3 research outputs found
Homo- and Heterometal Complexes of Oxido–Metal Ions with a Triangular [V(V)O–MO–V(V)O] [M = V(IV) and Re(V)] Core: Reporting Mixed-Oxidation Oxido–Vanadium(V/IV/V) Compounds with Valence Trapped Structures
A new
family of trinuclear homo- and heterometal complexes with
a triangular [VÂ(V)ÂO–MO–VÂ(V)ÂO] (M = VÂ(IV), <b>1</b> and <b>2</b>; ReÂ(V), <b>3</b>] all-oxido–metal
core have been synthesized following a single-pot protocol using compartmental
Schiff-base ligands, <i>N</i>,<i>N</i>′-bisÂ(3-hydroxysalicylidene)-diiminoalkanes/arene
(H<sub>4</sub>L<sup>1</sup>–H<sub>4</sub>L<sup>3</sup>). The
upper compartment of these ligands with N<sub>2</sub>O<sub>2</sub> donor combination (Salen-type) contains either a VÂ(IV) or a ReÂ(V)
center, while the lower compartment with O<sub>4</sub> donor set accommodates
two VÂ(V) centers, stabilized by a terminal and a couple of bridging
methoxido ligands. The compounds have been characterized by single-crystal
X-ray diffraction analyses, which reveal octahedral geometry for all
three metal centers in <b>1</b>–<b>3</b>. Compound <b>1</b> crystallizes in a monoclinic space group <i>P</i>2<sub>1</sub>/<i>c</i>, while both <b>2</b> and <b>3</b> have more symmetric structures with orthorhombic space group <i>Pnma</i> that renders the vanadiumÂ(V) centers in these compounds
exactly identical. In DMF solution, compound <b>1</b> displays
an 8-line EPR at room temperature with ⟨<i>g</i>⟩
and ⟨<i>A</i>⟩ values of 1.972 and 86.61 ×
10<sup>–4</sup> cm<sup>–1</sup>, respectively. High-resolution
X-ray photoelectron spectrum (XPS) of this compound shows a couple
of bands at 515.14 and 522.14 eV due to vanadium 2p<sub>3/2</sub> and
2p<sub>1/2</sub> electrons in the oxidation states +5 and +4, respectively.
All of these, together with bond valence sum (BVS) calculation, confirm
the trapped-valence nature of mixed-oxidation in compounds <b>1</b> and <b>2</b>. Electrochemically, compound <b>1</b> undergoes
two one-electron oxidations at <i>E</i>
<sub>1/2</sub> =
0.52 and 0.83 V vs Ag/AgCl reference. While the former is due to a
metal-based VÂ(IV/V) oxidation, the latter one at higher potential
is most likely due to a ligand-based process involving one of the
catecholate centers. A larger cavity size in the upper compartment
of the ligand H<sub>4</sub>L<sup>3</sup> is spacious enough to accommodate
ReÂ(V) with larger size to generate a rare type of all-oxido heterotrimetallic
compound (<b>3</b>) as established by X-ray crystallography
Heterobimetallic μ‑Oxido Complexes Containing Discrete V<sup>V</sup>–O–M<sup>III</sup> (M = Mn, Fe) Cores: Targeted Synthesis, Structural Characterization, and Redox Studies
Heterobimetallic compounds [L′OV<sup>V</sup>(μ-O)ÂM<sup>III</sup>L]<sub><i>n</i></sub> (<i>n</i> = 1, M = Mn, <b>1</b>–<b>5</b>; <i>n</i> = 2, M = Fe, <b>6</b> and <b>7</b>) containing
a discrete unsupported V<sup>V</sup>–O–M<sup>III</sup> bridge have been synthesized through a targeted synthesis route.
In the V–O–Mn-type complexes, the vanadiumÂ(V) centers
have a square-pyramidal geometry, completed by a dithiocarbazate-based
tridentate Schiff-base ligand (H<sub>2</sub>L′), while the
manganeseÂ(III) centers have either a square-pyramidal (<b>1</b> and <b>3</b>) or an octahedral (<b>2</b> and <b>5</b>) geometry, made up of a Salen-type tetradentate ligand (H<sub>2</sub>L) as established by X-ray diffraction analysis. The V–O–Mn
bridge angle in these compounds varies systematically from 155.3°
to 128.1° in going from <b>1</b> to <b>5</b> while
the corresponding dihedral angle between the basal planes around the
metal centers changes from 86.82° to 20.92°, respectively.
