Further insight into magnetostructural correlations in binuclear copper(II) species related to methemocyanin: x-ray crystal structure of 1,2-.mu.-nitrito complex

McKee, Vickie; Zvagulis, M.; Reed, Christopher A.

doi:10.1021/ic00213a009

Cited by 188 publications

(96 citation statements)

References 2 publications

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“…A similar coormethyl groups are omitted for clarity [a] dination mode with bridging µ-NO 2 -N,O groups has been observed before in several coordination compounds of the transition metals. As expected, the NϪO distances of the bridging NO groups of these complexes are elongated compared to those of terminal NϭO groups by up to 17 pm [22] . The atoms of the nitrito group (N1, O1, O2) and the aluminium atom coordinated by nitrogen (Al2) lie almost ideally within a plane (sum of the angles 359.8 pm).…”

supporting

confidence: 82%

A Methylene-Bridged Dialuminium Compound as a Chelating Lewis Acid: Complexation of Nitrite and Nitrate Anions by R2Al–CH2–AlR2[R = CH(SiMe3)2]⋆

Uhl

Hannemann

Saak

et al. 1998

Eur. J. Inorg. Chem.

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supporting

confidence: 82%

A Methylene-Bridged Dialuminium Compound as a Chelating Lewis Acid: Complexation of Nitrite and Nitrate Anions by R2Al–CH2–AlR2[R = CH(SiMe3)2]⋆

Uhl

Hannemann

Saak

et al. 1998

Eur. J. Inorg. Chem.

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“…The coupling would then be ferromagnetic (or antiferromagnetic) under a given q AO value and antiferromagnetic (or ferromagnetic) above, where q AO is the angle for accidental orthogonality. This phenomenon was observed by Thompson and co-workers for diazine/azide copper complexes, with q AO = 108.58, [14] but it was established by the same group [15] and Escuer et al [16] that the antiferromagnetic nature found for diazine/azide copper complexes for q AO > 108.58 was due to the complementary antibonding overlap phenomenon, [17] and not simply to an effect of an increase of the q 3 ; [8] however, for this compound, the azido ligand is in an axial position, and this lack of magnetic coupling is quite understandable considering that the unpaired electrons of the Cu II centers are localized in the d x 2 Ày 2 orbitals. Our results (i.e.…”

mentioning

confidence: 85%

A Polyoxometalate Containing the {Ni₂N₃} Fragment: Ferromagnetic Coupling in a Ni^II μ‐1,1 Azido Complex with a Large Bridging Angle

et al. 2004

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Dedicated to Professor M. T. Pope on the occasion of his 70th birthday.The chemistry of polyoxometalates (POMs) continues to attract much attention, particularly with respect to potential catalytic activity. [1] In the last few years it has also been noted that POMs are ideal models for the study of exchange interactions in magnetic clusters, as they represent a class of well-insulated complexes of controlled nuclearity and topology.[ [5] and that N 3 À is certainly one of the most interesting magnetic couplers known in molecular chemistry, we have decided to investigate the interaction of this ligand with magnetic POMs. Very recently, we have shown that the paramagnetic center of a Cu II POM can bind an azido group;[3e] nevertheless, the lack of structural information prevents any investigation of the magnetic properties of the compound obtained. We report herein the synthesis, the structural characterization, and the magnetic properties of complex KRb 5 [(PW 10 O 37 )(Ni(H 2 O)) 2 (m-N 3 )]·19 H 2 O (1), which is the first example of a fully characterized azido polyoxometalate. Moreover, the topology of the {Ni(m-1,1-N 3 )Ni} core in 1 is unprecedented, as no corner-sharing azido-bridged Ni II complex has been obtained to date. It follows that the Ni-N-Ni angle q in 1 is by far the largest observed in azido-ligand bridged Ni II compounds, a feature which should help the understanding of the relationships between structural parameters and the value of the magnetic exchange parameter J for m-1,1-N 3 complexes.Compound 1 9À species in solution, is known. [6] Crystal structure analysis of compound 1 [7] shows that 1 can be described as the result of the formal removing of a {W 3 O 13 } group from the [a-PW 12 O 40 ] 3À ion followed by its replacement by a {WO 10 Ni 2 -(H 2 O) 2 N 3 } fragment (Figure 1). Two crystallographically non-6À subunits (1 a and 1 b, containing the ions Ni(1) and Ni(2), respectively) have been found in the unit cell. The dinuclear {[Ni(H 2 O)] 2 N 3 } entities are highly similar in 1 a and 1 b (see Figure 1), and will be considered as identical for the forthcoming discussion. The paramagnetic centers are in an axially distorted octahedral environment. Indeed, an elongated NiÀO(PO 3 ) bond (d Ni-O = 2.273(5), 2.283(4) ) is observed in the position trans to the Ni À OH 2 bond (d NiÀOH 2 = 2.007(2), 2.018(4) ), the remaining Ni-O/N bonds are in the range 1.990(5)-2.081(5) . The two paramagnetic centers are bridged by one of the terminal nitrogen atoms of the azido ligand, which connects the

