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Dearomatization of the PCP Pincer Ligand in a Re V Oxo Complex
Author(s) -
Kosanovich Alex J.,
Komatsu Christopher H.,
Bhuvanesh Nattamai,
Pérez Lisa M.,
Ozerov Oleg V.
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201802589
Subject(s) - rhenium , deprotonation , ligand (biochemistry) , chemistry , pincer movement , carbenoid , cycloaddition , stereochemistry , pincer ligand , medicinal chemistry , osmium , catalysis , ruthenium , organic chemistry , rhodium , ion , biochemistry , receptor
A high‐valent, rhenium(V) oxo complex (PCP)ReOCl 2 ( 1 ; PCP=bis(2,6‐di‐tert‐butylphosphinomethyl)phenyl) undergoes a deprotonation and “dearomatization” upon treatment with LiN(SiMe 3 ) 2 to give (P*CP)ReOCl ( 2 a ), in which Re is bound to a new dianionic P*CP ligand. Compound 2 a was studied spectroscopically, structurally, and computationally and was determined to have non‐negligible Re=C multiple bond character, leading to its formulation as a new pseudo‐carbenoid species. Reaction of 2 a or its iodo analogue (P*CP)ReOI ( 2 b ) with CO 2 provided access to (PCP)ReOX(CO 2 ) (X=Cl or I, 3 a/b ), the product of 1,3‐cycloaddition and C−C bond formation.
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