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• W2053261608 abstract "The synthesis of highly strained bicyclic phosphirane and phosphirene iron-tetracarbonyl complexes, that is, complexes with 2-aza-1-phosphabicyclo[n.1.0]alkanes and -alkenes (n = 3-5), is explored by using intramolecular cycloaddition of an in situ generated electrophilic phosphinidene complex, [R(iPr)NP=Fe(CO)(4)], to its C=C- and C[triple chemical bond]C-containing R substituent. Saturated bicyclic complexes 7 a-c with n = 4-2 are remarkably stable, as illustrated by the X-ray crystal structure for 7 b (n=3), yet all readily undergo retroaddition to react with phenylacetylene. Shuttling of the phosphinidene iron complex between two equivalent C=C groups is demonstrated for a 1-butene-substituted 2-aza-1-phosphabicyclo[3.1.0]hexane by selective (1)H NMR magnetization transfer from the phosphirane protons to the olefinic protons. Even the more strained unsaturated bicycles 17 a,b (n = 4,3) are surprisingly stable as illustrated by the X-ray crystal structure for 17 a (n = 4), but the smaller phosphabicyclo[3.1.0]hex-5-ene (17 c, n = 2) dimerizes to tricyclic 19 with a unique ten-membered heterocyclic ring; an X-ray crystal structure is reported. Like their saturated analogues also the bicyclic phosphirenes readily undergo retroaddition as shown by the reaction of their phosphinidene iron moiety with phenylacetylene." @default.
• W2053261608 created "2016-06-24" @default.
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• W2053261608 date "2005-05-30" @default.
• W2053261608 modified "2023-10-17" @default.
• W2053261608 title "Strained, Stable 2-Aza-1-Phosphabicyclo[n.1.0]alkane and -alkene Fe(CO)4 Complexes with Dynamic Phosphinidene Behavior" @default.
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• W2053261608 doi "https://doi.org/10.1002/chem.200401249" @default.
• W2053261608 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/15812871" @default.
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