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Complexes of Group III metal salts and titanium halides with tertiary pnictogen oxide and crown ether ligands

Complexes of Group III metal salts and titanium halides with tertiary pnictogen oxide and crown ether ligands
Complexes of Group III metal salts and titanium halides with tertiary pnictogen oxide and crown ether ligands

The compounds [Y(R3PO)2(EtOH)(NO3)3] (R3 = Ph3 or Ph2Me), [Y(Me3PO)2(H2O)(NO3)3], [Y(R3PO)3(NO3)3] (R3 = Ph3, Ph2Me or Me3) and [Y(Ph3PO)4(NO3)2]NO3 were prepared by reaction of R3PO with Y(NO3)3,6H2O in EtOH.  Similar reactions with Sc(NO3)3.5H2O gave [Sc(Ph3PO)2(NO3)3], [Sc(Ph2MePO)3(NO3)3], [Sc(Ph2MePO)4(NO3)2]NO3, [Sc(Me3PO)2(EtOH)(NO3)3] and [Sc(Me3PO)6][NO3].  Crystal structures of [Sc(Ph3PO)2(NO3)3], [Sc(EtOH)(NO3)3] are reported.  Similar reactions of R3AsO (R = Ph or Me) with M(NO3)3.nH2O (M = La, Sc or Y) in Me2CO yielded the complexes [Sc(Ph3AsO)2(NO3)3], [Y(Ph3AsO)4(NO3)2]NO3, [La(Ph3AsO)4(NO3)2]NO3 and [La(Me3AsO)6](NO3)3.  From ethanolic solution, [Sc(Ph3AsO)3(NO3)2]NO3.  [M(Ph3AsO)2(EtOH)(NO3)3] (M = La or Y) and [M(Me3AsO)6] (NO3)3 (M = Y or Sc) were isolated.  X-ray structures are reported for [M(Me3AsO)6](NO3)3 (M = Sc or Y), [Sc(Ph3AsO)3(NO3)2]NO3, [M(Ph3AsO)4(NO3)2]NO3 (M = Y or La) and [La(Ph3AsO)2(EtOH)(NO3)3.  Reactions of YX3.nH2O (X = Cl, Br or I) with the above ligands were carried out in EtOH or Me2CO solution.  Complexes isolated include [YX2(Ph3PO)4]Z (X = Cl, Br or I, Z = X or PF6), [YX3(Ph2MePO)3], [YCl2(Ph2MePO)4]PF6, [YCl(Ph3PO)5][SbCl6]2, [Y(Me3PO)6]X3, [YX2(Ph3AsO)4X, and [Y(Me3AsO)6]Cl3.  In addition, the X-ray crystal structures of [YCl2(Ph3PO)4[CI.2.5EtOH.H2O, [YBr2(Ph3PO)4] PF6.ET2O and [Y(Me3PO)6Br3 are reported.  No reaction was observed between YF3.1/2H2O and the same set of ligands.  Studies examining complexes of ScX3.nH2O (X = Cl, Br or I) with the same ligand were carried out.  Compounds isolated include [ScX2(Ph3PO)4]X, [ScX2(Ph3AsO)4]X, [ScCl(Me3PO)5]Cl2, [Sc(Me3PO)6]Z3 (Z = Br or I) and [Sc(Me3AsO)6]X3.  X-ray crystal structures of [ScBr2(Ph3PO)4Br, [ScCl2(Ph3AsO)4]Cl and [Sc(Me3ASO)6]Br3 are reported.  All of the above complexes were characterised using a combination of analysis, conductance measurements, IR and 1H NMR spectroscopy.  Solution speciation was established by variable temperature 31P-{1H} and either 89Y or 45Sc NMR spectroscopy.

University of Southampton
Popham, Michael Charles
dca0c74d-1862-4edb-889e-8dc0f6378c21
Popham, Michael Charles
dca0c74d-1862-4edb-889e-8dc0f6378c21

Popham, Michael Charles (2003) Complexes of Group III metal salts and titanium halides with tertiary pnictogen oxide and crown ether ligands. University of Southampton, Doctoral Thesis.

