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Phospha(III)guanidinate complexes of titanium(IV) and zirconium(IV) amides

Phospha(III)guanidinate complexes of titanium(IV) and zirconium(IV) amides
Phospha(III)guanidinate complexes of titanium(IV) and zirconium(IV) amides

Two procedures for the synthesis of group 4 phosphaguanidine compounds M(R2PC{NR′}2)(NR″2)3 (M = Ti, Zr; R = Ph, Cy; R′ = iPr, Cy; R″ = Me, Et) are described. Spectroscopic characterization indicated symmetrical bonding of the phosphaguanidinate ligand in solution for the P-diphenyl derivatives whereas the P-dicyclohexyl analogs adopt a more rigid geometry with inequivalent N amidine substituents within the phosphaguanidinate ligand. X-ray diffraction studies show exclusively monomeric tbp metal centers for a series of derivatives, with a chelating phosphaguanidinate ligand that spans an axial and an equatorial position. Two different conformers have been identified in the solid-state that differ in the relative orientation of the phosphorus R 2P?C substituents with respect to the equatorial plane of the tbp metal. The synthetic protocol was extended to the bimetallic complex, [PhP(C{NiPr}2Ti{NMe2}3)CH 2?]2, which was characterized by crystallography as the meso-form.

Coordination compounds, Crystal structure, Phosphaguanidinates, Titanium amides, Zirconium amides
0277-5387
2481-2488
Mansfield, Natalie E.
4d6b9a06-2b2e-4ba9-916e-8f8ff27c2ac5
Grundy, Joanna
0bc72187-8dce-41fc-b809-93a6adbe0980
Coles, Martyn P.
4cb5ee08-daf9-4b58-9627-61732e0a818b
Hitchcock, Peter B.
4c0fe381-c3e8-452c-a284-fe14acd3b748
Mansfield, Natalie E.
4d6b9a06-2b2e-4ba9-916e-8f8ff27c2ac5
Grundy, Joanna
0bc72187-8dce-41fc-b809-93a6adbe0980
Coles, Martyn P.
4cb5ee08-daf9-4b58-9627-61732e0a818b
Hitchcock, Peter B.
4c0fe381-c3e8-452c-a284-fe14acd3b748

Mansfield, Natalie E., Grundy, Joanna, Coles, Martyn P. and Hitchcock, Peter B. (2010) Phospha(III)guanidinate complexes of titanium(IV) and zirconium(IV) amides. Polyhedron, 29 (12), 2481-2488. (doi:10.1016/j.poly.2010.05.017).

Record type: Article

Abstract

Two procedures for the synthesis of group 4 phosphaguanidine compounds M(R2PC{NR′}2)(NR″2)3 (M = Ti, Zr; R = Ph, Cy; R′ = iPr, Cy; R″ = Me, Et) are described. Spectroscopic characterization indicated symmetrical bonding of the phosphaguanidinate ligand in solution for the P-diphenyl derivatives whereas the P-dicyclohexyl analogs adopt a more rigid geometry with inequivalent N amidine substituents within the phosphaguanidinate ligand. X-ray diffraction studies show exclusively monomeric tbp metal centers for a series of derivatives, with a chelating phosphaguanidinate ligand that spans an axial and an equatorial position. Two different conformers have been identified in the solid-state that differ in the relative orientation of the phosphorus R 2P?C substituents with respect to the equatorial plane of the tbp metal. The synthetic protocol was extended to the bimetallic complex, [PhP(C{NiPr}2Ti{NMe2}3)CH 2?]2, which was characterized by crystallography as the meso-form.

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More information

Accepted/In Press date: 19 May 2010
e-pub ahead of print date: 1 June 2010
Published date: 11 August 2010
Keywords: Coordination compounds, Crystal structure, Phosphaguanidinates, Titanium amides, Zirconium amides

Identifiers

Local EPrints ID: 426150
URI: http://eprints.soton.ac.uk/id/eprint/426150
ISSN: 0277-5387
PURE UUID: 7cced30b-dc38-43a7-b4d8-5c2095c0e65d

Catalogue record

Date deposited: 15 Nov 2018 17:30
Last modified: 15 Nov 2018 17:30

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