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Frustrated Lewis Pair Chemistry Enables N 2 Borylation by Formal 1,3‐Addition of a B−H Bond in the Coordination Sphere of Tungsten
Author(s) -
Coffinet Anaïs,
Specklin David,
Vendier Laure,
Etienne Michel,
Simonneau Antoine
Publication year - 2019
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.201904084
Subject(s) - borylation , frustrated lewis pair , chemistry , lewis acids and bases , phosphine , hydride , borane , coordination complex , medicinal chemistry , electrophile , reactivity (psychology) , coordination sphere , stereochemistry , oxidative addition , crystallography , metal , organic chemistry , crystal structure , catalysis , alkyl , aryl , medicine , alternative medicine , pathology
The first example of a formal 1,3‐B−H bond addition across the M−N≡N unit of an end‐on dinitrogen complex has been achieved. The use of Piers’ borane HB(C 6 F 5 ) 2 was essential to observe this reactivity and it plays a triple role in this transformation: 1) electrophilic N 2 ‐borylation agent, 2) Lewis acid in a frustrated Lewis pair‐type B−H bond activation, and 3) hydride shuttle to the metal center. This chemistry is supported by NMR spectroscopy and solid‐state characterization of products and intermediates. The combination of chelate effect and strong σ donation in the diphosphine ligand 1,2‐bis(diethylphosphino)ethane was mandatory to avoid phosphine dissociation that otherwise led to complexes where borylation of N 2 occurred without hydride transfer.