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 SM ISO690:2012LACH, Jochen, JEREMIES, Alexander, LOZAN, Vasile, LOOSE, Claudia, HAHN, Torsten, KORTUS, Jens, KERSTING, Berthold. Stabilization of hypophosphite in the binding pocket of a dinuclear macrocyclic complex: Synthesis, structure, and properties of [Ni 2L(μ-O 2PH 2)]BPh 4 (L = N 6S 2 Donor Ligand). In: Inorganic Chemistry, 2012, vol. 51, pp. 12380-12388. ISSN 0020-1669. DOI: https://doi.org/10.1021/ic301710b |
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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/ic301710b | ||||||
| Pag. 12380-12388 | ||||||
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The dinickel(II) complex [Ni 2L(ClO 4)]ClO 4 (1), where L 2- represents a 24-membered macrocyclic hexaamine-dithiophenolate ligand, reacts with [nBu 4N]H 2PO 2 to form the hypophosphito-bridged complex [Ni 2L(μ-O 2PH 2)] +, which can be isolated as an air-stable perchlorate [Ni 2L(μ-O 2PH 2)]ClO 4 (2) or tetraphenylborate [Ni 2L(μ- O 2PH 2)]BPh 4 (3) salt. 3·MeCN crystallizes in the triclinic space group P1̄. The bisoctahedral [Ni 2L(μ-O 2PH 2)] + cation has a N 3Ni(μ 1,3-O 2PH 2)(μ-S) 2NiN 3 core structure with the hypophosphito ligand attached to the two Ni II ions in a μ 1,3-bridging mode. The hypophosphito ligand is readily replaced by carboxylates, in agreement with a higher affinity of the [Ni 2L] 2+ dication for more basic oxoanions. Treatment of [Ni 2L(μ-O 2PH 2)]ClO 4 with H 2O 2 or MCPBA results in the oxidation of the bridging thiolato to sulfonato groups. The hypophosphito group is not oxidized under these conditions due to the steric protection offered by the supporting ligand. An analysis of the temperature-dependent magnetic susceptibility data for 3 reveals the presence of ferromagnetic exchange interactions between the Ni II (S = 1) ions with a value for the magnetic exchange coupling constant J of +22 cm -1 (H = -2JS 1S 2). These results are additionally supported by DFT (density functional theory) calculations. |
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