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Ligand-Centered Redox Activity in Cobalt (II) and Nickel (II) Bis (Phenolate) - Dipyrrin Complexes
Ligand-Centered Redox Activity in Cobalt (II) and Nickel (II) Bis (Phenolate) - Dipyrrin Complexes
201202882
The chemistry of coordinated radicals has recently attract- both ligand families, but their electronic structures remain
ed considerable interest.[1] This research has improved the speculative because of their high reactivity.
understanding of the interaction between transition metals Bloom and Garcia in the early 1970s introduced a fasci-
and non-innocent ligands, and spurred transition-metal cata- nating class of ligands that combine a “half-porphyrin” (di-
lyst development incorporating redox-active ligands.[2] pyrrin) and two phenol moieties in a single and highly elec-
Metal-coordinated ligand radicals are found naturally in the tron-rich trianionic ligand.[9] The use of this ligand system
active site of a number of metalloenzymes and the most has increased recently, especially for catalytic purposes.[10, 11]
ubiquitous ones are porphyrinyls (as in cytochrome P450)[3] Although this ligand architecture may support an extraordi-
and tyrosinyls (as in galactose oxidase).[4] These two classes narily rich ligand-based redox activity, no data supporting
of radicals are formed by oxidation of either coordinated co- this fact has yet been reported in the literature, and oxida-
factors or amino-acids and exhibit distinct properties, stabili- tion catalysis is proposed to occur through metal-centered
ties, and generation pathways. In principle, one-electron oxi- processes.[10, 11]
dation of a Mn + –L species involving a redox-active ligand We present in this paper the first evidence for ligand-cen-
leads to either M(n + 1) + –L or the species Mn + –LC, where the tered, as opposed to metal-centered oxidative redox activity
radical is centered on the ligand. Modeling studies on repre- in the bisACHTUNGRE(phenol)–dipyrrin ligand family. For that purpose
sentative Mn + –phenolate and Mn + –porphyrin systems reveal we investigated the oxidative chemistry of the bis(di-tert-
that several interdependent factors such as the solvent, tem- butyl-phenol)–dipyrrin ligand, H3L, coordinated to Ni2 + and
perature, nature of the metal ion, and substituents may in- Co2 + metal ions (Scheme 1). The one-electron (a radical)
fluence the site of oxidation. As an example, square-planar
Ni2 + –bis(phenolate)[5] and Ni2 + –porphyrin[6] complexes un-
dergo a reversible one-electron oxidative electron transfer,
which is assigned to the Ni3 + /Ni2 + redox couple in coordinat-
ing solvent, whereas it corresponds to the LC/L redox couple
in CH2Cl2. Further, the Co2 + ion is oxidized more easily
than coordinated phenolates but less easily than porphyrin
macrocycles in CH2Cl2. Consequentely one-electron oxi-
dized Co2 + –salen complexes exhibit a marked Co3 + –bis-
ACHTUNGRE(phenolate) character,[7] whereas oxidized Co2 + –porphyrin
complexes exhibit a Co2 + –(porphyrinyl radical) character.[8]
Scheme 1. Bis(di-tert-butyl-phenol)–dipyrrin ligand, H3L, and metal com-
Interestingly, two-electron oxidized species are accessible in plexes thereof.
14590 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eur. J. 2012, 18, 14590 – 14593
COMMUNICATION
Figure 2. Mean bond lengths in one half of the ligand: (a) titanium, man-
ganese, and aluminum complexes of a trianionic bis(phenolate)—dipyrrin
ligand that does not have t-butyl groups;[9, 10] (b) 1 and 2; (c) 1 + ; (d) 2 + .
Unless a length range is indicated the values have an error of 0.01 .
(e) Simplified canonical forms of one phenol–pyrrole radical unit (full
delocalization occurs over the second unit).
Figure 1. ORTEP views of (a) 1 and (b) 2 + ; thermal ellipsoids are shown
at 30 % probability and hydrogen atoms are omitted for clarity, except from oxidation of the ligand could be so clearly evidenced
those of the water molecule. in 1 and 2: Extensive delocalization in the radical complexes
Ni—OEPC + [12] and Ni–(di-tert-butyl-salen)C + ,[13] which belong
to rare Ni2 + —(ligand-centered radical) complexes of the
Owing to the trianionic nature of the fully deprotonated two families structurally characterized, attenuates the struc-
ligand L3 the isolated complexes involve either a M2 + -coor- tural variations resulting from oxidation of the neutral pre-
dinated ligand radical or a M3 + –bis(phenolate) species. The cursors.
