Alkyl derivatives of europium(+2) and ytterbium(+2). Crystal structures of Eu[C(SiMe(3))(3)](2), Yb[C(SiMe(3))(2)(SiMe(2)CH=CH2)]I center dot OEt(2) and Yb[C(SiMe(3))(2)(SiMe(2)OMe)]I center dot OEt(2)
Alkyl derivatives of europium(+2) and ytterbium(+2). Crystal structures of Eu[C(SiMe(3))(3)](2), Yb[C(SiMe(3))(2)(SiMe(2)CH=CH2)]I center dot OEt(2) and Yb[C(SiMe(3))(2)(SiMe(2)OMe)]I center dot OEt(2)
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DOI：
10.1021/om960493
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发表时间：
1996-10-29
期刊：
影响因子：
2.8
通讯作者：
Smith, JD
中科院分区：
文献类型：
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作者：
Eaborn, C;Hitchcock, PB;Smith, JD
烷基EuR(2) (R = C(SiMe(3))(3)) 和YbR(2) (R = [C(SiMe(3))(2)(SiMe(2)X)], X = Me, CH=CH2, 或CH(2)CH(2)OEt) 是由KR 和MI(2) 之间的反应获得的，以及格氏试剂的镱类似物， Yb[C(SiMe(3))(2)(SiMe(2)X)][. RI 和 Yb 金属之间的反应产生 OEt(2)（X = Me、CH=CH2、Ph 或 OMe）。化合物 YbR(2) 和 EuR(2) 作为无溶剂单体结晶，C-M-C = 136-137 度。烷基镱碘化物从乙醚中以溶剂化的碘化物桥联二聚体形式结晶，其中当 X = Me 时，Yb 处的配位为 4，但当 X = OMe 时，通过与 X 基团的螯合而增加至 5。当 X = CH=CH2 时，Yb...X 相互作用较弱。当 X = Me 时，未观察到反应 2RYbI = R(2)Yb + YbI2，但当 X = Ph、CH=CH2 或 OMe 时很容易发生，并且当无法获得烷基钾 KR 时，例如当 X = OMe 时，提供通向二烷基 MR(2) 的途径。 X = Me 的二烷基 Yb[C(SiMe(3))(2)(SiMe(2)X)](2) 与醚 R'OEt (R' = Et, Bu, Bu(t)) 反应，得到乙烯和醇盐 RYbOR'。当X=OMe时，相应的反应不发生；当X=CH=CH2时，相应的反应非常缓慢。
The alkyls EuR(2) (R = C(SiMe(3))(3)) and YbR(2) (R = [C(SiMe(3))(2)(SiMe(2)X)], X = Me, CH=CH2, or CH(2)CH(2)OEt) have been obtained from reactions between KR and MI(2), and the ytterbium analogues of Grignard reagents, Yb[C(SiMe(3))(2)(SiMe(2)X)][. OEt(2) (X = Me, CH=CH2, Ph or OMe) from reactions between RI and Yb metal. The compounds YbR(2) and EuR(2) crystallize as solvent-free monomers with C-M-C = 136-137 degrees. The alkylytterbium iodides crystallize from diethyl ether as solvated iodide-bridged dimers in which the coordination at Yb is four when X = Me but is increased to five by chelation from the group X when X = OMe. When X = CH=CH2, the Yb...X interaction is weak. The reaction 2RYbI = R(2)Yb + YbI2 is not observed when X = Me, but takes place readily when X = Ph, CH=CH2, or OMe and provides a route to the dialkyls MR(2) when the alkylpotassium KR cannot be obtained, e.g., when X = OMe. The dialkyl Yb[C(SiMe(3))(2)(SiMe(2)X)](2) with X = Me reacts with ethers R'OEt (R' = Et, Bu, Bu(t)) to give ethene and alkoxides RYbOR'. The corresponding reaction does not take place when X = OMe and is very slow when X = CH=CH2.