Coordination chemistry of polyoxomolybdates: The versatile behavior of amidoximes

Roh, Soo-Gyun; Proust, Anna; Robert, Françis; Gouzerh, Pierre

doi:10.1007/bf01165804

Cited by 17 publications

(16 citation statements)

References 27 publications

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“…40 On our part, we have recently prepared and characterized several hexanuclear Mn(III) complexes with salicylamidoxime and its alkyl derivatives R 2 N-saoH 2 (R = H, Me, Et, see Scheme 1). Although amidoximes 41 may display quite versatile coordination behaviour, 42,43 salicylamidoximes behave as derivatized salicylaldoxime in the present case. Accordingly several hexanuclear Mn(III) complexes of the type [Mn 6 O 2 (R 2 Nsao) 6 (L) 2 (solvent) 4-6 ] (L = carboxylate, chloride, 2-cyanophenolate; solvent = H 2 O, MeOH, EtOH, py) have been obtained.…”

Section: Introductionmentioning

confidence: 78%

Synthesis, crystal structure and magnetism of new salicylamidoxime-based hexanuclear manganese(iii) single-molecule magnets

Martı́nez-Lillo

Tomsa

et al. 2012

Dalton Trans.

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Salicylamidoxime was used to synthesize 13 new polynuclear Mn(III) complexes. We present the crystallographic structures, the magnetic susceptibility and the magnetization measurements of eight of them (1-8) with the general formula [Mn(6)O(2)(H(2)N-sao)(6)(L)(2)(solvent)(4-6)] (L = carboxylate, chloride, 2-cyanophenolate; solvent = H(2)O, MeOH, EtOH, py). These complexes consist of two trinuclear {Mn(III)(3)(μ(3)-O)(H(2)N-sao)(3)}(+) cationic units linked together via two oximate and two phenolate oxygen atoms. All behave as single-molecule magnets, with the spin ground state varying from 4 to 12 and anisotropy energy barriers from 24 to 86 K, the latter being as high as the present record barrier in the Mn(6) complexes. DFT calculations were performed to compute the exchange magnetic coupling constants J between the metallic ions and to provide an orbital interpretation of exchange. Our results are in line with previously reported results with the parent salicylaldoxime derivatives. The Mn-N-O-Mn torsion angle appears as the main parameter controlling the J values. The critical angle where the exchange coupling between two Mn(III) switches from antiferromagnetic to ferromagnetic is 27°, less than the one found in related complexes with salicylaldoxime (30°). We propose a structural classification of the {Mn(6)} complexes in four classes depending on the coordination of the axial carboxylate. The work points out the structural flexibility of such systems, their sensitivity to solvent effects and their ability to achieve high anisotropy energy barriers by simple desolvation.

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Section: Introductionmentioning

confidence: 78%

Synthesis, crystal structure and magnetism of new salicylamidoxime-based hexanuclear manganese(iii) single-molecule magnets

Martı́nez-Lillo

Tomsa

et al. 2012

Dalton Trans.

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“…Type 1 complexes, such as CUHJUK, 55 NEKLEW, 56 and POLFED, 57 are the most prevalent amidoximate complexes observed in the absence of additional amidoximates, amines, and pyridines (B18%). The remaining 4% of complexes observed were Type 3, such as RASBOC 58 and BASBIW. 58 However, RASBIW is listed as a Type 4 complex in Fig.…”

Section: Implications For Ligand Designmentioning

confidence: 99%

“…The remaining 4% of complexes observed were Type 3, such as RASBOC 58 and BASBIW. 58 However, RASBIW is listed as a Type 4 complex in Fig. 12 because it was the only complex that exhibited the Type 4 binding motif.…”

Section: Implications For Ligand Designmentioning

confidence: 99%

Theoretical study of the coordination behavior of formate and formamidoximate with dioxovanadium(v) cation: implications for selectivity towards uranyl

Mehio

Johnson

Dai

et al. 2015

Phys. Chem. Chem. Phys.

