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Title: A Nontrigonal Tricoordinate Phosphorus Ligand Exhibiting Reversible “Nonspectator” L/X‐Switching
Abstract

We report here a “nonspectator” behavior for an unsupportedL‐function σ3‐P ligand (i.e. P{N[o‐NMe‐C6H4]2},1a) in complex with the cyclopentadienyliron dicarbonyl cation (Fp+). Treatment of1a⋅Fp+with [(Me2N)3S][Me3SiF2] results in fluoride addition to theP‐center, giving the isolable crystalline fluorometallophosphorane1aF⋅Fp that allows a crystallographic assessment of the variance in the Fe−P bond as a function of P‐coordination number. The nonspectator reactivity of1a⋅Fp+is rationalized on the basis of electronic structure arguments and by comparison to trigonal analogue (Me2N)3P⋅Fp+(i.e.1b⋅Fp+), which is inert to fluoride addition. These observations establish a nonspectator L/X‐switching in (σ3‐P)–M complexes by reversible access to higher‐coordinate phosphorus ligand fragments.

 
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NSF-PAR ID:
10117159
Author(s) / Creator(s):
 ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Angewandte Chemie
Volume:
131
Issue:
42
ISSN:
0044-8249
Page Range / eLocation ID:
p. 15147-15151
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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