Mechanistic elucidation of the stepwise formation of a tetranuclear manganese pinned butterfly cluster via N-N bond cleavage, hydrogen atom transfer, and cluster rearrangement

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[1] Hamilton, Clifton R.
[2] Gau, Michael R.
[3] 1,Baglia, Regina A.
[4] 1,McWilliams, Sean F.
[5] Zdilla, Michael J.
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Zdilla, Michael J. | 1600年 / American Chemical Society卷 / 136期
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A mechanistic pathway for the formation of the structurally characterized manganese-amide-hydrazide pinned butterfly complex; Mn4(μ3-PhN-NPh-κ3N; N)2(μ-PhN-NPh-κ2-N; N)(μ-NHPh)2L4; (L; THF; py); is proposed and supported by the use of labeling studies; kinetic measurements; kinetic competition experiments; kinetic isotope effects; and hydrogen atom transfer reagent substitution; and via the isolation and characterization of intermediates using X-ray diffraction and electron paramagnetic resonance spectroscopy. The data support a formation mechanism whereby bis[bis(trimethylsilyl)amido]manganese(II) (Mn(NR2)2; where R = SiMe3) reacts with N; N-diphenylhydrazine (PhNHNHPh) via initial proton transfer; followed by reductive N-N bond cleavage to form a long-lived MnIV imido multinuclear complex. Coordinating solvents activate this cluster for abstraction of hydrogen atoms from an additional equivalent of PhNHNHPh resulting in a Mn(II)phenylamido dimer; Mn2(μ-NHPh)2(NR2)2L2. This dimeric complex further assembles in fast steps with two additional equivalents of PhNHNHPh replacing the terminal silylamido ligands with η1-hydrazine ligands to give a dimeric Mn2(μ-NHPh)2(PhN-NHPh)2L4 intermediate; and finally; the addition of two additional equivalents of Mn(NR2)2 and PhNHNHPh gives the pinned butterfly cluster. © 2014 American Chemical Society;
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