1995 .

[2]  P. Power,et al.  Silylamines with Pyramidal Coordination at Nitrogen , 1993 .

[3]  I. Haiduc.  A Graph-Based Classification and Enumeration of Inorganic Homo- And Heterocycles , 1992 .

[4]  P. Ho,et al.  Theoretical study of the thermochemistry of molecules in the silicon-nitrogen-hydrogen-fluorine system , 1991 .

[5]  R. R. Holmes,et al.  Fluorine and chlorine apicophilicities in five-coordinated phosphorus and silicon compounds via molecular orbital calculations. A model for nucleophilic substitution , 1988 .

[6]  G. V. Gibbs,et al.  Modeling the configuration about the nitrogen atom in methyl- and silyl-substituted amines , 1988 .

[7]  J. A. Armstrong,et al.  Preparations, properties, and vibrational spectra of some (dimethylamino)halogenosilanes , 1988 .

[8]  C. Wu.  A mass spectrometric study of mercury-photosensitized reactions of monosilane and ammonia mixtures: observation of silylated amines , 1987 .

[9]  Michael W. Schmidt,et al.  π Bond Strengths in the Second and Third Periods , 1987 .

[10]  A. J. Blake,et al.  Molecular structures of some (dimethylamino)halogenosilanes in the gas phase by electron diffraction and the crystal and molecular structures of mono- and di-chloro(dimethylamino)silane by X-ray diffraction at low temperatures , 1987 .

[11]  I. Haiduc,et al.  The Chemistry of inorganic homo- and heterocycles , 1987 .

[12]  D. Stalke,et al.  Cyclodisilazan‐Kationen – Synthese und Kristallstruktur , 1986 .

[13]  M. Gordon.  The molecular structure of silylamine , 1986 .

[14]  Eamonn F. Healy,et al.  Revised MNDO Parameters for Silicon , 1986 .

[15]  J. Chandrasekhar,et al.  A theoretical survey of unsaturated or multiply bonded and divalent silicon compounds. Comparison with carbon analogs , 1986 .

[16]  M. Voronkov,et al.  Quantum-chemical analysis of silicon atom pentacoordination , 1985 .

[17]  D. Rankin,et al.  Determination of the molecular structure of dimethyl (silyl) amine, dimethyl (methylsilyl) amine and dimethyl (dimethylsilyl) amine in the gas phase by electron diffraction , 1984 .

[18]  M. Mckee,et al.  Photoelectron spectroscopic and theoretical study of tris(trimethylsilyl)amine and related silylamines. Real and hypothetical planar tertiary amines , 1983 .

[19]  C. Thomson,et al.  The structure and acid–base properties of methyl and silyl amines and phosphines: An ab‐initio SCF study , 1982 .

[20]  W. Wolfsberger.  N-Bromdimethylsilyl- und N-ioddimethylsilyl-triorganophosphinimine , 1979 .

[21]  Sin‐Shong Lin.  Mass Spectrometric Detection of Intermediates in Chemical Vapor Deposition of Si3 N 4 , 1977 .

[22]  Walter Thiel,et al.  Ground States of Molecules. 38. The MNDO Method. Approximations and Parameters , 1977 .

[23]  W. Sheldrick,et al.  Crystal and Molecular Structure of N-(Trifluorosilyl)trimethylphosphinimine Dimer , 1977 .

[24]  R. Cavell,et al.  Apicophilicity of substituent groups and the structures of some trigonal bipyramidal trifluoromethylphosphoranes , 1974 .

[25]  G. Sheldrick,et al.  An electron diffraction determination of the molecular structures of trichloro- and trifluoro-silyl-dimethylamine , 1971 .

[26]  B. Munsch,et al.  Nitrogen inversion barrier and nature of the Si–N bond in silylamine: an ab initio SCF–LCAO–MO study , 1970 .