One Step Forward to “Stapled” Bis(phthalocyanine) Metal Complexes: Synthesis,
Characterization, and Redox Properties of Bis(phthalocyaninato)niobium(IV). X-ray
Crystal Structure of the Monoelectronically Oxidized Species [Pc<sub>2</sub>Nb](I<sub>3</sub>)(I<sub>2</sub>)<sub>0.5</sub>(ClNP)<sub>3.5</sub>
(ClNP = 1-Chloronaphthalene)
Maria Pia Donzello
Claudio Ercolani
Angiola Chiesi-Villa
Corrado Rizzoli
10.1021/ic970841f.s002
https://acs.figshare.com/articles/journal_contribution/One_Step_Forward_to_Stapled_Bis_phthalocyanine_Metal_Complexes_Synthesis_Characterization_and_Redox_Properties_of_Bis_phthalocyaninato_niobium_IV_X-ray_Crystal_Structure_of_the_Monoelectronically_Oxidized_Species_Pc_sub_2_sub_Nb_I_sub_3_sub_I_sub_2_sub_su/3619851
Bis(phthalocyaninato)niobium(IV) has
been prepared and isolated as a monosolvate,
[Pc<sub>2</sub>Nb]·ClNP (ClNP =
1-chloronaphthalene). It is a light-brown, stable-to-air
Nb(IV) (d<sup>1</sup>) paramagnetic sandwich-like species,
which,
upon oxidation by I<sub>2</sub> under mild conditions, undergoes a
metal-centered monoelectronic oxidation to give the
diamagnetic Nb(V) (d<sup>0</sup>)
[Pc<sub>2</sub>Nb]<sup>+</sup> fragment, with formation of
saltlike species of formula
[Pc<sub>2</sub>Nb](I<sub>3</sub>)(I<sub>2</sub>)0.5(ClNP)<sub>3.5</sub> (<b>I</b>). The structure of <b>I</b>
has been elucidated by single-crystal X-ray work. Crystals are
triclinic: formula
C<sub>64</sub>H<sub>32</sub>N<sub>16</sub>Nb·I<sub>3</sub>·0.5I<sub>2</sub>·3.5C<sub>10</sub>H<sub>7</sub>Cl,
<i>M</i> = 2194.8, <i>a</i> = 17.702(3) Å,
<i>b</i> = 18.708(3) Å, <i>c</i> = 13.504(2) Å,
<i>V</i> = 4267.5(13) Å<sup>3</sup>, α = 106.00(2)°, β =
93.39(2)°, γ = 83.26(1)°, <i>Z</i> = 2, space
group <i>P</i>1̄. The structure of the
[Pc<sub>2</sub>Nb]<sup>+</sup>
fragment, “stapled” by two inter-ligand C−C σ bonds
(C11A−C11B and C31A−C31B = 1.574(15) Å),
together
with its color and UV−visible spectral behavior, allows a
straightforward assignment of the same “stapled”
structure
to the unoxidized [Pc<sub>2</sub>Nb]. The present niobium
sandwiched materials reiterate the peculiar structural
findings
shown only by the previously reported
[Pc<sub>2</sub>Ti].
1998-02-19 00:00:00
Pc 2 Nb
C 11A
Step Forward
saltlike species
UV
C 31A
Redox Properties
Monoelectronically Oxidized Species
ClNP