ISSN:
1434-1948
Keywords:
Coordination chemistry
;
α-Imino ketones
;
CO complexes
;
Iron complexes
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The reaction of Fe2(CO)9 at room temperature in THF or toluene with the α-imino ketones R1N=C(R2)-C(R3)=O (L) (R1 = alkyl, R2 = H, Me, Ph, R3 = Me, Ph) (a-k), initially results in the formation of the mononuclear chelate Fe(CO)3(α-imino ketone) complexes 6 which can be isolated in moderate (6h) to high (6e-g) yield. Under these reaction conditions, complexes 6 subsequently react with [Fe(CO)4] fragments or dimerise, to form the dinuclear complexes Fe2(CO)6(α-imino ketone) (7a-j) or Fe2(CO)4(L-L) (8a,b,k), respectively. The complexes 8 contain two α-imino ketone ligands C-C coupled at the ketone carbon atoms. Complexes 8a,b react with CO at elevated temperatures to quantitatively yield Fe(CO)3(α-imino ketone) (6a,b). This reaction can be reversed photochemically. Irradiation of a solution of 6a,b in the low-energy band results in the reformation of 8a,b in almost quantitative yield. The extremely air-sensitive complexes 6 and the dinuclear complexes 7 and 8 have been characterised spectroscopically (IR, UV/Vis, 1H and 13C NMR) and by elemental analysis. The solid state structures of complexes 6g and 8a have been determined by single-crystal X-ray diffraction. The molecular structure of 6g confirms the flat σ-O,σ-N chelate coordination of the α-imino ketone. The structure of 8a consists of two metal-metal-bonded Fe(CO)2 units, bridged by a formally 10e-donating dianionic C-C coupled (tBu-ADO) ligand. A mechanism for the formation of complexes 8 is discussed.Supporting information for this article is available on the WWW under -//_/_http://www.wiley-vch.de/contents/jc_2005/2000/99351_s.pdf or from the author.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
