G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Tropinina 49, Nizhny Novgorod 603600, Russia.
Inorg Chem. 2010 Mar 15;49(6):2901-10. doi: 10.1021/ic902439x.
The reduction of 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-Bian) with an excess of samarium in 1,2-dimethoxyethane (dme) affords the Sm(II) complex (dpp-Bian)Sm(dme)(3) (1). The reaction of 1 with 0.5 mol equiv of 1,2-dibromostilbene proceeds with the formation of the dimeric Sm(III) complex (dpp-Bian)SmBr(dme) (2). Oxidation of both the metal and the dpp-Bian ligand takes place if 1 is reacted with equimolar amounts of 1,2-dibromostilbene or iodine, yielding the monomeric Sm(III) derivatives (dpp-Bian)SmBr(2)(dme) (3) and (dpp-Bian)SmI(2)(THF)(2) (4; THF = tetrahydrofuran), respectively. The reaction of 1 with 0.5 mol equiv of iodine followed by 0.5 mol equiv of tetramethylthiuram disulfide gives the Sm(III) complex (dpp-Bian)SmISC(S)NMe(2) (5). Compound 4 and tBuOK react with the formation of the iodine-bridged dimer (dpp-Bian)SmI(OtBu)(THF) (6). Complexes 1 and 2 have been characterized by (1)H NMR spectroscopy and complexes 2-6 by their molecular structures, which were determined by single-crystal X-ray diffraction.
1,2-双[(2,6-二异丙基苯基)亚氨基]吖啶（dpp-Bian）与过量钐在 1,2-二甲氧基乙烷（dme）中还原得到 Sm(II)配合物(dpp-Bian)Sm(dme)(3)（1）。1 与 0.5 mol 当量的 1,2-二溴二苯乙烯反应生成二聚 Sm(III)配合物(dpp-Bian)SmBr(dme)（2）。如果 1 与等摩尔量的 1,2-二溴二苯乙烯或碘反应，金属和 dpp-Bian 配体都会发生氧化，分别得到单体 Sm(III)衍生物(dpp-Bian)SmBr(2)(dme)（3）和(dpp-Bian)SmI(2)(THF)(2)（4；THF = 四氢呋喃）。1 与 0.5 mol 当量的碘反应，然后与 0.5 mol 当量的四甲基秋兰姆二硫化物反应，得到 Sm(III)配合物(dpp-Bian)SmISC(S)NMe(2)（5）。化合物 4 和 tBuOK 反应生成碘桥联二聚体(dpp-Bian)SmI(OtBu)(THF)（6）。配合物 1 和 2 通过（1）H NMR 光谱进行了表征，配合物 2-6 通过其分子结构进行了表征，这些结构通过单晶 X 射线衍射确定。
