Abstract
An extended range of novel ruthenium phosphaalkene complexes of the type [Ru{η1-N:η2-P,C-P(pz′)=CH(SiMe2R)}(CO)(PPh3)2] (R = Tol, C6H4CF3-p; pz′ = pzMe2, pzCF3, pzMe,CF3; R = Me, C6H4CF3-p; pz′ = pzPh) have been prepared from the respective ruthenaphosphaalkenyls [Ru{P=CH(SiMe2R)}Cl(CO)(PPh3)2] upon treatment with Lipz′. Where R = C6H4CF3-p and pz′ = pzMe2 the complex is characterized by single crystal X-ray diffraction, only the second example of such species being structurally characterized. This indicates enhanced pyramidalisation of the alkenic carbon center when compared with precedent data (R = Me, pz′ = pz) implying an enhanced Ru→π*PC contribution, which can be correlated with the greater donor power of pzMe2. This is similarly reflected in spectroscopic data that reveal significant influence of the pyrazolyl substituents upon the phosphaalkene, stronger donors imparting significantly enhanced shielding to phosphorus; in contrast, a much lesser influence if noted for the silyl substituents.
Highlights
After almost half a century of study, the chemistry of low-coordinate phosphorus continues to fascinate both organic and inorganic chemists alike [1,2,3,4,5,6,7,8]
1a–b to engage in that demonstrate a nucleophilic phosphorus center [35,36,37,38,39]; in common with these precedent reaction with electrophilic fragments at phosphorus reports, we have found 1a–b to engage in reaction with electrophilic fragments at phosphorus
In seeking to assess the influence of reactivity, weand report the synthesis and means characterization an reactivity, extended range of these novel such factors, thusherein potentially to elaborate of control of over we report the pyrazolylphosphaalkene complex
Summary
After almost half a century of study, the chemistry of low-coordinate phosphorus continues to fascinate both organic and inorganic chemists alike [1,2,3,4,5,6,7,8]. Dominated by the isolobal and isoelectronic relationship between phosphorus and the “CH” fragment, the chemistry of phosphacarbons is often familiar from their carbo-centric and nitrogenous counterparts, yet they simultaneously embody appreciable dichotomy in terms of their underlying electronic and chemical nature Nowhere is this more apparent than in the chemistry of phosphaalkenes (RP=CR0 R”) and phosphaalkynes (RC≡P), which rank among the most heavily studied classes of phosphacarbon. The phosphaalkyne lone-pair is appreciably stabilized, but can be engaged chemically under appropriately directing conditions The study of these compounds is, often complicated by an intrinsic lack of stability, which restricts the range of available substrates and necessitates some synthetic ingenuity. The formally related phosphaethynyloate ion “O–C≡P− ” is isolable as a sodium salt [13,14], which exhibits appreciable stability despite the lack of any steric “protection”; this fact is attributed to electronic influences, with
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
