Linear trinuclear oximato-bridged complexes MnIII,IVMIIMnIII,IV (M = Zn, Cu or Mn): synthesis, structure, redox behaviour and magnetism ‡

Birkelbach, Frank; Weyhermüller, Thomas; Lengen, M.; Gerdan, Michael; Trautwein, Alfred X.; Wieghardt, Karl; Chaudhuri, Phalguni

doi:10.1039/a704771a

Cited by 56 publications

(40 citation statements)

References 21 publications

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“…As expected the mononuclear precursors [NiL] 3 and [CuL] 4 effectively function as 'ligand complexes' to yield di-or trinuclear complexes (5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15). Complexes 3 and 4 are not involved in self-assembling processes.…”

Section: Synthesis and General Characterization Of The Di-and Tri-nucmentioning

confidence: 86%

“…Very generally double oximato bridges or association of a single N᎐O bridge with a second bridging ligand are involved in the resulting bi-or poly-nuclear complexes. Many types of homo-and heteropolynuclear complexes 1- 15 have been obtained and magnetic investigations have revealed a great variety of behaviours, strong antiferromagnetism, weak antiferromagnetism and even ferromagnetism. It may be noted that singlet-triplet energy gaps of the order of 1000 cm Ϫ1 have been reported for oximato bridged dinuclear copper() complexes in which the double oximato bridge adopts the cis conformation.…”

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confidence: 99%

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Bridging ability of a novel polydentate ligand (H2L) comprising an oxime function. Structures of a mononuclear precursor [NiL] and a dinuclear CuII2 complex. Magnetic properties of mononuclear (NiII and CuII), dinuclear (CuII2, NiII2, NiIICuII and CuIICrIII) and trinuclear (CuII3, CuIIMnIICuII and CuIIZnIICuII) complexes ‡

Costes¹,

Dahan²,

Dupuis³

et al. 1998

J. Chem. Soc., Dalton Trans.

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A novel non-symmetrical polydentate Schiff base ligand 3-({2-[(1-methyl-3-oxobut-1-enyl)amino]ethyl}imino)-butan-2-one oxime (H 2 L) comprising an oxime function among various donor sites yields neutral [Ni II L] and [Cu II L] complexes. The structural determination of [NiL] confirms the deprotonation of the oxime function. The deprotonated oxime oxygen atom can react with auxiliary complexes to give homo-and hetero-di-and tri-nuclear entities. The structural determination of a homodinuclear copper complex clearly shows the presence of the expected oxime bridge, along with an unexpected ketonic bridge between the two copper centres leading to a Cu[O,NO]Cu core. A moderate antiferromagnetic interaction is present in the di-and tri-nuclear copper complexes. A similar interaction is also observed in the heteronuclear complexes (Cu II Ni II and Cu II Mn II ) and, more surprisingly, in the heterodinuclear Cu II Cr III entity. A generalization of the Cu [O,NO]Cu structure leads to a justification of these magnetic properties.In search of new polydentate bridging ligands we have been interested in designing a ligand (H 2 L, Fig. 1) which comprises an oxime function among various donor sites.Indeed it has been known for more than twenty years that oximato groups (᎐ ᎐ N᎐O Ϫ ) can bridge metal ions through their imino nitrogen and deprotonated oxygen atoms. Very generally double oximato bridges or association of a single N᎐O bridge with a second bridging ligand are involved in the resulting bi-or poly-nuclear complexes. Many types of homo-and heteropolynuclear complexes 1-15 have been obtained and magnetic investigations have revealed a great variety of behaviours, strong antiferromagnetism, weak antiferromagnetism and even ferromagnetism. It may be noted that singlet-triplet energy gaps of the order of 1000 cm Ϫ1 have been reported for oximato bridged dinuclear copper() complexes in which the double oximato bridge adopts the cis conformation. 3,10,11The present paper reports on the preparation, characterization and magnetic study of mononuclear Cu II and Ni II , dinuclear complexes involving the Cu II Cu II , Cu II Ni II and Cu II Cr III pairs and trinuclear complexes Cu II Cu II Cu II , Cu II Zn II Cu II and Cu II Mn II Cu II deriving from H 2 L. The structures of a mononuclear [NiL] precursor and a homodinuclear Cu II 2 complex are also reported.

