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• W2044497791 startingPage "13405" @default.
• W2044497791 abstract "Abstract A first computational insight into the intrinsic strength of exocyclic bonds to phosphorus in oxaphosphirane κP‐pentacarbonylmetal(0) complexes 1 a – f (M=Cr, Mo) is provided using a set of PR derivatives (R=Me, t Bu, CPh 3 ). Whereas homolytic cleavage of the exocyclic PR bond was found to be always unfavored (for neutral complexes), heterolytic cleavage leading to a carbocation R + moiety and the oxaphosphiranide complex 2 − constitutes the lowest‐energy process, especially if R is bulky and can stabilize the positive charge, that is, triphenylmethyl (trityl), efficiently. The energies required for PM bond cleavage are about 30 kcal mol −1 , and decrease with the increasing bulk of the R substituent (from Me to trityl) and ongoing from Cr to Mo. The reactivities of complexes 1 a – f towards oxidative and reductive single electron transfer (SET) reactions were analyzed using the facile variation of bond‐strength‐related descriptors (VBSD) methodology, thus enabling the design of synthetically useful strategies addressing decomplexation and P‐functionalization. Reductive SET reactions with sodium naphthalenides enable selective PM bond cleavage (i.e., decomplexation) for the case of P‐Me and P‐ t Bu substitution, whereas reductive PR bond cleavage is favored in the case of the P‐trityl complexes 1 c , f , and results in the formation of the (anionic) oxaphosphiranide complex 2 − , which may be regarded as a potential key intermediate for further P‐functionalization." @default.
• W2044497791 created "2016-06-24" @default.
• W2044497791 creator A5055925650 @default.
• W2044497791 creator A5082971547 @default.
• W2044497791 date "2012-09-05" @default.
• W2044497791 modified "2023-10-18" @default.
• W2044497791 title "Exocyclic Bond Cleavage in Oxaphosphirane Complexes?" @default.
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• W2044497791 doi "https://doi.org/10.1002/chem.201201057" @default.
• W2044497791 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/22951978" @default.
• W2044497791 hasPublicationYear "2012" @default.
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