Reactivity of (C5Me5)(2)Sm(THF)(2) with nitriles: C-C bond cleavage to form cyanide complexes

Evans WJ; Montalvo E; Foster SE; Harada KA; Ziller JW

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Reactivity of (C5Me5)(2)Sm(THF)(2) with nitriles: C-C bond cleavage to form cyanide complexes

机译：（C5Me5）（2）Sm（THF）（2）与腈的反应性：C-C键裂解形成氰化物配合物

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The divalent organosamarium complex (C5Me5)(2)Sm(THF)(2) (1) reacts in toluene with Me3CCN to form the insoluble trivalent cyanide complex [(C5Me5)(2)SmCN](n) (2). The Me3CCN reaction was found to proceed through divalent (C5Me5)(2)Sm(NCCMe3)(THF)(x) (3). The bis(nitrile) analogue of 3, (C5Me5)(2)Sm(NCCMe3)(2)(THF) (4), is isolable from the reaction of 1 with Me3CCN in THF and has been characterized by X-ray crystallography. Both 3 and 4 transform via C-C bond cleavage to form the cyanide product 2 and (C5Me5)(2)Sm(NCHCMe3)(THF) (5). Complex 5 is the product of insertion of Me3CCN into a Sm-H bond presumably formed by beta-hydrogen elimination of a Me3C intermediate. Complexes 2 and 5 can also be generated by the stoichiometric reaction of crystalline 4 with 1 in toluene. Complex 5 can be synthesized directly from the reaction of [(C5Me5)(2)Sm(mu-H)](2) with Me3CCN and THF. Crystallographic data on the related nitrile adducts [(C5Me5)(2)Sm(NCCMe3)(mu-CN)](3) (6) and [(C5Me5)(2)Sm(NCCMe3)](2)(mu-O) (7) are also reported.

机译：二价有机sa络合物（C5Me5）（2）Sm（THF）（2）（1）在甲苯中与Me3CCN反应形成不溶性三价氰化物络合物[（C5Me5）（2）SmCN]（n）（2）。发现Me3CCN反应通过二价（C5Me5）（2）Sm（NCCMe3）（THF）（x）（3）进行。 3的双（腈）类似物（C5Me5）（2）Sm（NCCMe3）（2）（THF）（4）可从1与Me3CCN在THF中的反应中分离出来，并通过X射线晶体学进行了表征。 3和4均通过C-C键裂解而转化为氰化物产物2和（C5Me5）（2）Sm（NCHCMe3）（THF）（5）。配合物5是Me3CCN插入Sm-H键的产物，该Sm-H键大概是由Me3C中间体的β-氢消除形成的。配合物2和5也可以通过晶体4与1在甲苯中的化学计量反应生成。配合物5可以直接由[（C5Me5）（2）Sm（mu-H）]（2）与Me3CCN和THF反应合成。有关腈加合物[（C5Me5）（2）Sm（NCCMe3）（mu-CN）]（3）（6）和[（C5Me5）（2）Sm（NCCMe3）]（2）（mu-O）的晶体学数据）（7）也有报道。

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《Organometallics》 |2007年第11期|共7页
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Evans WJ; Montalvo E; Foster SE; Harada KA; Ziller JW;
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正文语种 eng
中图分类有机化学;
关键词
RAY CRYSTAL-STRUCTURE; EXHIBITING ENHANCED REACTIVITY; PLANAR TRIMETHYLENEMETHANE DIANION; OXIDATIVE-ADDITION-REACTIONS; ARYL HALIDES; CRYSTALLOGRAPHIC CHARACTERIZATION; LANTHANIDE METALLOCENES; REDUCTIVE DECYANATION; H ACTIVATION; ORGANOLANTHANIDE;

机译：射线晶体结构;显示出增强的反应性;平面三亚甲基亚乙基二阴离子;氧化加成反应;芳基卤化物;结晶学特征;镧系金属茂;还原性脱氰;H活化;有机;

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1. Reactivity of (C5Me5)(2)Sm(THF)(2) with nitriles: C-C bond cleavage to form cyanide complexes [J] . Evans WJ, Montalvo E, Foster SE, Organometallics . 2007,第11期

机译：（C5Me5）（2）Sm（THF）（2）与腈的反应性：C-C键裂解形成氰化物配合物
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Reactivity of (C5Me5)(2)Sm(THF)(2) with nitriles: C-C bond cleavage to form cyanide complexes

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