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Synthesize triangular trinuclear manganese(II) and magnesium(II) complexes supported by triamidophosphine ligands to investigate their magnetic properties, solid-state structures, and nuclear spin interactions.

November 1, 2006Journal of the American Chemical Society

Assembly of Triangular Trimetallic Complexes by Triamidophosphine Ligands: Spin-Frustrated Mn²⁺ Plaquettes and Diamagnetic Mg²⁺ Analogues with a Combined Through-Space, Through-Bond Pathway for ³¹P-³¹P Spin−Spin Coupling

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JHJillian A. HatneanWindsor Dermatology RRR. RaturiSimon Fraser University JLJulie LefebvreUniversité du Québec à Trois-Rivières

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Inorganic synthesis and spectroscopic study reveals spin frustration in trimanganese plaquettes and unusual phosphorus-phosphorus coupling in magnesium analogues, indicating coupled interaction...

Key Points

Synthesize triangular trinuclear manganese(II) and magnesium(II) complexes supported by triamidophosphine ligands to investigate their magnetic properties, solid-state structures, and nuclear spin interactions.
Synthesized Mn(II) complexes by reacting triamidophosphine precursors with Mn[N(SiMe3)2]2, and diamagnetic Mg(II) analogues via reaction with nBu2Mg.
Characterized structural and electronic features using X-ray crystallography, temperature-dependent magnetic susceptibility (1.8 to 300 K), and variable-temperature 1H and 31P{1H} NMR spectroscopy.
Performed density functional theory (DFT) calculations on model complexes to elucidate mechanisms underlying phosphorus-phosphorus spin-spin coupling.
Paramagnetic Mn(II) trimers adopt approximate C3 symmetry with magnetic Jahn-Teller distorted isosceles geometries, displaying spin frustration with an S = 1/2 ground state and transition to an S = 3/2 excited state above 3.8 T.
Diamagnetic Mg(II) complexes maintain their solid-state structures in solution, with NMR analysis demonstrating restricted aryl rotation driven by electronic effects.
Solution 31P{1H} NMR spectroscopy uncovered an unexpected 15 Hz 31P-31P coupling in Mg(II) analogues, which DFT calculations attribute to a combined through-space and through-bond pathway.

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Hatnean et al. (2006) studied this question.

synapsesocial.com/papers/6a71b6c42fdcb5703edb7e7e https://doi.org/10.1021/ja065597i

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Implication

Inorganic synthesis and spectroscopic study reveals spin frustration in trimanganese plaquettes and unusual phosphorus-phosphorus coupling in magnesium analogues, indicating coupled interaction...

Assembly of Triangular Trimetallic Complexes by Triamidophosphine Ligands: Spin-Frustrated Mn²⁺ Plaquettes and Diamagnetic Mg²⁺ Analogues with a Combined Through-Space, Through-Bond Pathway for ³¹P-³¹P Spin−Spin Coupling

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Assembly of Triangular Trimetallic Complexes by Triamidophosphine Ligands: Spin-Frustrated Mn²⁺ Plaquettes and Diamagnetic Mg²⁺ Analogues with a Combined Through-Space, Through-Bond Pathway for ³¹P-³¹P Spin−Spin Coupling

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