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

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 gi...
Ausführliche Beschreibung

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′ = tBu, 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). Ausführliche Beschreibung

Autor*in:	Albano, Vincenzo G. [verfasserIn] Busetto, Luigi Marchetti, Fabio Monari, Magda Zacchini, Stefano Zanotti, Valerio

Format:	Artikel

Erschienen:	2007

Systematik:	VA 8360

Anmerkung:	© 1946 – 2014: Verlag der Zeitschrift für Naturforschung

Übergeordnetes Werk:	Enthalten in: Zeitschrift für Naturforschung. B, Chemical sciences - Verlag der Zeitschrift für Naturforschung, 1947, 62(2007), 3 vom: 01. März, Seite 427-438
Übergeordnetes Werk:	volume:62 ; year:2007 ; number:3 ; day:01 ; month:03 ; pages:427-438

Links:	Volltext

DOI / URN:	10.1515/znb-2007-0317

Katalog-ID:	OLC2136497049