Synthesis and charaterisation of mixed s-/p-block organometallics and p-block ligand systems
Synthesis and charaterisation of mixed s-/p-block organometallics and p-block ligand systems
The reactivities of the polynuclear group 15 dimethylamido derivatives (Me2N)2Sb(CH2)3Sb(NMe2)2 and (Me2N)2AsCH2 AS(NMe2)2 towards a host of metallo-inorganic fragments has been investigated. Following these investigations it has been possible to synthesise and structurally characterise a number of novel stibine and arsine complexes.
Compound 4a 1,3-(RNLi)Sb]2(μ-NR)(CH2)3(RNHLi).(3THF)] contains the first example of an anionic antimony(III) complex built upon a polynuclear framework. Its core consists of a number of interlocking six-membered rings which contribute to its inherent stability. Subsequent reaction of this anionic complex with copper(I) chloride has yielded the dimeric complex [2-PyNCu]2 4b.
The macrocycle cyclo[(3-Me-1,2-C6H3O2)2SbNa(THF2]6 4c has been isolated and structurally characterised. Its toroidal core comprises of a Sb6O24Na6 metallacycle where the anionic antimony(III) fragments are linked via double oxy-bridges to sodium cations forming the cyclic structure and is the first example of a twenty-four-membered mixed s- / p-block macrocycle.
For the first time it has been possible to structurally characterise an imido antimony(III) complex based on an adamantyl core. Compound 4b contains a Sb4N6 core with the doubly deprotonated imidonaphthyl groups bridging the antimony centres.
Compound 5a [C6H4N2AsLi(THF)2]«problem!» is a two-dimensional coordination polymer and represents the first example of a complex containing a diazaarsolyl anionic fragment. These planar, delocalised aromatic AsN2C2 metallacycles are bridged via lithium cations.
Two further polymeric compounds {[C7H6ON(H)]2AsNa(THF)2}∞ 5b and {[C6H4ON(H)2AsNA(THF)3}«problem!» 5c have also been generated. These complexes contain mixed arsenic(III) / sodium cores consisting of AsR2 units bridged via sodium cations.
The syntheses and structural characterisations of organo-functionalised group 15 compounds has also been investigated. Several potential chelating Lewis base ligands based on polynuclear stibine or arsine cores have been characterised. These compounds [(2-PyS)2As]2CH2 6a, [(Me3SiC≡C)2As]2 6b [(Me3Si)2N)2As]2 CH26c, (C7H6O2As)2CH2 6d and [(PhC≡C-)2Sb]2 (CH2)3 6g all possess potentially reactive functional groups in addition to their Lewis base metal donors.
Its has also been possible to synthesise the structurally characterise the non-bridged organo-functionalised compounds As(C≡CPh)3 6e and [(C7H6O2)As(OC7H6OH) 6f via the cleavage of the polynuclear precursor.
All of these novel polyfunctional group 15 compounds should provide excellent addition to the library of Lewis base ligands currently employed by coordination chemists.
University of Southampton
2003
Joy, Jonathan Stuart
(2003)
Synthesis and charaterisation of mixed s-/p-block organometallics and p-block ligand systems.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
The reactivities of the polynuclear group 15 dimethylamido derivatives (Me2N)2Sb(CH2)3Sb(NMe2)2 and (Me2N)2AsCH2 AS(NMe2)2 towards a host of metallo-inorganic fragments has been investigated. Following these investigations it has been possible to synthesise and structurally characterise a number of novel stibine and arsine complexes.
Compound 4a 1,3-(RNLi)Sb]2(μ-NR)(CH2)3(RNHLi).(3THF)] contains the first example of an anionic antimony(III) complex built upon a polynuclear framework. Its core consists of a number of interlocking six-membered rings which contribute to its inherent stability. Subsequent reaction of this anionic complex with copper(I) chloride has yielded the dimeric complex [2-PyNCu]2 4b.
The macrocycle cyclo[(3-Me-1,2-C6H3O2)2SbNa(THF2]6 4c has been isolated and structurally characterised. Its toroidal core comprises of a Sb6O24Na6 metallacycle where the anionic antimony(III) fragments are linked via double oxy-bridges to sodium cations forming the cyclic structure and is the first example of a twenty-four-membered mixed s- / p-block macrocycle.
For the first time it has been possible to structurally characterise an imido antimony(III) complex based on an adamantyl core. Compound 4b contains a Sb4N6 core with the doubly deprotonated imidonaphthyl groups bridging the antimony centres.
Compound 5a [C6H4N2AsLi(THF)2]«problem!» is a two-dimensional coordination polymer and represents the first example of a complex containing a diazaarsolyl anionic fragment. These planar, delocalised aromatic AsN2C2 metallacycles are bridged via lithium cations.
Two further polymeric compounds {[C7H6ON(H)]2AsNa(THF)2}∞ 5b and {[C6H4ON(H)2AsNA(THF)3}«problem!» 5c have also been generated. These complexes contain mixed arsenic(III) / sodium cores consisting of AsR2 units bridged via sodium cations.
The syntheses and structural characterisations of organo-functionalised group 15 compounds has also been investigated. Several potential chelating Lewis base ligands based on polynuclear stibine or arsine cores have been characterised. These compounds [(2-PyS)2As]2CH2 6a, [(Me3SiC≡C)2As]2 6b [(Me3Si)2N)2As]2 CH26c, (C7H6O2As)2CH2 6d and [(PhC≡C-)2Sb]2 (CH2)3 6g all possess potentially reactive functional groups in addition to their Lewis base metal donors.
Its has also been possible to synthesise the structurally characterise the non-bridged organo-functionalised compounds As(C≡CPh)3 6e and [(C7H6O2)As(OC7H6OH) 6f via the cleavage of the polynuclear precursor.
All of these novel polyfunctional group 15 compounds should provide excellent addition to the library of Lewis base ligands currently employed by coordination chemists.
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Published date: 2003
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Local EPrints ID: 465245
URI: http://eprints.soton.ac.uk/id/eprint/465245
PURE UUID: 447869c2-7c4e-4155-8784-d036751cb9cf
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Date deposited: 05 Jul 2022 00:31
Last modified: 05 Jul 2022 00:31
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Author:
Jonathan Stuart Joy
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