Reaction of Me3SiONa with [Re(CO)5Cl] affords the new complex Na[Re2(CO)6(μ-OSiMe3)3], which could be generated via formation of [Re(CO)5OSiMe3] followed by immediate reaction with Me3SiO-. Substitution of some CO ligands by phosphines significantly decreases the electrophilicity of the Re(I) center, and therefore hinders further attack by Me 3SiO-. Thus, fac-[Re(CO)3(Ph2PCH2CH2PPh2)OTf] (OTf is the triflate anion) reacts with Me3SiONa to give fac-[Re(CO)3(Ph2PCH2CH2PPh2) OSiMe3], a molecular model of silica anchored [Re(CO)5OSi]. However, substitution of only one CO by triphenylphosphine is not enough to avoid the formation of [Re 2(CO)6(μ-OSiMe3)3]-. While fac-[Re(CO)3(Ph2PCH2CH 2PPh2)OSiMe3] is stable towards hydrolysis, [Re2(CO)6(μ-OSiMe3)3] - is readily hydrolyzed to [Re2(CO)6(μ-OH) (μ-OSiMe3)2]-, a molecular model of silica anchored [Re2(CO)6(μ-OH)(μ-OSi) 2]-, whose structure has been determined by single crystal X-ray diffraction.

Surface organometallic chemistry — Carbonyl complexes of Re(I) with silanolates as models of silica anchored rhenium carbonyl species

GALLI, SIMONA;
2005

Abstract

Reaction of Me3SiONa with [Re(CO)5Cl] affords the new complex Na[Re2(CO)6(μ-OSiMe3)3], which could be generated via formation of [Re(CO)5OSiMe3] followed by immediate reaction with Me3SiO-. Substitution of some CO ligands by phosphines significantly decreases the electrophilicity of the Re(I) center, and therefore hinders further attack by Me 3SiO-. Thus, fac-[Re(CO)3(Ph2PCH2CH2PPh2)OTf] (OTf is the triflate anion) reacts with Me3SiONa to give fac-[Re(CO)3(Ph2PCH2CH2PPh2) OSiMe3], a molecular model of silica anchored [Re(CO)5OSi]. However, substitution of only one CO by triphenylphosphine is not enough to avoid the formation of [Re 2(CO)6(μ-OSiMe3)3]-. While fac-[Re(CO)3(Ph2PCH2CH 2PPh2)OSiMe3] is stable towards hydrolysis, [Re2(CO)6(μ-OSiMe3)3] - is readily hydrolyzed to [Re2(CO)6(μ-OH) (μ-OSiMe3)2]-, a molecular model of silica anchored [Re2(CO)6(μ-OH)(μ-OSi) 2]-, whose structure has been determined by single crystal X-ray diffraction.
D'Alfonso, Giuseppe; Dragonetti, Claudia; Galli, Simona; Lucenti, Elena; Macchi, Piero; Roberto, Dominique; Ugo, Renato
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11383/6484
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