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“…In fact, when the bridging ligands are different, the two bridges may either add or counterbalance their effects. This problem has been treated by Nishida et al [26] and McKee et al, [27] and these phenomena are known as orbital complementarity and countercomplementarity, respectively. In the present case, the splitting of the molecular magnetic orbitals is reversed for each type of bridging ligand, thus leading an almost negligible energy difference between them (see qualitative MO diagram in Scheme 1).…”

Section: Magnetic Propertiesmentioning

confidence: 99%

Analysis of the Interaction between Adenine Nucleobase and Metal‐Malonato Complexes

et al. 2009

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The synthesis, crystal structure and variable-temperature magnetic measurements of compounds Co (2 and 3)] units where the 7H-tautomeric form of the nucleobase and the malonate dianion act as µ-κN3:κN9 and µ-κ 2 O1,O2:κO1 bridging ligands, respectively. The supramolecular crystal structures of 1-3 are essentially maintained by hydrogen-bonding interactions involving the nucleobases, the carboxylate groups and crystallisation water molecules (in compounds 1 and 2). Compounds 4 and 5 show a hybrid inorganic-organic lamellar structure containing layers of anionic metal-malonato complexes and supramolecular aggregates of the 1H,9H-adeninium cation. Their overall three-dimensional architectures are controlled,

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Further insight into magnetostructural correlations in binuclear copper(II) species related to methemocyanin: x-ray crystal structure of 1,2-.mu.-nitrito complex

Cited by 188 publications

References 2 publications

A Methylene-Bridged Dialuminium Compound as a Chelating Lewis Acid: Complexation of Nitrite and Nitrate Anions by R2Al–CH2–AlR2[R = CH(SiMe3)2]⋆

A Methylene-Bridged Dialuminium Compound as a Chelating Lewis Acid: Complexation of Nitrite and Nitrate Anions by R2Al–CH2–AlR2[R = CH(SiMe3)2]⋆

A Polyoxometalate Containing the {Ni₂N₃} Fragment: Ferromagnetic Coupling in a Ni^II μ‐1,1 Azido Complex with a Large Bridging Angle

Analysis of the Interaction between Adenine Nucleobase and Metal‐Malonato Complexes

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Further insight into magnetostructural correlations in binuclear copper(II) species related to methemocyanin: x-ray crystal structure of 1,2-.mu.-nitrito complex

Cited by 188 publications

References 2 publications

A Methylene-Bridged Dialuminium Compound as a Chelating Lewis Acid: Complexation of Nitrite and Nitrate Anions by R2Al–CH2–AlR2[R = CH(SiMe3)2]⋆

A Methylene-Bridged Dialuminium Compound as a Chelating Lewis Acid: Complexation of Nitrite and Nitrate Anions by R2Al–CH2–AlR2[R = CH(SiMe3)2]⋆

A Polyoxometalate Containing the {Ni2N3} Fragment: Ferromagnetic Coupling in a NiII μ‐1,1 Azido Complex with a Large Bridging Angle

Analysis of the Interaction between Adenine Nucleobase and Metal‐Malonato Complexes

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A Polyoxometalate Containing the {Ni₂N₃} Fragment: Ferromagnetic Coupling in a Ni^II μ‐1,1 Azido Complex with a Large Bridging Angle