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Regioselective Nucleophilic Additions to Diiron Carbonyl Complexes Containing a Bridging Aminocarbyne Ligand: A Synthetic, Crystallographic and DFT Study
Author(s) -
Agonigi Gabriele,
Bortoluzzi Marco,
Marchetti Fabio,
Pampaloni Guido,
Zacchini Stefano,
Zanotti Valerio
Publication year - 2018
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.201701115
Subject(s) - chemistry , moiety , carbyne , regioselectivity , nucleophile , isocyanide , aryl , steric effects , hydride , carbanion , ligand (biochemistry) , cyclopentadiene , methylene , medicinal chemistry , fulvene , stereochemistry , crystallography , organic chemistry , carbene , catalysis , metal , biochemistry , alkyl , receptor
Diiron µ‐aminocarbyne compounds, 1a – e , are prepared in two steps from Fe 2 Cp 2 (CO) 4 , negating the need for difficult purification procedures of intermediate species; they are efficiently isolated by alumina chromatography. Minor amounts of µ‐aminocarbyne aryl isocyanide compounds, 2a – c , are obtained as side products. The structures of the cations in 1a , c , e are calculated using DFT; the carbyne carbon is generally predicted to be the thermodynamic site of hydride addition, in agreement with a previous experimental finding concerning 1a . Accordingly, the reaction of 1e with NaBH 4 affords a bridging aminocarbene complex, 4 , in 85 % yield. Otherwise, the reaction of 1c with NaBH 4 yields the aminocarbyne–cyclopentadiene derivative 3 (70 %), presumably as a consequence of the steric protection exerted by the xylyl–methyl groups towards the carbyne moiety. The sequential treatment of 1a , c with Li 2 CuCNMe 2 and MeSO 3 CF 3 affords 5a , b , comprising both aminocarbyne and alkoxycarbene ligands. In accordance with DFT calculations, the alkoxycarbene moiety in 5a is the most favourable site for nucleophilic attack. Thus, the reactions of 5a with NH 2 R (R = Et, i Pr) and NBu 4 CN, respectively, give the aminocarbyne/aminocarbene complexes, 6a , b , and the aminocarbyne‐α‐cyanoalkyl 7 . All the products are fully characterized by spectroscopic and analytical methods; moreover, the structures of 1a , 1d , 6a and 7 are elucidated by single‐crystal X‐ray diffraction studies.