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Section: Synthesis and General Characterization Of The Di-and Tri-nucmentioning

confidence: 86%

mentioning

confidence: 99%

Bridging ability of a novel polydentate ligand (H2L) comprising an oxime function. Structures of a mononuclear precursor [NiL] and a dinuclear CuII2 complex. Magnetic properties of mononuclear (NiII and CuII), dinuclear (CuII2, NiII2, NiIICuII and CuIICrIII) and trinuclear (CuII3, CuIIMnIICuII and CuIIZnIICuII) complexes ‡

Costes¹,

Dahan²,

Dupuis³

et al. 1998

J. Chem. Soc., Dalton Trans.

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“…[13] The linear angle upon cooling to 77 K (peak-to-peak separation 9.5 mT) Cu1ϪCu2ϪCu3 is 174.96 (11)°and is close to those for and a very weak g // at ca. g ϭ 2.3 becomes visible (no A // other species [9,10a] of this type.…”

Section: Crystal Structure Of Compoundmentioning

confidence: 89%

“…[8b,9,10a] Several mixed MnϪCuϪMn linear Dinuclear systems are well documented not only because trinuclear compounds are also known. [11] of their interesting magnetic interactions, [1] but also beIn a preliminary communication [9] we described a novel cause of their relevance for bioinorganic model systems for template synthesis of a new N 4 -donor ligand and, as an copper in enzymes.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, Spectroscopy, and Magnetism of Unique Propeller-Type Linear Trinuclear CuII Complexes with In-situ Prepared Formamidine Ligands

Albada

Koningsbruggen

Mutikainen

et al. 1999

Eur. J. Inorg. Chem.

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“…39,40 Additionally there are several examples of cryptands consisting of tris-glyoximato moieties with the oxygen donors bound to antimony, tin, iron, manganese, or chromium. [41][42][43][44][45][46][47] Given the utilization of macrocycles for many applications including biomimetic chemistry, catalysis, and solar fuels, facile synthetic access to diverse metallomacrocycles is of interest as a complementary strategy for tuning of the electronic and steric environment of coordinated metal centers. We report herein on the synthesis of metallomacrocycles based on aluminium bridged bisglyoximato frameworks and their coordination chemistry with iron and palladium.…”

Section: Introductionmentioning

confidence: 99%

Metallomacrocycles as ligands: synthesis and characterisation of aluminium-bridged bisglyoximato complexes of palladium and iron

et al. 2012

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Dialuminiummacrocycles based on bisglyoximato moieties were prepared and their coordination chemistry with Fe II and Pd II was investigated. The bridging aluminium centers were supported by several types of tetradentate diphenoxide diamine ligands. The nature of the ancillary ligands bound to aluminium was found to affect the overall geometry and symmetry of the metallomacrocycles. Enantiopure, chiral diphenoxide ligands based on the (R,R)-trans-1,2-diaminocyclohexane backbone afforded cleanly one metallomacrocycle isomer. The size and electronic properties of remote substituents on aluminium-bound ligands affected the binding mode and electronic properties of the central iron.A structurally characterized iron complex shows trigonal prismatic coordination mode, with phenoxide bridges between iron and aluminium. Increasing the size of the phenoxide substituents led to square bipyramidal coordination at iron. Employing p-NO 2 -instead of p-tBu-substituted phenoxide as supporting ligands for aluminium caused a 0.27 V positive shift of the Fe III /Fe II reduction potential. These results indicate that the present synthetic approach can be applied to a variety of metallomacrocycles based on bisglyoximato motifs to affect the chemistry at the central metal.

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Linear trinuclear oximato-bridged complexes MnIII,IVMIIMnIII,IV (M = Zn, Cu or Mn): synthesis, structure, redox behaviour and magnetism ‡

Cited by 56 publications

References 21 publications

Synthesis, Structure, Spectroscopy, and Magnetism of Unique Propeller-Type Linear Trinuclear CuII Complexes with In-situ Prepared Formamidine Ligands

Metallomacrocycles as ligands: synthesis and characterisation of aluminium-bridged bisglyoximato complexes of palladium and iron

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