Phospha(III)guanidinate complexes of titanium(IV) and zirconium(IV) amides |
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| Authors: | Natalie E. Mansfield Joanna GrundyMartyn P. Coles Peter B. Hitchcock |
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| Affiliation: | Department of Chemistry, University of Sussex, Falmer, Brighton, BN1 9QJ, UK |
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| 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 Namidine 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 R2P–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)CH2–]2, which was characterized by crystallography as the meso-form. |
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| Keywords: | Coordination compounds Titanium amides Zirconium amides Phosphaguanidinates Crystal structure |
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