(Tetramethylcyclobutadiene)cobalt Complexes with Five-Electron Carbo- and Heterocyclic Ligands†
(Tetramethylcyclobutadiene)cobalt Complexes with Five-Electron Carbo- and Heterocyclic Ligands†
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具有五电子碳环和杂环配体的（四甲基环丁二烯）钴配合物†
DOI：
10.1021/om0495832
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发表时间：
2004
期刊：
影响因子：
2.8
通讯作者：
A. Kudinov
中科院分区：
文献类型：
--
作者：
E. V. Mutseneck;D. Loginov;D. Perekalin;Z. Starikova;D. G. Golovanov;P. Petrovskii;P. Zanello;M. Corsini;F. Laschi;A. Kudinov
四甲基环丁二烯（Ⅲ）钴配合物Cb*Co（C5 H4 R）（Cb* = η4-C4Me4; R = H（5a），Me（5b），SiMe3（5d），C（O）H（5f），和C（O）Me（5g））通过环戊二烯阴离子与（羰基）碘络合物Cb*Co（CO）2 I（1）（方法A）或与更具反应性的乙腈络合物[Cb*Co（MeCN）3]+（2）（方法B）。类似化合物CB*CoCp*（5 c）、CB*Co（1，3-C5 H3（SiMe 3）2）（5 e）和CB*Co（η5-茚基）（6）只能通过方法B制备。用NaBH 4/AlCl 3或LiAlH 4处理5 f，g分别得到烷基衍生物5 b和5 h（R = Et）或醇5i（R = CH 2 OH）和5 j（R = CH（OH）Me）。1与芴/AlCl_3反应生成配合物[Cb ~*Co（η ~ 6-芴）]~+（8），用KOBut脱质子得到Cb ~*Co（η ~ 6-芴基）（9）。9在可见光照射下发生η6→η5亲触重排反应，生成Cb*Co（η5-芴基）（7）。吡咯基和磷酰基配合物Cb*Co（C4 R4 N）（R = H（10a），Me（10 c））和Cb*Co（C4 R4 P）（R = H（11 a），Me（11 c）; R4 = H2 Me 2（1.
Tetramethylcyclobutadiene(cyclopentadienyl)cobalt complexes Cb*Co(C5H4R) (Cb* = η4-C4Me4; R = H (5a), Me (5b), SiMe3 (5d), C(O)H (5f), and C(O)Me (5g)) were obtained by reaction of cyclopentadienide anions either with the (carbonyl)iodide complex Cb*Co(CO)2I (1) (method A) or with the more reactive acetonitrile complex [Cb*Co(MeCN)3]+ (2) (method B). Analogous compounds Cb*CoCp* (5c), Cb*Co(1,3-C5H3(SiMe3)2) (5e), and Cb*Co(η5-indenyl) (6) can be prepared only by method B. Treatment of 5f,g with NaBH4/AlCl3 or LiAlH4 affords the alkyl derivatives 5b and 5h (R = Et) or the alcohols 5i (R = CH2OH) and 5j (R = CH(OH)Me), respectively. The reaction of 1 with fluorene/AlCl3 yields complex [Cb*Co(η6-fluorene)]+ (8), which was deprotonated by KOBut to give Cb*Co(η6-fluorenyl) (9). Visible light irradiation of 9 induces η6→η5 haptotropic rearrangement to afford Cb*Co(η5-fluorenyl) (7). The pyrrolyl and phospholyl complexes Cb*Co(C4R4N) (R = H (10a), Me (10c)) and Cb*Co(C4R4P) (R = H (11a), Me (11c); R4 = H2Me2 (1...