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Poly(acrylamidoxime)-based fibers bearing random mixtures of carboxylate and amidoxime groups are the most widely utilized materials for extracting uranium from seawater. However, the competition between uranyl (UO2(2+)) and vanadium ions poses a significant challenge to the industrial mining of uranium from seawater using the current generation of adsorbents. To design more selective adsorbents, a detailed understanding of how major competing ions interact with carboxylate and amidoxime ligands is required. In this work, we employ density functional theory (DFT) and wave-function methods to investigate potential binding motifs of the dioxovanadium ion, VO2(+), with water, formate, and formamidoximate ligands. Employing higher level of theory calculations (CCSD(T)) resolve the existing controversy between the experimental results and previous DFT calculations for the structure of the hydrated VO2(+) ion. Consistent with the EXAFS data, CCSD(T) calculations predict higher stability of the distorted octahedral geometry of VO2(+)(H2O)4 compared to the five-coordinate complex with a single water molecule in the second hydration shell, while all seven tested DFT methods yield the reverse stability of the two conformations. Analysis of the relative stabilities of formate-VO2(+) complexes indicates that both monodentate and bidentate forms may coexist in thermodynamic equilibrium in solution. Investigations of VO2(+) coordination with the formamidoximate anion has revealed the existence of seven possible binding motifs, four of which are within ∼4.0 kcal mol(-1) of each other. Calculations establish that the most stable binding motif entails the coordination of oxime oxygen and amide nitrogen atoms via a tautomeric rearrangement of amidoxime to imino hydroxylamine. The difference in the most stable VO2(+) and UO2(2+) binding conformation has important implications for the design of more selective UO2(2+) ligands.

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“…They can ligate either as neutral RC(NH 2 )NOH, zwitterionic RC(NH 2 )NHO, RC(NH 2 )NO - , RC(NH)NHO - , or RC(NH)NO 2- species. They display a range of coordination modes (Table ) , In addition, they can act as nitrosylating reagents, and they can transform into amides or amidines, which further increases the diversity of products.…”

Section: Amide Oximesmentioning

confidence: 99%

Main-Group Element, Organic, and Organometallic Derivatives of Polyoxometalates

1998

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ContentsI. Introduction 77 II. Scope and Organization of the Review 78 III. Polyoxometalates Incorporating Halides 79 IV. Polyoxometalates Incorporating Group 16 Element-Centered Ligands 81 A. Peroxopolyoxometalates 81 B. Polyoxoalkoxometalates 82 1. Polyoxoalkoxometalates Involving Unidentate Alcohols 82 2. Polyoxoalkoxometalates Involving Chelating Triols 83 C. Heavier Group 16 Element-Centered Ligands 85 1. Thiopolyoxometalates 85 2. Organosulfur and Organoselenium Ligands 85 V. Polyoxometalates Incorporating Group 15 Element-Centered Ligands 86 A. Singly Bonded Nitrogen-Donating Ligands 86 1. Amine and Related Ligands 86 2. Amide Oximes [RC(NH 2 )NOH] and Oximes 87 B. Multiply Bonded Nitrogen Ligands 89 1. Nitrido Derivatives 89 2. Organoimido Derivatives 89 3. Hydrazido and Diazenido Derivatives of Polyoxometalates 90 4. Nitrosyl Derivatives 92 C. Organophosphorus, Organoarsenic, and Organoantimony Ligands 94 1. Organophosphonate and Organoarsonate Ligands 94 2. Organophosphinate and Organoarsinate Ligands 97 VI. Polyoxometalates Incorporating Group 14 Element-Centered Ligands 97 A. Oxocarbon Ligands 97 1. Carbonate 97 2. Carboxylates 97 3. Oxalate and Squarate 97 4. Carbonyl Derivatives 98 B. Silicon Derivatives 98 C. Germanium Derivatives 99 D. Tin and Lead Derivatives 99 VII. Organometallic Derivatives of Polyoxometalates 100 A. Cyclopentadienyl Derivatives of Polyoxometalates 100 B. Cyclopentadienyl Oxide Clusters of Groups 5 and 6 100 C. Organometallic Polyoxometalates 100 1. Polyoxometalate-incorporated Organometalic Complexes 101 2. Polyoxometalate-Supported Organometallic Complexes 101 3. Integrated Cubane-Type Clusters 105 4. Organometallic Cation Salts of Keggin-Type Anions 105 VIII. Concluding Remarks 106 IX. Acknowledgments 106 X. Abbreviations 106 XI. References 106

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Coordination chemistry of polyoxomolybdates: The versatile behavior of amidoximes

Cited by 17 publications

References 27 publications

Synthesis, crystal structure and magnetism of new salicylamidoxime-based hexanuclear manganese(iii) single-molecule magnets

Synthesis, crystal structure and magnetism of new salicylamidoxime-based hexanuclear manganese(iii) single-molecule magnets

Theoretical study of the coordination behavior of formate and formamidoximate with dioxovanadium(v) cation: implications for selectivity towards uranyl

Main-Group Element, Organic, and Organometallic Derivatives of Polyoxometalates

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