10.1021/jacs.5b10074.s002
Balazs Pinter
Balazs
Pinter
Kyle T. Smith
Kyle T.
Smith
Masahiro Kamitani
Masahiro
Kamitani
Eva M. Zolnhofer
Eva M.
Zolnhofer
Ba L. Tran
Ba L.
Tran
Skye Fortier
Skye
Fortier
Maren Pink
Maren
Pink
Gang Wu
Gang
Wu
Brian C. Manor
Brian C.
Manor
Karsten Meyer
Karsten
Meyer
Mu-Hyun Baik
Mu-Hyun
Baik
Daniel J. Mindiola
Daniel J.
Mindiola
Cyclo‑P<sub>3</sub> Complexes of Vanadium:
Redox Properties and Origin of the <sup>31</sup>P NMR Chemical Shift
American Chemical Society
2015
monomeric species 1
31 P NMR resonances
nacnac
31 P NMR spectroscopic signature
endocyclic angle
Redox Properties
redox behavior
NMR spectroscopic signature
structure analysis
Structural metrics
novel complexes
chemical shifts
31 P NMR Chemical ShiftThe synthesis
DFT calculations
2015-12-09 00:00:00
Dataset
https://acs.figshare.com/articles/dataset/Cyclo_P_sub_3_sub_Complexes_of_Vanadium_Redox_Properties_and_Origin_of_the_sup_31_sup_P_NMR_Chemical_Shift/2101057
The
synthesis and characterization of two high-valent vanadium–<i>cyclo</i>-P<sub>3</sub> complexes, (nacnac)V(<i>cyclo</i>-P<sub>3</sub>)(Ntolyl<sub>2</sub>) (<b>1</b>) and (nacnac)V(<i>cyclo</i>-P<sub>3</sub>)(OAr) (<b>2</b>), and an inverted
sandwich derivative, [(nacnac)V(Ntolyl<sub>2</sub>)]<sub>2</sub>(μ<sub>2</sub>-η<sup>3</sup>:η<sup>2</sup>-<i>cyclo</i>-P<sub>3</sub>) (<b>3</b>), are presented. These novel complexes
are prepared by activating white phosphorus (P<sub>4</sub>) with three-coordinate
vanadium(II) precursors. Structural metrics, redox behavior, and DFT
electronic structure analysis indicate that a [<i>cyclo</i>-P<sub>3</sub>]<sup>3–</sup> ligand is bound to a V(V) center
in monomeric species <b>1</b> and <b>2</b>. A salient
feature of these new <i>cyclo</i>-P<sub>3</sub> complexes
is their significantly downfield shifted (by ∼300 ppm) <sup>31</sup>P NMR resonances, which is highly unusual compared to related
complexes such as (Ar[<sup>i</sup>Pr]N)<sub>3</sub>Mo(<i>cyclo</i>-P<sub>3</sub>) (<b>4</b>) and other <i>cyclo</i>-P<sub>3</sub> complexes that display significantly upfield shifted
resonances. This NMR spectroscopic signature was thus far thought
to be a diagnostic property for the <i>cyclo</i>-P<sub>3</sub> 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 <sup>31</sup>P NMR spectroscopic signature by relating the nuclear magnetic
shielding with the electronic structure of the molecule, especially
with the characteristics of metal–<i>cyclo</i>-P<sub>3</sub> bonding.