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One‐Pot Synthesis of a 1,2‐Diphospholide by Double C–H Deprotonation
Author(s) -
Dixon Lily S. H.,
Matthews Peter D.,
Solomon Sophia A.,
Wright Dominic S.
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201500177
Subject(s) - chemistry , deprotonation , ligand (biochemistry) , cyclopentadienyl complex , phosphorus , medicinal chemistry , stereochemistry , organometallic chemistry , catalysis , ion , organic chemistry , receptor , biochemistry
The relationship between phosphorus and carbon chemistry has been realized for many years. Phosphorus relatives of classical organic ligands (like cyclopentadienide, Cp – ) in which carbon atoms have been substituted for phosphorus atoms are important classes of organometallic ligands, which are relevant to catalysis. Often, however, a limit to applying the phosphorus counterparts is the low‐yielding and circuitous nature of their synthesis. A case in point is the 1,2‐diphospholide ligand framework, an important analogue of the cyclopentadienyl ligand, which has only been obtained from multistep syntheses. We report in this paper a high‐yielding and direct route to this type of framework using a very simple approach. Treatment of MesPHLi (Mes = 2,4,6‐trimethylphenyl) with Sb(NMe 2 ) 3 generates the 5,7‐dimethyl‐1,2‐benzodiphosphol‐1‐ide anion ( 1 ), the first 1,2‐diphospholide analogue of indenyl. Structural and NMR spectroscopic investigations suggest that this unique reaction, involving double C–H deprotonation of a CH 3 group of the Mes ligand, occurs through the rearrangement of a tetraphospha‐1,4‐diide anion.