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Mixed Alkyl Hydrido Complexes of Zinc: Synthesis, Structure, and Reactivity

Abstract : The (NNNN)-type macrocycle 1,4,7-trimethyl-1,4,7,10-tetraazacyclododecane (Me3TACD, 1,4,7-Me3[12]aneN4) reacted with 1 equiv of ZnEt2 under ethane elimination to give the mononuclear ethyl complex [(Me3TACD)ZnEt] (1). Upon treatment of (Me3TACD)H with 2 equiv of ZnEt2, the dinuclear complex [(Me3TACD)(ZnEt)(ZnEt2)] (2) was formed, which was converted with an additional 1 equiv of (Me3TACD)H to 1. Reaction of 1 with PhSiH3 led to the formation of a tetranuclear ethyl hydrido complex [{(Me3TACD)ZnEt}2(ZnEtH)2] (3). Single-crystal X-ray diffraction study revealed 3 to be a centrosymmetric dimer featuring two [(Me3TACD)ZnEt] units coordinated to a [Zn(μ-H)2Zn] core via amido nitrogen atoms of the Me3TACD ligands. Substitution of the two [(Me3TACD)ZnEt] units in 3 by N-heterocyclic carbene IMes [1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene] gave [(IMes)ZnEtH]2 (4b). The mixed alkyl hydrido complexes [(IMes)ZnRH]2 (R = Me, 4a; Et, 4b) were alternatively synthesized in quantitative yield by reacting [(IMes)ZnR2] (R = Me, Et) with [(IMes)ZnH2]2 in 2:1 ratio. Methyl complex 4a reacted with CO2 (p(CO2) = 0.5 bar) under facile insertion of CO2 into Zn–H bonds to give dinuclear formate complex [(IMes)ZnMe(O2CH)]2 (5a). Treatment of 4b with CO2 (p(CO2) = 0.5 bar) afforded a mixture of di- and trinuclear formate complexes [(IMes)ZnEt(O2CH)]2 (5b) and [(IMes)2Zn3Et3(O2CH)3] (6) under elimination of one IMes as CO2 adduct IMes·CO2.
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Submitted on : Friday, January 4, 2019 - 11:05:07 AM
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  • HAL Id : hal-01969495, version 1


Arnab Rit, Thomas Spaniol, Laurent Maron, Jun Okuda. Mixed Alkyl Hydrido Complexes of Zinc: Synthesis, Structure, and Reactivity. Organometallics, American Chemical Society, 2014, 33 (8), pp.2039-2047. ⟨hal-01969495⟩



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