Novel ligand transformations in cluster complexes. Activation of C–F bonds in a perfluorovinyldiiron(I) complex by primary and secondary amines

Abstract

Reactions of primary amines with the perfluorovinyl complex [{Fe(CO)3}2{p-C(SMe)(CF3)CCF2}] 1 proceed with cleavage of two C-F bonds to give 2, whereas with secondary amines fluorine migration and C-F bond rupture afford the novel organometallic complex 3; both 2 and 3 have been characterized by X-ray analysis.

The reaction of ortho-halogenated aromatic aldazine ligands with Fe2(CO)9: symmetrical cleavage of the azine and carbon–halogen activation

“…One of the CO ligands at Fe2 shows a semi-bridging coordination mode towards Fe3 leading to a slightly enhanced iron carbon bond length Fe2-C13 compared to the corresponding bond lengths of terminal CO ligands and a bond angle of Fe2-C13-O6 of 164.0°. Similar trinuclear iron carbonyl cluster compounds with a bridging hydride ligand instead of a formal carbanion have been observed from the reaction of carbonylferrates with nitriles in the presence of a proton source and from the iron induced disproportionation reaction of aromatic azines [15,16]. So we think that the formation of 2a is also due to a disproportionation of 1a into a primary imine and a nitrile and 2a being the product of the reaction of the nitrile with Fe 2 (CO) 9 .…”

“…Scheme 4 shows the reaction of 6 with phosphoric acid leading to the quantitative formation of 7. In analogy to derivatives of 7 the molecular structure is closely related to 6 with the exception, that the iron iron bond between Fe2 and Fe3, which are not coordinated to arylidenamido ligand, now are bridged by a hydride ligand [15,16]. Fig.…”

“…In analogy to the corresponding hydrocarbons the reaction with Fe 2 (CO) 9 proceeds via cleavage of the central N-N bond of the ligand or via the activation of a carbon halogen bond in terms of an ortho-metallation reaction. The latter reactivity is somehow related to the reactions of (perfluorovinyl)diiron complexes with amines, hydrazines, thiols or alcohols with the activation of a vinylic carbon fluorine bond as the initial step of the reaction [16]. The activation of carbon chlorine bonds has been reported during the reaction of Fe 2 (CO) 9 with chlorobutadienes [17].…”

Activation and Functionalization of Vinylic C−F Bonds by Transition Metal Compounds: The Factors Determining Reactions between Nucleophiles and a (Perfluorovinyl)diiron(I) Complex; Syntheses of Diiron Derivatives Containing New C−N, C−S, C−H and C−O Bonds

“…Column chromatography was carried out with silica gel purchased from SDS and deoxygenated before use. The starting materials 1, [18] A, [4d] D [4c] and F [4c] were prepared as described in the literature. All other reagents were purchased commercially.…”

“…After evaporation of the solvent, the residue was washed at Ϫ50°C with pentane (5 mL) to afford 4d as an analytically pure orange solid in 95% yield (59 mg). C 18 3.4 [s,6 H,N(CH 3 ) 2 ], 3.6 (m, 2 H, C α H 2 ), 3.9 (t, 2 H, C α H 2 ). 13 C{ 1 H} NMR (CDCl 3 ): δ ϭ 24.3 (s, C β H 2 ), 26.4 (s, C β H 2 ), 49.8 [s, N(CH 3 ) 2 ], 51.1 (s, C α H 2 ), 54.9 (s, C α H 2 ), 59.7 (q, 2 J C,F ϭ 33.0 Hz, CCF 3 ), 126.8 (q, J C,F ϭ 274.0 Hz, CF 3 ), 192.6 (s, CϭS).…”