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An Organotin Route for the Preparation of 2,6‐Bis(diphenylphosphino)bromo‐benzene and the Related Bis(Phosphine Oxide). Precursors for Novel Ligands
Author(s) -
Meyer Fabio,
Kuzmera Thomas,
Lork Enno,
Vogt Matthias,
Beckmann Jens
Publication year - 2021
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.202100210
Subject(s) - chemistry , phosphine oxide , phosphine , medicinal chemistry , bromobenzene , ligand (biochemistry) , benzene , diphenylphosphine oxide , lithium (medication) , phenylphosphine , decomposition , nucleophilic substitution , substitution reaction , oxide , organic chemistry , catalysis , medicine , biochemistry , receptor , endocrinology
The 2,6‐difluorophenyltrialkylstannanes 2,6‐F 2 C 6 H 3 SnR 3 ( 1 , R=Me; 2 , R=Bu) were prepared from commercial products. With Ph 2 PLi, 1 and 2 underwent nucleophilic substitution to give the 2,6‐bis(diphenylphosphino)phenyltrialkylstannanes 2,6‐(Ph 2 P) 2 C 6 H 3 SnR 3 ( 3 , R=Me; 4 , R=Bu). The reaction of 3 with n ‐BuLi and BrCH 2 CH 2 Br afforded 2,6‐bis(diphenylphosphino)bromobenzene (2,6‐(Ph 2 P) 2 C 6 H 3 Br, 5 ), the oxidation of which gave the related bis(phosphine oxide) 2,6‐[Ph 2 P(O)] 2 C 6 H 3 Br ( 6 ). The reaction of 5 with n ‐BuLi gave rise to the formation of 2,6‐bis(diphenylphosphino)phenyl lithium, 2,6‐(Ph 2 P) 2 C 6 H 3 Li ( 7 ). Attempts to prepare the related bis(phosphine oxide) 2,6‐[Ph 2 P(O)] 2 C 6 H 3 Li ( 8 ) from 6 in a similar way at low temperatures was hampered by decomposition. Compounds 3 , 5 and 7 hold potential for a new anionic tridentate PCP−coordinating ligand, namely, the bis(2,6‐diphenyl)phosphinophenyl ion [2,6‐(Ph 2 P) 2 C 6 H 3 ] − .