Record type: Thesis (Doctoral)

Abstract

The compounds [Y(R3PO)2(EtOH)(NO3)3] (R3 = Ph3 or Ph2Me), [Y(Me3PO)2(H2O)(NO3)3], [Y(R3PO)3(NO3)3] (R3 = Ph3, Ph2Me or Me3) and [Y(Ph3PO)4(NO3)2]NO3 were prepared by reaction of R3PO with Y(NO3)3,6H2O in EtOH.  Similar reactions with Sc(NO3)3.5H2O gave [Sc(Ph3PO)2(NO3)3], [Sc(Ph2MePO)3(NO3)3], [Sc(Ph2MePO)4(NO3)2]NO3, [Sc(Me3PO)2(EtOH)(NO3)3] and [Sc(Me3PO)6][NO3].  Crystal structures of [Sc(Ph3PO)2(NO3)3], [Sc(EtOH)(NO3)3] are reported.  Similar reactions of R3AsO (R = Ph or Me) with M(NO3)3.nH2O (M = La, Sc or Y) in Me2CO yielded the complexes [Sc(Ph3AsO)2(NO3)3], [Y(Ph3AsO)4(NO3)2]NO3, [La(Ph3AsO)4(NO3)2]NO3 and [La(Me3AsO)6](NO3)3.  From ethanolic solution, [Sc(Ph3AsO)3(NO3)2]NO3.  [M(Ph3AsO)2(EtOH)(NO3)3] (M = La or Y) and [M(Me3AsO)6] (NO3)3 (M = Y or Sc) were isolated.  X-ray structures are reported for [M(Me3AsO)6](NO3)3 (M = Sc or Y), [Sc(Ph3AsO)3(NO3)2]NO3, [M(Ph3AsO)4(NO3)2]NO3 (M = Y or La) and [La(Ph3AsO)2(EtOH)(NO3)3.  Reactions of YX3.nH2O (X = Cl, Br or I) with the above ligands were carried out in EtOH or Me2CO solution.  Complexes isolated include [YX2(Ph3PO)4]Z (X = Cl, Br or I, Z = X or PF6), [YX3(Ph2MePO)3], [YCl2(Ph2MePO)4]PF6, [YCl(Ph3PO)5][SbCl6]2, [Y(Me3PO)6]X3, [YX2(Ph3AsO)4X, and [Y(Me3AsO)6]Cl3.  In addition, the X-ray crystal structures of [YCl2(Ph3PO)4[CI.2.5EtOH.H2O, [YBr2(Ph3PO)4] PF6.ET2O and [Y(Me3PO)6Br3 are reported.  No reaction was observed between YF3.1/2H2O and the same set of ligands.  Studies examining complexes of ScX3.nH2O (X = Cl, Br or I) with the same ligand were carried out.  Compounds isolated include [ScX2(Ph3PO)4]X, [ScX2(Ph3AsO)4]X, [ScCl(Me3PO)5]Cl2, [Sc(Me3PO)6]Z3 (Z = Br or I) and [Sc(Me3AsO)6]X3.  X-ray crystal structures of [ScBr2(Ph3PO)4Br, [ScCl2(Ph3AsO)4]Cl and [Sc(Me3ASO)6]Br3 are reported.  All of the above complexes were characterised using a combination of analysis, conductance measurements, IR and 1H NMR spectroscopy.  Solution speciation was established by variable temperature 31P-{1H} and either 89Y or 45Sc NMR spectroscopy.

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Published date: 2003
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Local EPrints ID: 465009
URI: http://eprints.soton.ac.uk/id/eprint/465009
PURE UUID: 8e9f4230-c7b2-4003-a682-a94023b82fcb

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Date deposited: 05 Jul 2022 00:16
Last modified: 16 Mar 2024 19:53

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Author: Michael Charles Popham

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