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Mixed alkyl hydrido complexes of zinc: Synthesis, structure, and reactivity
, Spaniol T.P., Maron L., Okuda J.
Published in American Chemical Society
Volume: 33
Issue: 8
Pages: 2039 - 2047
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 [(Me 3TACD)(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)ZnEt2(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)2Zn 3Et3(O2CH)3] (6) under elimination of one IMes as CO2 adduct IMes·CO2. © 2014 American Chemical Society.
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JournalData powered by TypesetOrganometallics
PublisherData powered by TypesetAmerican Chemical Society
Open AccessNo