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 SM ISO690:2012LOZAN, Vasile, LACH, Jochen, KERSTING, Berthold. Synthesis, structure, and reactivity of dinuclear nickel amino-thiophenolate complexes bearing bridging VO 2(OH) 2 -and VO 2(OR) 2 - coligands. In: Inorganic Chemistry, 2012, vol. 51, pp. 5213-5233. ISSN 0020-1669. DOI: https://doi.org/10.1021/ic300085f |
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  Inorganic Chemistry |
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| Volumul 51 / 2012 / ISSN 0020-1669 | ||||||
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| DOI:https://doi.org/10.1021/ic300085f | ||||||
| Pag. 5213-5233 | ||||||
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A series of novel mixed ligand dinickel complexes of the type [Ni II 2L(μ-L′)] +, where L′ is a tetrahedral oxo-alkoxo vanadate (L′ = [O 2V V(OR) 2] -, R = H or alkyl) and L a macrocyclic N 6S 2 supporting ligand, have been prepared, and their esterification reactivity has been studied. The orthovanadate complex [Ni 2L(μ-O 2V(OH) 2)] + (2), prepared by reaction between [Ni 2L(μ-Cl)]ClO 4 with Na 3VO 4 and a phase transfer reagent in CH 3CN, reacts smoothly with MeOH and EtOH forming the vanadate diesters [Ni 2L(μ-O 2V(OMe) 2)] + (3) and [Ni 2L(μ-O 2V(OEt) 2)] + (4). The dialkyl orthovanadate esters in 3 and 4 are readily transesterified with mono- and difunctional alcohols. Complex 3 can also be generated from 4 by transesterification with MeOH. Complexes 3 and 4 react with diols (ethylene glycol, propylene glycol and diethylene glycol) as well to afford the complexes [Ni 2L(μ-O 2V(OH)(OCH 2CH 2OH))] + (5), [Ni 2L(μ-O 2V(OCH 2) 2CH 2)] + (6), and [Ni 2L(μ-O 2V(OCH 2CH 2) 2O)] (7). The crystal structures of the tetraphenylborate salts of complexes 3-7 reveal in each case four-coordinate O 2V V(OR) 2 - groups bonded in a μ 1,3-bridging mode to generate trinuclear complexes with a central N 3Ni(μ-S) 2(μ 1,3-O 2V(OR) 2)NiN 3 core. The stabilization of the four-coordinate V VO 2(OR) 2 - moieties is a consequence of both the two-point coordinative fixation to and the steric protection of the bowl-shape binding pocket of the [Ni 2L] 2+ fragment. Cyclic voltammetry experiments reveal that the encapsulated vanadate esters are not reduced in a potential window of -2.0 to +2.5 V vs SCE. The spins of the nickel(II) (S i = 1 ions) in 3 are weakly ferromagnetically coupled (J = +23 cm -1, (H = -2JS 1S 2)) to produce an S = 2 ground state. |
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