The room-temperature reactions of the diruthenium μ-allenyl complex [Ru2Cp2(CO)2(NCMe){μ-η1:η2-CH═C═CMe2}]BF4, 3-NCMe, with a series of alkenes, RCH═CH2, afforded the complexes [Ru2Cp2(CO)2{μ-η3:η2-CH(R)CHC(Me)C(Me)CH2}]BF4(R═Ph, 4; 4-C6H4Me, 5; Me, 6; nBu, 7; CO2Me, 8; and H, 9), containing an uncommon pentacarbon alkenyl-allyl ligand. Cross experiments with deuterated reagents, i.e., [Ru2Cp2(CO)2(NCMe){μ-η1:η2-CD═C═CMe2}]BF4(3b-NCMe) and CD2═CD(C6H5) (styrene-d3), revealed that the formation of 4-9 is initiated by an attack of the alkene to the central carbon of the allenyl moiety, triggering two distinct C-H activation processes. Compounds 4-9 were characterized by analytical and spectroscopic methods and by single-crystal X-ray diffraction in the cases of 4, 7, and 8. Reported here is the clean coupling on a metallic scaffold between two C2and C3functions invoked in Fischer-Tropsch mechanistic models.

Carbon???Carbon Bond Coupling of Vinyl Molecules with an Allenyl Ligand at a Diruthenium Complex

Stefano Zacchini
Membro del Collaboration Group
;
2022

Abstract

The room-temperature reactions of the diruthenium μ-allenyl complex [Ru2Cp2(CO)2(NCMe){μ-η1:η2-CH═C═CMe2}]BF4, 3-NCMe, with a series of alkenes, RCH═CH2, afforded the complexes [Ru2Cp2(CO)2{μ-η3:η2-CH(R)CHC(Me)C(Me)CH2}]BF4(R═Ph, 4; 4-C6H4Me, 5; Me, 6; nBu, 7; CO2Me, 8; and H, 9), containing an uncommon pentacarbon alkenyl-allyl ligand. Cross experiments with deuterated reagents, i.e., [Ru2Cp2(CO)2(NCMe){μ-η1:η2-CD═C═CMe2}]BF4(3b-NCMe) and CD2═CD(C6H5) (styrene-d3), revealed that the formation of 4-9 is initiated by an attack of the alkene to the central carbon of the allenyl moiety, triggering two distinct C-H activation processes. Compounds 4-9 were characterized by analytical and spectroscopic methods and by single-crystal X-ray diffraction in the cases of 4, 7, and 8. Reported here is the clean coupling on a metallic scaffold between two C2and C3functions invoked in Fischer-Tropsch mechanistic models.
2022
Giulio Bresciani; Stefano Zacchini; Guido Pampaloni; Fabio Marchetti
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11585/889942
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