NDLI: F-element metalated dipyrrins: synthesis and characterization of a family of uranyl bis(dipyrrinate) complexes

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Fortier, Skye Bolotaulo, Duer Metta-magaña, Alejandro
Description	Author Affiliation: Bolotaulo D ( Department of Chemistry, University of Texas at El Paso, El Paso, Texas 79968, USA. asfortier@utep.edu.); Metta-Magaña A ( Department of Chemistry, University of Texas at El Paso, El Paso, Texas 79968, USA. asfortier@utep.edu.); Fortier S ( Department of Chemistry, University of Texas at El Paso, El Paso, Texas 79968, USA. asfortier@utep.edu.)
Abstract	Using an improved, chromatography-free dipyrrin synthesis, the α,β-unsubstituted dipyrrins $[RC(C_{4}H_{2}N)_{2}H]$ (2) (R = tolyl $(2^{tolyl}),$ $p-OMe-C_{6}H_{4}$ $(2^{anis}),$ mesityl $(2^{mes}),$ ferrocenyl $(2^{Fc}))$ were isolated in good to excellent yields. Deprotonation of 2 with $Na[N(SiMe_{3})_{2}]$ gives the alkali metal salts $[Na(DME)_{n}][RC(C_{4}H_{2}N)_{2}]$ (3) which reacts with $UO_{2}Cl_{2}(THF)_{3}$ to give the uranyl bis(dipyrrinates) $UO_{2}[RC(C_{4}H_{2}N)_{2}]_{2}(L)$ (L = THF $(4^{R}-THF);$ DMAP $(4^{R}-DMAP))$ (R = tolyl, $p-OMe-C_{6}H_{4},$ mesityl, ferrocenyl). The THF adducts, $4^{R}-THF,$ are unstable in aromatic and nonpolar solvents and rapidly decompose to 2 and an intractable uranium-containing solid. On the other hand, the DMAP adducts, $4^{R}-DMAP,$ are indefinitely stable in solution. The solid-state structures of $4^{R}-THF$ and $4^{R}-DMAP$ reveal distorted trigonal bipyramidal geometries. In the solid-state, the dipyrrinate ligands exhibit significant distortions including bowing and, in some instances, out-of-plane equatorial N-atom coordination, likely as a consequence of steric crowding and interligand repulsion. The complexes, $4^{R}-DMAP,$ have been fully characterized by NMR, UV/Vis, and fluorescence spectroscopies, and their electrochemical properties have been investigated through cyclic voltammetry. The cyclic voltammograms of $4^{R}-DMAP$ display several redox features but present a reversible wave at ca. −1.9 V (vs. $Fc^{0/+})$ attributable to a ligand centred reduction. Fluorescence measurements of all compounds reveal that only the mesityl derivatives $2^{mes},$ $3^{mes},$ and $4^{mes}$ fluoresce with modest Stokes shift that ranges from ca. 30–70 nm, with $4^{mes}$ displaying the greatest relative emission intensity.
ISSN	14779226
Issue Number	10
Journal	Dalton Trans.
Volume Number	46
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2017-03-07
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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