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Adaptable Ligand Donor Strength: Tracking Transannular Bond Interactions in Tris(2-pyridylmethyl)-azaphosphatrane (TPAP)

Abstract

Flexible ligands that can adapt their donor strength have enabled unique reactivity in a wide range of inorganic complexes. Most examples are composed of flexible multi-dentate ligands containing a donor that can vary its interaction through its distance to the metal center. We describe an alternative type of adaptable ligand interaction in the neutral multi-dentate ligand tris(2-pyridylmethyl)-azaphosphatrane (TPAP), which contains a proazaphosphatrane unit. Prozaphosphatranes are intrinsically strong phosphorous donors; upon coordinated to more Lewis acidic atoms the phosphorous can accept additional electron density from a tertiary nitrogen to form a transannular bond, increasing its donor strength. An experimental and computational investigation of the varying degree of transannular interaction in TPAP when coordinated to late transition metals is reported. The synthesis and characterization of the complexes M(TPAP), where M = Co(I)Cl, Ni(0)(1,5-cyclooctadiene), Ni(II)(CH3CN)(BF4)2, Pd(II)(CH3CN)(BF4)2, Pt(II)Cl(PF6) is described. Structural characterization and density functional theory calculation of these complexes, along with the previously reported [Co(II)(TPAP)(CH3CN)](BF4)2 establish significant increases in the degree of transannular interaction of the proazaphosphatrane unit when coordinated to more electron deficient metal ions.

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Publication details

The article was received on 03 Aug 2018, accepted on 13 Sep 2018 and first published on 14 Sep 2018


Article type: Paper
DOI: 10.1039/C8DT03180K
Citation: Dalton Trans., 2018, Accepted Manuscript
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    Adaptable Ligand Donor Strength: Tracking Transannular Bond Interactions in Tris(2-pyridylmethyl)-azaphosphatrane (TPAP)

    Z. Thammavongsy, D. W. Cunningham, N. Sutthirat, R. Eisenhart, J. W. Ziller and J. Y. Yang, Dalton Trans., 2018, Accepted Manuscript , DOI: 10.1039/C8DT03180K

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