UBC Theses and Dissertations
Reactions of CpW(NO)(CH₂SiMe₃)₂ with Lewis acids : characteristic chemistry of CpW(NO)(CH₂SiMe₃)(CH₂CPh₃) Brunet, Nathalie
The nitrosyl complex CpW(NO)R₂ (R = CH₂SiMe₃) forms 1:1 adducts via isonitrosyl linkages to Lewis acids such as AlMe₃ and Cp₃Er, i.e. CpWR₂(NO→A) (A = AlMe₃, ErCp₃). These adducts regenerate the starting dialkyl complex when treated with water. Protonation of CpW(NO)R₂ by HBF₄⋅0Me₂ can also be effected. Whether the site of protonation is the nitrogen or the oxygen atom of the nitrosyl ligand is not known with certainty, although O-protonation is postulated by analogy with the other Lewis-acid adducts of CpW(NO)R₂. In these adducts, the nitrosyl stretching frequency is shifted to lower wavenumbers relative to that of the parent dialkyl, to an extent which increases as harder Lewis acids are employed. The colour of the adducts also ranges from red to orange to yellow as progressively harder acids are used. Treatment of CpW(NO) (CH₂SiMe₃)₂ with [Ph₃C]⁺ PF₆⁻ in Ch₂CL₂ results in electrophilic cleavage of a carbon-silicon bond to yield the mixed dialkyl CpW(NO)(CH₂SiMe₃)(CH₂CPh₃), which has been fully characterized by spectroscopic methods and by a single-crystal X-ray crystallographic study. The formation of Me₃SiF and PF₅ (coordinated to Lewis bases in the reaction mixture) as by-products of this reaction has been confirmed by ³¹P and ¹⁹F NMR spectroscopy of the reaction mixture in CD₂CL₂. Preliminary attempts to extend this novel reaction of a silicon-containing ligand by using other carbocations were unsuccessful. This is attributed to the high reactivity of the required carbocations and the large number of possible reaction sites on the metal complex. Some reactions of the mixed dialkyl CpW(NO)RR¹ (R = CH₂SiMe₃ R¹ = CH₂CPh₃) were found to be analogous to those of the parent CpW(NO)R₂, while other reactions followed a different course because of the ability of the CH₂CPh₃ ligand to orthometallate. Thus, CpW(NO)RR¹ is much less thermally stable than CpW(NO)R₂. As a solid or a solution in non-coordinating solvents, it decomposes in a matter of days at room temperatures to a mixture of products which were not identified. In acetonitrile solution, an orthometallated complex derived from CpW(NO)RR¹ can be trapped by coordination of solvent. The product CpW(NO)(CH₂C(C₆H₄)Ph₂)(NCMe) has been isolated and crystallographically characterized. Cyclic voltammograms of CpW(NO)R₂ and CpW(NO)RR¹ show that both complexes undergo an apparently chemically reversible reduction and an irreversible oxidation. The mixed dialkyl CpW(NO)RR¹ is somewhat easier both to reduce and to oxidize than CpW(NO)R₂. Like CpW(NO)R₂, CpW(NO)RR¹ reversibly forms a 1:1 adduct with PMe₃. Also analogously to CpW(NO)R₂, it reacts with 0₂ to form a 5:1 mixture of dioxoalkyl complexes CpW(0)₂R and CpW(0)₂R¹, and with NO(g) to form 2 CpW(NO)R¹(ƞ² -0₂N₂R). In this product, insertion of NO has occurred exclusively in the W-CH₂SiMe₃ bond. Upon photolysis, both complexes CpW(NO)R¹¹(ƞ²-0₂N₂R) (R¹¹ = CH₂SiMe₃ or CH₂CPh₃) form dioxo alkyls CpW(O)₂R¹¹ in an unprecedented reaction. The ability of CpW(NO)RR¹ to orthometallate also results in the formation, when this complex is treated with sulphur, of CpW(O)(CH₂C(C₆H₄)Ph₂)-(SR). No analogue to this compound can be obtained from reaction of CpW(NO)R₂ with sulphur. The sequence of reactions leading to the formation of this product is not known.
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