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A Nontrigonal Tricoordinate Phosphorus Ligand Exhibiting Reversible “Nonspectator” L/X‐Switching
Author(s) -
Cleveland Gregory T.,
Radosevich Alexander T.
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201909686
Subject(s) - chemistry , ligand (biochemistry) , reactivity (psychology) , crystallography , fluoride , trigonal crystal system , crystal structure , phosphorus , stereochemistry , inorganic chemistry , organic chemistry , receptor , medicine , biochemistry , alternative medicine , pathology
We report here a “nonspectator” behavior for an unsupported L ‐function σ 3 ‐P ligand (i.e. P{N[ o ‐NMe‐C 6 H 4 ] 2 }, 1a ) in complex with the cyclopentadienyliron dicarbonyl cation (Fp + ). Treatment of 1a ⋅Fp + with [(Me 2 N) 3 S][Me 3 SiF 2 ] results in fluoride addition to the P ‐center, giving the isolable crystalline fluorometallophosphorane 1a F ⋅Fp that allows a crystallographic assessment of the variance in the Fe−P bond as a function of P‐coordination number. The nonspectator reactivity of 1a ⋅Fp + is rationalized on the basis of electronic structure arguments and by comparison to trigonal analogue (Me 2 N) 3 P⋅Fp + (i.e. 1b ⋅Fp + ), which is inert to fluoride addition. These observations establish a nonspectator L/X‐switching in (σ 3 ‐P)–M complexes by reversible access to higher‐coordinate phosphorus ligand fragments.