Cyclo-P3 Complexes of Vanadium: Redox Properties and Origin of the 31P NMR Chemical Shift

Pinter B, Smith KT, Kamitani M, Zolnhofer E, Tran BL, Fortier S, Pink M, Wu G, Manor BC, Meyer K, Baik MH, Mindiola DJ (2015)

Publication Type: Journal article

Publication year: 2015

Journal

Journal of the American Chemical Society American Chemical Society

Book Volume: 137

Pages Range: 15247-15261

Journal Issue: 48

DOI: 10.1021/jacs.5b10074

Abstract

The synthesis and characterization of two high-valent vanadium-cyclo-P3 complexes, (nacnac)V(cyclo-P3)(Ntolyl2) (1) and (nacnac)V(cyclo-P3)(OAr) (2), and an inverted sandwich derivative, [(nacnac)V(Ntolyl2)]2(2-³:²-cyclo-P3) (3), are presented. These novel complexes are prepared by activating white phosphorus (P4) with three-coordinate vanadium(II) precursors. Structural metrics, redox behavior, and DFT electronic structure analysis indicate that a [cyclo-P3]^3- ligand is bound to a V(V) center in monomeric species 1 and 2. A salient feature of these new cyclo-P3 complexes is their significantly downfield shifted (by 300 ppm) ³¹P NMR resonances, which is highly unusual compared to related complexes such as (Ar[ⁱPr]N)3Mo(cyclo-P3) (4) and other cyclo-P3 complexes that display significantly upfield shifted resonances. This NMR spectroscopic signature was thus far thought to be a diagnostic property for the cyclo-P3 ligand related to its acute endocyclic angle. Using DFT calculations, we scrutinized and conceptualized the origin of the unusual chemical shifts seen in this new class of complexes. Our analysis provides an intuitive rational paradigm for understanding the experimental ³¹P NMR spectroscopic signature by relating the nuclear magnetic shielding with the electronic structure of the molecule, especially with the characteristics of metal-cyclo-P3 bonding.

Authors with CRIS profile

Eva Zolnhofer Lehrstuhl für Anorganische und Allgemeine Chemie Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Indiana University

United States (USA) (US) University of Pennsylvania

United States (USA) (US) Queen's University

United Kingdom (GB)

How to cite

APA:

Pinter, B., Smith, K.T., Kamitani, M., Zolnhofer, E., Tran, B.L., Fortier, S.,... Mindiola, D.J. (2015). Cyclo-P3 Complexes of Vanadium: Redox Properties and Origin of the 31P NMR Chemical Shift. Journal of the American Chemical Society, 137(48), 15247-15261. https://dx.doi.org/10.1021/jacs.5b10074

MLA:

Pinter, Balazs, et al. "Cyclo-P3 Complexes of Vanadium: Redox Properties and Origin of the 31P NMR Chemical Shift." Journal of the American Chemical Society 137.48 (2015): 15247-15261.

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