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Construction of a Functionalized Selenophene‐Allylidene Ligand via Alkyne Double Action at a Diiron Complex
Author(s) -
De Palo Alice,
Zacchini Stefano,
Pampaloni Guido,
Marchetti Fabio
Publication year - 2020
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202000371
Subject(s) - chemistry , alkyne , ligand (biochemistry) , stereochemistry , cycloaddition , reactivity (psychology) , thiophene , medicinal chemistry , catalysis , medicine , receptor , alternative medicine , organic chemistry , pathology , biochemistry
The diiron µ‐vinyliminium compounds [Fe 2 Cp 2 (CO)(µ‐CO){µ‐η 1 :η 3 ‐C 3 HC 2 HC 1 NMe(R)}]CF 3 SO 3 (R = Me, 2a ; R = Xyl = 2,6‐C 6 H 3 Me 2 , 2b ; Cp = η 5 ‐C 5 H 5 ) reacted with grey selenium, in the presence of sodium methoxide, to give the corresponding Se‐functionalized derivatives [Fe 2 Cp 2 (CO)(µ‐CO){µ‐η 1 :η 3 ‐C 3 HC 2 (Se)C 1 NMe(R)}], 3a – b , in ca. 50 % yields. The monoiron zwitterionic complex [FeCp(CO){SeC 1 (NMe 2 )C 2 HC 3 H}], 4 , was obtained as a side‐product (31 %) of the reaction leading to 3a . The treatment of 3b with S 8 /NaOMe afforded the 2‐ferra‐thiophene [FeCp(CO){SC 3 HC 2 HC 1 NMe(Xyl)}], 5 , in 49 % yield. The straightforward reactions of 3a with a two‐fold excess of dialkylacetylenedicarboxylates led to functionalized 3‐amino‐selenophenes appended to the diiron frame through a bridging allylidene ligand, [Fe 2 Cp 2 (CO)(µ‐CO){µ‐η 1 :η 3 ‐C 7 (CO 2 R)C 6 (CO 2 R)C 3 HC 2 SeC 5 (CO 2 R)C 4 (CO 2 R)C 1 (NMe 2 )}] (R = Me, 6a ; R = Et, 6b ; R = t Bu, 6c ), in approximately 50 % yields. The synthesis of 6a – c is the result of two distinct modes of reactivity exhibited by the alkyne reactant in one pot, i.e. 1,3‐dipolar cycloaddition to C and Se atoms and insertion into Fe‐µ‐alkylidene. All the products were characterized by means of elemental analysis, IR and multinuclear NMR spectroscopy, and the molecular structure of 6a was elucidated by a single‐crystal X‐ray diffraction study.