C-H versus C-C Activation of Biphenylene in Its Reactions with Iron Group Carbonyl Clusters
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- 作者：Wen-Yann Yeh and ; Sodio C. N. Hsu ; Shie-Ming Peng and ; and Gene-Hsiang Lee
- 刊名：Organometallics
- 出版年：1998
- 出版时间：June 8, 1998
- 年：1998
- 卷：17
- 期：12
- 页码：2477 - 2483
- 全文大小：130K
- 年卷期：v.17,no.12(June 8, 1998)
- ISSN：1520-6041
文摘
Co-thermolysis of biphenylene((C6H4)2) withFe3(CO)12 orFe2(CO)9 leads to activationofa biphenylene C-C bond to generateFe2(CO)5(
ntities/mgr.gif">-CO)(ntities/mgr.gif">-
chars/eta.gif" BORDER=0 >2,chars/eta.gif" BORDER=0 >4-(C6H4)2)(1). Similar reactionwith Ru3(CO)12 affordsRu2(CO)5(ntities/mgr.gif">-CO)(ntities/mgr.gif">-chars/eta.gif" BORDER=0 >2,chars/eta.gif" BORDER=0 >4-(C6H4)2)(2) andRu6(CO)17(ntities/mgr.gif">6-C)(3), and thereaction with Os3(CO)12 affordsOs2(CO)6(ntities/mgr.gif">-chars/eta.gif" BORDER=0 >2,chars/eta.gif" BORDER=0 >4-(C6H4)2)(4) andOs4(CO)12(ntities/mgr.gif">4-chars/eta.gif" BORDER=0 >2-(C6H3)Ph)(5). In contrast, treating biphenylene withOs3(CO)10(NCMe)2 leads to C-Hbond activationto give(ntities/mgr.gif">-H)2Os3(CO)9(ntities/mgr.gif">3-chars/eta.gif" BORDER=0 >2-C6H2(C6H4))(6). The new compounds have beencharacterizedby elemental analyses and mass, IR, and NMR spectroscopy. Thestructures of 2, 4, and 5were determined by an X-ray diffraction study. Compound2 and 4 can be viewed to containa metallacyclopentadienyl unit which binds the other metal atom in anchars/eta.gif" BORDER=0 >5-fashion. Compound5 is the first butterfly cluster of the typeOs4(CO)12(aryne).
ntities/mgr.gif">-CO)(ntities/mgr.gif">-chars/eta.gif" BORDER=0 >2,chars/eta.gif" BORDER=0 >4-(C6H4)2)(1). Similar reactionwith Ru3(CO)12 affordsRu2(CO)5(ntities/mgr.gif">-CO)(ntities/mgr.gif">-chars/eta.gif" BORDER=0 >2,chars/eta.gif" BORDER=0 >4-(C6H4)2)(2) andRu6(CO)17(ntities/mgr.gif">6-C)(3), and thereaction with Os3(CO)12 affordsOs2(CO)6(ntities/mgr.gif">-chars/eta.gif" BORDER=0 >2,chars/eta.gif" BORDER=0 >4-(C6H4)2)(4) andOs4(CO)12(ntities/mgr.gif">4-chars/eta.gif" BORDER=0 >2-(C6H3)Ph)(5). In contrast, treating biphenylene withOs3(CO)10(NCMe)2 leads to C-Hbond activationto give(ntities/mgr.gif">-H)2Os3(CO)9(ntities/mgr.gif">3-chars/eta.gif" BORDER=0 >2-C6H2(C6H4))(6). The new compounds have beencharacterizedby elemental analyses and mass, IR, and NMR spectroscopy. Thestructures of 2, 4, and 5were determined by an X-ray diffraction study. Compound2 and 4 can be viewed to containa metallacyclopentadienyl unit which binds the other metal atom in anchars/eta.gif" BORDER=0 >5-fashion. Compound5 is the first butterfly cluster of the typeOs4(CO)12(aryne).