Synthesis of a Reduced Tridecavanadate Dimer Linked by Eight Hydrogen Bonds

Abstract

The reaction of highly condensed heptadecavanadate with labile metal compound gave the first reduced tridecavanadate with hydrogen bonds to make a novel dimeric structure: the protonated and reduced sites were unambiguously determined by X-ray analysis. The reduced tridecavanadate was not directly converted chemically or electrochemically into the oxidized form.

The first tridecanuclear nickel(II) cluster: [Ni13(OH)6(O2CMe)8(btaO)12(H2O)6(nPrOH)4] (btaOH=1-hydroxybenzotriazole)

“…Tridecanuclear complexes are particularly uncommon. For the 3d metals, there are only few non-organometallic M 13 complexes containing N-or/and O-donors; homometallic tridecanuclear clusters are limited to V [18], Mn [19], Fe [20] and Co [21].…”

One Octasubstituted Trisalkoxotetradecavanadate Cluster

“…The V5O21 i bond length [1.652(3) Å] is slightly longer than those of other VO terminal bonds [1.593(4)–1.608(3) Å] because of the influence of the O21 i atom further bonding to the V6 i atom. The V–O bond distances are in the range of 1.951(3)–2.427(3) Å, and the V–N bond distances vary from 2.096(4) to 2.148(4) Å, which are compared with the values (1.848–2.457 Å for V–O and 2.031–2.187 Å for V–N) in other compounds . The O 2– anions show four coordination environments, namely, terminal O and μ 2 -O, μ 4 -O, and μ 5 -O bridging modes, where the μ 5 -O 2– anion adopts a rare oxo-centered square-pyramidal [OV 5 ], because the μ 2 -O, μ 3 -O, and μ 6 -O bridging modes are common within the POVs. − Seven VO units are bridged together by one μ 4 -O and one μ 5 -O to create a unsaturated [V 7 O 2 ] unit, which is further coordinated by the HCOO – , tri 3– , and Htri 2– bridging ligands, resulting in a novel tetrasubstituted trisalkoxoheptavanadate cluster, [V 7 O 9 (tri)­(Htri) 3 (HCOO)] (Figure a,d).…”

Structure Transformation among Deca-, Dodeca- and Tridecavanadates and Their Properties for Thioanisole Oxidation

“…After the pioneering work on the chemistry of [V13O34] 3− , few further investigations were reported. Our group successfully synthesized the four electron reduced tridecavanadate [H4V13O34] 3− [24]. During our investigation, the electrochemical oxidation of [H4V13O34] 3 [25].…”