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A Comparative Study on the Thermodynamics of Halogen Bonding of Group 10 Pincer Fluoride Complexes
Author(s) -
Joksch Markus,
Agarwala Hemlata,
Ferro Monica,
Michalik Dirk,
Spannenberg Anke,
Beweries Torsten
Publication year - 2020
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.201904863
Subject(s) - isostructural , pincer movement , chemistry , adduct , halogen , fluoride , halogen bond , stereochemistry , medicinal chemistry , crystallography , inorganic chemistry , crystal structure , organic chemistry , catalysis , alkyl
The thermodynamics of halogen bonding of a series of isostructural Group 10 metal pincer fluoride complexes of the type [(3,5‐R 2 ‐ t Bu POCOP t Bu )MF] (3,5‐R 2 ‐ t Bu POCOP t Bu = κ 3 ‐C 6 HR 2 ‐2,6‐(OP t Bu 2 ) 2 with R=H, t Bu, COOMe; M=Ni, Pd, Pt) and iodopentafluorobenzene was investigated. Based on NMR experiments at different temperatures, all complexes 1‐ t Bu (R= t Bu, M=Ni), 2‐H (R=H, M=Pd), 2‐ t Bu (R= t Bu, M=Pd), 2‐COOMe (R=COOMe, M=Pd) and 3‐ t Bu (R= t Bu, M=Pt) form strong halogen bonds with Pd complexes showing significantly stronger binding to iodopentafluorobenzene. Structural and computational analysis of a model adduct of complex 2‐ t Bu with 1,4‐diiodotetrafluorobenzene as well as of structures of iodopentafluorobenzene in toluene solution shows that formation of a type I contact occurs.