fact that the metal center resides in a square-planar geome- The 100 K EPR spectrum of 1 displays an anisotropic (S =
1
try in 1 and 2 rules out a formal + 3 oxidation state for the =2 ) signal at g1 = 2.025, g2 = 2.008, and g3 = 1.975 (gav = 2.003),
metal ion. The ligand thus exhibits radical character, and thus being consistent with a radical character of the ligand.
will be referred to as LC2. Detailed investigations on the C Interestingly, the g value is lower for 1 than for Ni—(radical
C, CN, and CO bond lengths indicate that the two halves salen) complexes involving similar di-tert-butyl-phenol moi-
of the ligand exhibit very similar structural parameters, con- eties.[13, 14] These data highlights a much smaller Ni contribu-
sistent with a radical that is delocalized. Notably, the bond tion to the SOMO (calculated as ca. 6 % versus 16 % for
lengths of the ligand show little change upon metal-ion sub- Ni–(di-tert-butyl-salen)C + complexes,[13] and shows that the
stitution. Comparison of the LC2 bond lengths with the radical form of bis(di-tert-butyl-phenol)–dipyrrin ligand is
values published for the Ti4 + , Mn3 + , and Al3 + complexes in- more accessible than that of salen ligands. Complex 2 exhib-
volving nonoxidized trianionic bis(phenolate)–dipyrrin li- its magnetic coupling between the radical and the Co2 +
gands is very instructive.[10, 11] From the mean bond lengths spins, thus resulting in EPR silence at 100 K. Interestingly,
listed in Figure 2 (individual bond lengths for 1 and 2 are DFT calculations on 2 predict the triplet state (S = 1) to be
given in the Supporting Information, Table S1) several es- only 0.4 kcal mol1 lower in energy in comparison to the
sential features are notable: The C1O1 (and the corre- broken symmetry (BS)[15] state, suggesting that the high spin
sponding bond on the other side of the metal, C20O2), and antiferromagnetically-coupled spin states are similar in
C2C15 (and C21C34), and C16C17 (and C35C36) energy.
bond lengths are shorter in the ligand radical. In contrast, The Vis/NIR spectra of 1 (Figure 3) and 2 (see the Sup-
the C1C6 (and C20C25) bond is longer in LC2. These porting Information, Figure S8) are dominated by an intense
structural parameters, which are nicely predicted by DFT transition at the approximate range 600–700 nm, as well as
calculations (see the Supporting Information, Figure S7), are lower intensity transitions in the region, 1000–1400 nm.
clear evidence that the radical is delocalized among the Time-dependent density-functional theory (TD-DFT) calcu-
phenol and pyrrole rings (Figure 2). LC2 thus exhibits unpre- lations were used to gain insight into the nature of the low-
cedented mixed porphyrinyl–phenoxyl radical character. energy transitions of 1 and 2.[16] For 1, two low-energy bands
The predicted spin densities for both 1 and 2 (see the Sup- were predicted at 1090 nm and 1260 nm (Figure 3), thus
porting Information, Figure S10 and S11) are symmetrically matching the envelope of low-energy transitions in the ex-
distributed with significant spin density on the dipyrrin perimental spectrum. Both transitions involve orbitals delo-
(30 %, 1; 20 %, 2) and phenolate (65 %, 1; 60 %, 2) moieties. calized over the ligand radical framework with very little Ni
It is remarkable that the changes in bond distances resulting character (see the Supporting Information, Figure S12), and
Chem. Eur. J. 2012, 18, 14590 – 14593 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemeurj.org 14591
F. Thomas et al.
14592 www.chemeurj.org 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eur. J. 2012, 18, 14590 – 14593
Ligand-Centered Redox Activity
COMMUNICATION
ligand exists in the closed-shell form, Lox, in both 1 + and
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[17] The oxidation process at E1/23 for 2 is assigned mainly to the Co3 +
/Co2 + redox couple. It results in the formation of an EPR-silent
Acknowledgements Co3 + complex that is coordinated to a two-electron oxidized closed-
shell ligand.
This work is supported by an NSERC Discovery Grant to T. S. from [18] A minor signal (less than 5 %) could be detected at giso = 2.005 (see
Canada, and a doctoral fellowship to A. K. from the DCM. L. C. thanks the Supporting Information, Figure S5–6), which is assigned to a
the Governments of Canada and France for an exchange scholarship. contaminant monoradical species.
[19] A. Wolberg, J. Manassen, J. Am. Chem. Soc. 1970, 92, 2982.
Keywords: cobalt · dipyrrin · nickel · porphyrins · redox Received: August 10, 2012
chemistry Published online: October 5, 2012
Chem. Eur. J. 2012, 18, 14590 – 14593 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemeurj.org 14593