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Medientyp:
E-Artikel
Titel:
Dearomatization of the PCP Pincer Ligand in a ReV Oxo Complex
Beteiligte:
Kosanovich, Alex J.;
Komatsu, Christopher H.;
Bhuvanesh, Nattamai;
Pérez, Lisa M.;
Ozerov, Oleg V.
Erschienen:
Wiley, 2018
Erschienen in:Chemistry – A European Journal
Sprache:
Englisch
DOI:
10.1002/chem.201802589
ISSN:
0947-6539;
1521-3765
Entstehung:
Anmerkungen:
Beschreibung:
<jats:title>Abstract</jats:title><jats:p>A high‐valent, rhenium(V) oxo complex (PCP)ReOCl<jats:sub>2</jats:sub> (<jats:bold>1</jats:bold>; PCP=bis(2,6‐di‐tert‐butylphosphinomethyl)phenyl) undergoes a deprotonation and “dearomatization” upon treatment with LiN(SiMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub> to give (P*CP)ReOCl (<jats:bold>2 a</jats:bold>), in which Re is bound to a new dianionic P*CP ligand. Compound <jats:bold>2 a</jats:bold> 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 <jats:bold>2 a</jats:bold> or its iodo analogue (P*CP)ReOI (<jats:bold>2 b</jats:bold>) with CO<jats:sub>2</jats:sub> provided access to (PCP)ReOX(CO<jats:sub>2</jats:sub>) (X=Cl or I, <jats:bold>3 a/b</jats:bold>), the product of 1,3‐cycloaddition and C−C bond formation.</jats:p>