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Hard/soft interactions : Group IV metal halide complexes with soft donor ligands of groups 15 and 16

Hard/soft interactions : Group IV metal halide complexes with soft donor ligands of groups 15 and 16
Hard/soft interactions : Group IV metal halide complexes with soft donor ligands of groups 15 and 16

The complexes fac-(Mn(CO)33-L)]CF3SO3 (L = [12]-, [14], [16]-aneS4 and [15]aneS5) have been prepared and characterised by mass spectroscopy, IR and multinuclear (1H, 13C{1H}, 55Mn) NMR spectroscopy and elemental analysis. Single crystal X-ray diffraction of adducts with L = [12]aneS4 and [15]aneS5 confirmed fac coordination of the ligand. Decarbonylation with Me3NO afforded cis-[Mn(CO)24-L)]CF3SO3 as the first examples of thioether stabilised [Mn(CO)2]+. These were characterised as above and X-ray crystallography of adducts with L = [12]-, [16]-aneS4 and [15]aneS5 revealed the consequences of increasing macrocyclic coordination.

The coordination chemistry of soft donor ligands with Group IV metal halides has been investigated. The complexes [TiX4(L2)] (L2 = MeE(CH2)nEMe, o-C6H4(EMe)2, X = Cl, Br; L2 = PhE(CH2)nEPh, X = Cl; E = S, Se, n = 2,3) and [TiI4(L2)] (L2 = MeSe-(CH2)nSeMe, o-C6H4(SeMe)2) have been prepared and characterised by electronic, IR and multinuclear (1H, 13C{1H}, 77Se{1H}) NMR spectroscopy and elemental analysis. NMR spectroscopy revealed dynamic inversion and dissociation processes in solution. X-ray crystallography of [TiCl4(L2)] (L2 = o-C6H4(SeMe)2 and MeE(CH2)nEMe, E = S, n = 2,3; E = Se, n = 3) confirmed cis coordination of the ligands and revealed trends in the coordination geometry at Ti(IV).

Analogous reactions with Group 15 ligands afforded [TiX4(L2)] (L2 = Ph2As-(CH2)2AsPh2, Ph2P(CH2)nPPh2 (n = 1,2,3), o-C6H4(PPh2)2, o-C6H4(EMe2)2, E = As, P) and [TiI4{o-C6H4(EMe2)2}] (E = As, P). Reactions with 2 equivalents of ligand afforded rare 8-coordinate [TiX4(L2)2] for L2 = o-C6H4(EMe2)2, E = As, P, X = Cl, Br, I. The complexes were characterised by electronic, IR and multinuclear (1H, 13C{1H}, 31P{1H}) NMR spectroscopy and elemental analysis. X-ray crystallography of [TiCl4(o-C6H4(PMe2)2)] and [TiX4(o-C6H4(EMe2)2)2] (E = P, X = Cl, Br; E = As, X = Br) revealed changes in the geometry at Ti(IV) on increasing coordination number.

University of Southampton
Patel, Bhavesh
d08a7519-a670-4a58-9155-0810d9c85f7a
Patel, Bhavesh
d08a7519-a670-4a58-9155-0810d9c85f7a

Patel, Bhavesh (2002) Hard/soft interactions : Group IV metal halide complexes with soft donor ligands of groups 15 and 16. University of Southampton, Doctoral Thesis.

Record type: Thesis (Doctoral)

Abstract

The complexes fac-(Mn(CO)33-L)]CF3SO3 (L = [12]-, [14], [16]-aneS4 and [15]aneS5) have been prepared and characterised by mass spectroscopy, IR and multinuclear (1H, 13C{1H}, 55Mn) NMR spectroscopy and elemental analysis. Single crystal X-ray diffraction of adducts with L = [12]aneS4 and [15]aneS5 confirmed fac coordination of the ligand. Decarbonylation with Me3NO afforded cis-[Mn(CO)24-L)]CF3SO3 as the first examples of thioether stabilised [Mn(CO)2]+. These were characterised as above and X-ray crystallography of adducts with L = [12]-, [16]-aneS4 and [15]aneS5 revealed the consequences of increasing macrocyclic coordination.

The coordination chemistry of soft donor ligands with Group IV metal halides has been investigated. The complexes [TiX4(L2)] (L2 = MeE(CH2)nEMe, o-C6H4(EMe)2, X = Cl, Br; L2 = PhE(CH2)nEPh, X = Cl; E = S, Se, n = 2,3) and [TiI4(L2)] (L2 = MeSe-(CH2)nSeMe, o-C6H4(SeMe)2) have been prepared and characterised by electronic, IR and multinuclear (1H, 13C{1H}, 77Se{1H}) NMR spectroscopy and elemental analysis. NMR spectroscopy revealed dynamic inversion and dissociation processes in solution. X-ray crystallography of [TiCl4(L2)] (L2 = o-C6H4(SeMe)2 and MeE(CH2)nEMe, E = S, n = 2,3; E = Se, n = 3) confirmed cis coordination of the ligands and revealed trends in the coordination geometry at Ti(IV).

Analogous reactions with Group 15 ligands afforded [TiX4(L2)] (L2 = Ph2As-(CH2)2AsPh2, Ph2P(CH2)nPPh2 (n = 1,2,3), o-C6H4(PPh2)2, o-C6H4(EMe2)2, E = As, P) and [TiI4{o-C6H4(EMe2)2}] (E = As, P). Reactions with 2 equivalents of ligand afforded rare 8-coordinate [TiX4(L2)2] for L2 = o-C6H4(EMe2)2, E = As, P, X = Cl, Br, I. The complexes were characterised by electronic, IR and multinuclear (1H, 13C{1H}, 31P{1H}) NMR spectroscopy and elemental analysis. X-ray crystallography of [TiCl4(o-C6H4(PMe2)2)] and [TiX4(o-C6H4(EMe2)2)2] (E = P, X = Cl, Br; E = As, X = Br) revealed changes in the geometry at Ti(IV) on increasing coordination number.

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Published date: 2002

Identifiers

Local EPrints ID: 464669
URI: http://eprints.soton.ac.uk/id/eprint/464669
PURE UUID: aa9d53f5-ab5e-49dd-80a4-9006521f59f8

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Date deposited: 04 Jul 2022 23:55
Last modified: 05 Jul 2022 02:51

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Author: Bhavesh Patel

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