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The Reactivity Studies on the Binuclear Heterobimetallic Y/Al "Methylidyne" Complex
Wen Jiang1, Yumeng Yang1, Mengyue Guo1
1Department of Chemistry, Jiangwan Campus, Fudan University, 2005 Songhu Road, Shanghai 200438, P. R. China.
None:
The low activity of metal bridging carbynes has been widely known. Herein, a binuclear heterobimetallic Y/Al "methylidyne" complex 1 underwent nucleophilic addition reactions toward 2, 6-Me2C6H3NC and PhCH2CN, respectively yielding monoinsertion products L2Y2[μ-η1:η3:η3-HCC(2,6-Me2C6H3)N](AlMe3)(μ2-Me) (L = (PhCH2)2NC(NC6H3iPr2-2,6)2) (2) and L2Y2[μ-η1:η3:η3-HCC-(CH2Ph)N](AlMe3)(μ2-Me) (3). Additionally, complex 1 was treated with iPrN═C═NiPr (DIC) (5 equiv), obtaining a yttrium complex LY[(AlMe2)(NiPr2)2CCHC(NiPr2)2(AlMe2)][(NiPr2)2CMe] (4) featuring an Al-heterocyclic six-membered ring structure and a mixed guanidinate/amidinate yttrium complex LY[(NiPr2)2CMe]2 (5). Complex 1 reacted with CS2 (2 equiv), leading to the formation of the binuclear yttrium disulfides L2Y2(μ2-S)(μ2-η1:η2-S2)(AlMe3)2 (6) through the cleavage of both C═S bonds in CS2. Furthermore, a mixed μ4-CH/μ2-C≡CSiMe3 yttrium complex [LY(AlMe3)]2(μ2-C≡CSiMe3)(μ4-CH) (9) was synthesized through the protonolysis of Me3SiC≡CH (1 equiv) with complex 1. Interestingly, the bimetallic alkynyl-bridged yttrium complex [LY(μ-C≡CSiMe3)]2(μ-(Z)-Me3SiC═C═C═CSiMe3) (10) was isolated when the Me3SiC≡CH (4 equiv) was treated with complex 1. Notably, in the presence of PhSSPh, complex 1 exhibited distinctive reactivity to CO, undergoing a CO deoxygenative coupling reaction that ultimately yielded a yttrium oxo complex L2Y2(μ3-O)(AlMe3)(μ2-SPh)(μ2-C≡CMe) (12), and the mixed μ4-CH/μ2-SPh yttrium complex L2Y2(μ4-CH)(μ2-SPh)(AlMe3)2 (11) was identified as a key intermediate in this transformation.
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