The V–O–Fe-type complexes (<b>6</b> and <b>7</b>) are tetranuclear, in which the two dinuclear VÂ(μ-O)ÂFe
units are connected together by apical ironÂ(III)–aryl oxide
interactions, forming a dimeric structure with a pair of Fe–O–Fe
bridges. The X-ray data also confirm the VO → M canonical
form to contribute predominantly on the overall V–O–M
bridge structure. The molecules in solution also retain their heterobinuclear
composition, as established by electrospray ionization mass spectrometry
and <sup>51</sup>V NMR spectroscopy. Electrochemically, these complexes
are quite interesting; the manganeseÂ(III) complexes (<b>1</b>–<b>5</b>) display three successive reductions (processes
I–III), each with a monoelectron stoichiometry. Process I is
due to a Mn<sup>III</sup>/Mn<sup>II</sup> reduction (<i>E</i><sub>1/2</sub> ranges between −0.32 and −0.05 V), process
II is a ligand-based reduction, and process III (<i>E</i><sub>1/2</sub> = ∼1.80 V) owes its origin to a V<sup>V</sup>O/V<sup>IV</sup>O reduction; all potentials are versus Ag/AgCl. The
ironÂ(III) compounds (<b>6</b> and <b>7</b>), on the other
hand, show at least four irreversible processes, appearing at <i>E</i><sub>pc</sub> = −0.20, −1.0, −1.58,
and −1.68 V in compound <b>6</b> (processes IV–VII),
together with a reversible process (process VIII) at <i>E</i><sub>1/2</sub> = −1.80 V (Δ<i>E</i><sub>p</sub> = 80 mV). While the first two of these are due to Fe<sup>III</sup>/Fe<sup>II</sup> reductions at the two ironÂ(III) centers of these
tetranuclear cores, the reversible reduction at a more negative potential
(ca. −1.80 V) is due to a V<sup>V</sup>O/V<sup>IV</sup>O-based
electron transfer
Homo- and Heterometal Complexes of Oxido–Metal Ions with a Triangular [V(V)O–MO–V(V)O] [M = V(IV) and Re(V)] Core: Reporting Mixed-Oxidation Oxido–Vanadium(V/IV/V) Compounds with Valence Trapped Structures
A new
family of trinuclear homo- and heterometal complexes with
a triangular [VÂ(V)ÂO–MO–VÂ(V)ÂO] (M = VÂ(IV), <b>1</b> and <b>2</b>; ReÂ(V), <b>3</b>] all-oxido–metal
core have been synthesized following a single-pot protocol using compartmental
Schiff-base ligands, <i>N</i>,<i>N</i>′-bisÂ(3-hydroxysalicylidene)-diiminoalkanes/arene
(H<sub>4</sub>L<sup>1</sup>–H<sub>4</sub>L<sup>3</sup>). The
upper compartment of these ligands with N<sub>2</sub>O<sub>2</sub> donor combination (Salen-type) contains either a VÂ(IV) or a ReÂ(V)
center, while the lower compartment with O<sub>4</sub> donor set accommodates
two VÂ(V) centers, stabilized by a terminal and a couple of bridging
methoxido ligands. The compounds have been characterized by single-crystal
X-ray diffraction analyses, which reveal octahedral geometry for all
three metal centers in <b>1</b>–<b>3</b>. Compound <b>1</b> crystallizes in a monoclinic space group <i>P</i>2<sub>1</sub>/<i>c</i>, while both <b>2</b> and <b>3</b> have more symmetric structures with orthorhombic space group <i>Pnma</i> that renders the vanadiumÂ(V) centers in these compounds
exactly identical. In DMF solution, compound <b>1</b> displays
an 8-line EPR at room temperature with ⟨<i>g</i>⟩
and ⟨<i>A</i>⟩ values of 1.972 and 86.61 ×
10<sup>–4</sup> cm<sup>–1</sup>, respectively. High-resolution
X-ray photoelectron spectrum (XPS) of this compound shows a couple
of bands at 515.14 and 522.14 eV due to vanadium 2p<sub>3/2</sub> and
2p<sub>1/2</sub> electrons in the oxidation states +5 and +4, respectively.
All of these, together with bond valence sum (BVS) calculation, confirm
the trapped-valence nature of mixed-oxidation in compounds <b>1</b> and <b>2</b>. Electrochemically, compound <b>1</b> undergoes
two one-electron oxidations at <i>E</i>
<sub>1/2</sub> =
0.52 and 0.83 V vs Ag/AgCl reference. While the former is due to a
metal-based VÂ(IV/V) oxidation, the latter one at higher potential
is most likely due to a ligand-based process involving one of the
catecholate centers. A larger cavity size in the upper compartment
of the ligand H<sub>4</sub>L<sup>3</sup> is spacious enough to accommodate
ReÂ(V) with larger size to generate a rare type of all-oxido heterotrimetallic
compound (<b>3</b>) as established by X-ray crystallography