Oliver Fey

Synthese und reaktivität von silicium-übergangsmetallkomplexen. XXIX. Trihydridosilyl-komplexe von eisen und ruthenium: Ein einfacher Zugang, ligandaustauschreaktionen am metall und schwingungsspektroskopische analyse

Abstract The ferro- and ruthenio-trihydridosilanes (C5R5)(OC)2MSiH3 [R  H, M  Fe (3a), Ru (3b); R  Me, M  Fe (3c), Ru (3d)] are prepared via reaction of the ferro- and ruthenio-dichlorosilanes (C5R5(OC)2 MSiHCl2 (2a−d) with LiAlH4 in Et2O. Photo-induced substitution of CO can be achieved in the case of 3a with Me3P (4a) or Ph3P (4b), leading to the formation of the phosphane-substituted ferro-trihydridosilanes Cp(OC)(L)FeSiH3 [L  Me3P (5a), Ph3P (5b)] and Cp(Me3P)2FeSiH3 (6). The new silicon-transition metal complexes were characterized in detail spectroscopically (NMR, IR, Raman). The structure of 3c has been determined by X-ray structural analysis.

[2+2]-Cycloaddukte PH-funktioneller Phosphenium-Komplexe mit Alkylisothiocyanaten: Darstellung von C5R5(OC)2M–P(H)(t-Bu)–C(NR′)–S (R=H, Me; M=Mo, W; R′=Me, Et, t-Bu) und Reaktion unter Beanspruchung der PH-Funktion: Phosphenium-Übergangsmetallkomplexe, 37

Abstract The phosphenium complex C5Me5(OC)2WP(H)t-Bu (2c) reacts with the alkylisothiocyanates RNCS (R=Me, Et, t-Bu) (3a–c) via [2+2]-cycloaddition to form the PH-functionalized phosphametallacycles C5Me5(OC)2 W–P(H)(t-Bu)–C(NR)–S (R=Me, Et, t-Bu) (4a–c). In the case of the Cp-substituted phosphenium complexes Cp(OC)2MP(H)t-Bu (M=Mo, W) (2a,b) additional insertion of the isothiocyanate into the PH bond occurs yielding the cycloadducts Cp(OC)2 M–P[C(S)NHR](t-Bu)–C(NR)–S (M=Mo, W; R=Me, Et, t-Bu) (5a–c) with high diastereoselectivity. The analogous C5Me5-substituted compounds C5Me5(OC)2 W–P[C(S)N(H)R](t-Bu)–C(NR)–S (R=Me, t-Bu) (5d,e) are only obtained by treatment of 2c with a large excess of 3a,c. Insertion is realized as a separate step for 4c and EtNCS (3b) leading to the formation of isomeric C5Me5(OC)2 W–P[C(S)N(H)R 1 ](t-Bu)–C(NR 2 )–S [R1=Et, R2=t-Bu (6a); R1=t-Bu, R2=Et (6b)]. The structure of 5d is characterized by X-ray diffraction analysis.

Metallo-silanole und metallo-siloxane VII. Zur oxofunktionalisierung von Ruthenio-hydridosilanen mit dimethyldioxiran: Darstellung der ersten Ruthenio-silanole☆☆☆

The ruthenio-hydridosilanes C5Me5(OC)2RuSiR2H [R  Me (3a), o-Tol (3b)] are accessible from the metallating reagent K[Ru(CO)2C5Me5] (1a and the corresponding chlorosilanes R2SiHCl (2a,b). Similarly obtained Cp(OC)2RuSi(H)(p-Tol)Cl (3c) is converted to the ruthenio-dihydridosilane Cp(OC)2RuSi(p-Tol)H2 (4) with LiAlH4.Oxofunctionalization of 3a,b and 4 with dimethyldioxirane affords the novel ruthenio-silanols C5Me5(OC)2RuSiR2OH [R  Me (6a), o-Tol (6b) and Cp(OC)2RuSi(p-Tol)(OH)2 (7). Compound 6b undergoes condensation with Me2Si(H)Cl (2a) to yield the ruthenio-disiloxane C5Me5(OC)2RuSi(o-Tol)2OSiMe2H (8). The structure of 6b, established by X-ray anlaysis, reveals the formation of discrete dimeric units linked by one hydrogen bond. Compound 6b undergoes condensation with The structure of 6b, established by X-ray analysis, reveals the formation of discrete dimeric units linked by one hydrogen bond.

Ubergangsmetall-substituierte Phosphane, Arsane und Stibane, LIX [1], Ein Addukt des Me3P-substituierten Ferrio-diphenylphosphans Cp(OC)(Me3P)Fe-PPh2 mit Methylisothiocyanat: Darstellung, Protonierung und Methylierung / Transition Metal Substituted Phosphanes, Arsanes and Stibanes, LIX [1]. An Adduct of the Me3P-Substituted Ferrio-diphenylphosphane Cp(OC)(Me3P)Fe-PPh2 and Methylisothiocyanate: Synthesis, Protonation, and Methylation

Abstract Treatment of the ferrio-phosphane Cp(OC)2Fe-PPh2 (1) with Me3P (2) yields Cp(OC)(Me3P)Fe-PPh2 (3) via CO-substitution. Reaction of 3 with methylisothiocyanate (4) leads to the formation of the adduct Cp(OC)(Me3P)Fe-PPh2 -C(S)NMe (5), which is regioselectively methylated at the sulfur atom with Mel (6a) or MeSO3CF3 (6b), respectively, to give the cationic complexes [Cp(OC)(Me3P)Fe-PPh2 -C(SMe)=NMe]I/CF3 SO3(7a,b). In contrast, protonation with CF3SO3H (8 ) occurs at the nitrogen atom, yielding [Cp(OC)(Me3P)Fe-PPh2- C(S)-N(H)Me]CF3SO3 (9). The structures of 7b and 9 have been determined by X-ray diffraction analysis