Reactions of Scorpionate-Anchored Yttrium and Lutetium Dialkyls with Terminal Alkynes: From Bimetallic Complexes with Bridging Enynediyl Ligands to Monomeric Terminal Dialkynyl Complexes†
Reactions of Scorpionate-Anchored Yttrium and Lutetium Dialkyls with Terminal Alkynes: From Bimetallic Complexes with Bridging Enynediyl Ligands to Monomeric Terminal Dialkynyl Complexes†
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DOI：
10.1021/om100393w
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发表时间：
2010-11
期刊：
影响因子：
2.8
通讯作者：
Kuburat O Saliu;Jianhua Cheng;R. McDonald;Michael J. Ferguson;J. Takats
中科院分区：
文献类型：
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作者：
Kuburat O Saliu;Jianhua Cheng;R. McDonald;Michael J. Ferguson;J. Takats
研究了蝎尾酸盐锚定的钇和镥二烷基与末端炔的反应，发现络合物的性质取决于辅助蝎尾酸盐配体和炔取代基。（TpMe_2）Ln（CH_2SiMe_3）_2（THF）（1; Ln = Y，Lu）与端炔HC_CR（R = Ph，SiMe_3，tBu，金刚烷基（Ad））反应，得到二聚体配合物。通过单晶X射线衍射测定了其固态结构，结果表明，该配合物由两个不对称的炔基配体和一个偶联的二炔基配体构成两个金属中心，后者表现出不寻常的烯炔键结构：[{（TpMe 2）Ln（μ-C≡CR）}2（μ-RC 4 R）]（Ln = Y，Lu，R = Ph（3），SiMe 3（4），tBu（5）; Ln = Y，R = Ad（6-Y））.配合物3-Y和4-Y与2，4，6-三甲基苯酚的质子分解得到游离炔和（Z）-烯炔的2：1混合物;然而，与5-Y和6-Y一起，除了游离炔之外还得到烯炔和丁三烯。二聚体3-Lu和4-Y在THF中溶解导致桥连单元断裂，
The reactions of scorpionate-anchored yttrium and lutetium dialkyls with terminal alkynes were investigated, and the nature of the complexes was found to depend on both the ancillary scorpionate ligand and the alkyne substituent. Reaction of (TpMe2)Ln(CH2SiMe3)2(THF) (1; Ln = Y, Lu) with the terminal alkynes HC≡CR (R = Ph, SiMe3, tBu, adamantyl (Ad)) afforded dimeric complexes. The solid-state structures, determined by single-crystal X-ray diffraction, showed the two metal centers bridged by two asymmetric alkynyl ligands and a coupled dialkynyl ligand, the latter exhibiting the unusual enyne bonding motif: [{(TpMe2)Ln(μ-C≡CR)}2(μ-RC4R)] (Ln = Y, Lu, R = Ph (3), SiMe3 (4), tBu (5); Ln = Y, R = Ad (6-Y)). Protonolysis of complexes 3-Y and 4-Y with 2,4,6-trimethylphenol gave a 2:1 mixture of free alkyne and (Z)-enyne; however, with 5-Y and 6-Y both enyne and butatriene were obtained in addition to the free alkyne. Dissolution of dimeric 3-Lu and 4-Y in THF resulted in cleavage of the bridging units to give ...