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Synthesis and Characterization of New Diiron and Diruthenium μ-Aminocarbyne Complexes Containing Terminal S-, P- and C-Ligands

2007; De Gruyter; Volume: 62; Issue: 3 Linguagem: Inglês

10.1515/znb-2007-0317

1865-7117

Vincenzo G. Albano, Luigi Busetto, Fabio Marchetti, Magda Monari, Stefano Zacchini, Valerio Zanotti,

Synthesis and characterization of novel inorganic/organometallic compounds

The diiron aminocarbyne complexes [Fe 2 {μ-CN(Me)(R)}(μ-CO)(CO)(NCMe)(Cp) 2 ][SO 3 CF 3 ] (R = Xy1, 1a; R = Me, 1b; R = CH 2 Ph, 1c; Xy1 = 2,6-Me 2 C 6 H 3 ) undergo replacement of the coordinated nitrile by halides, diethyldithiocarbamate, and dicyanomethanide to give [Fe 2 {μ-CN(Me) (R)}(μ-CO)(CO)(X)(Cp) 2 ] complexes (R = Me, X = Br, 4a; R = Me, X = I, 4b; R = CH 2 Ph, X = Cl, 4c; R = CH 2 Ph, X = Br, 4d; R = CH 2 Ph, X = I, 4e; R = Xy1, X = SC(S)NEt 2 , 5a; R = Me, X = SC(S)NEt 2 , 5b; R = Xy1, X = CH(CN) 2 , 7), in good yields. The molecular structure of 5a shows an unusual η 1 coordination mode of the dithiocarbamate ligand. Similarly, treatment of [M 2 {μ-CN(Me) (R)}(μ-CO)(CO)(NCMe)(Cp) 2 ][SO 3 CF 3 ] (M = Fe, R = Xy1, 1a; M = Fe, R = Me, 1b; M = Ru, R = Xy1, 2a; M = Ru, R = Me, 2b) with a series of phosphanes generates the cationic complexes [M 2 {μ- CN(Me)(R)}(μ-CO)(CO)(P)(Cp) 2 ][SO 3 CF 3 ] (M = Fe, R = Xy1, P = PPh 2 H, 6a; M = Fe, R = Xy1, P = PPh 3 , 6b; M = Fe, R = Xy1, P = PMe 3 , 6c; M = Fe, R = Me, P = PMe 2 Ph, 6d; M = Fe, R = Me, P = PPh 3 , 6e; M = Fe, R = Me, P = PMePh 2 , 6f; M = Ru, R = Xy1, P = PPh 2 H, 6g; M = Ru, R = Me, P = PPh 2 H, 6h), in high yields. The molecular structure of 6a has been elucidated by an X-ray diffraction study. The reactions of [Fe 2 {μ-CN(Me)(Xyl)}(μ-CO)(CO)(NCR′)(Cp) 2 ][SO 3 CF 3 ] [R′ = Me, 1a; R′ = t Bu, 3] with PhLi and PPh 2 Li yield [Fe 2 {μ-CN(Me)(Xy1)}(μ-CO)(CO)(Ph)(Cp) 2 ] (8) and [Fe 2 {μ-CN(Me)(Xy1)}(μ-CO)(CO)(PPh 2 )(Cp) 2 ] (9), respectively. The molecular structure of 8 has been ascertained by X-ray diffraction. Conversely, the reaction of 1a with MeLi generates the aminoalkylidene compound [Fe 2 {C(Me)N(Me)(Xy1)}(μ-CO) 2 (CO)(Cp) 2 ] (10). Finally, the acetone complex [Fe 2 {μ-CN(Me)(Xy1)}(μ-CO)(CO)(OCMe 2 )(Cp) 2 ][SO 3 CF 3 ] (12) reacts with lithium acetylides to give complexes [Fe 2 {μ-CN(Me)(Xy1)}(μ-CO)(CO)(C≡CR)(Cp) 2 ] (R = p-C 6 H 4 Me, 11a; R = Ph, 11b; R = SiMe 3 , 11c), in high yields. Filtration through alumina of a solution of 11a in CH 2 Cl 2 results in hydration of the acetylide group and C-Si bond cleavage, affording [Fe 2 {μ-CN(Me)(Xy1)}(μ-CO)(CO){C(O)Me}(Cp) 2 ] (12).