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Computational Analysis of Mesomerism in para ‐Substituted mer ‐NCN Pincer Platinum(II) Complexes, Including its Relationships with Hammett σ p Substituent Parameters
Author(s) -
Canty Allan J.,
Ariafard Alireza,
Koten Gerard
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.202003023
Subject(s) - pincer movement , substituent , chemistry , platinum , density functional theory , stereochemistry , medicinal chemistry , atomic orbital , ring (chemistry) , crystallography , computational chemistry , catalysis , physics , organic chemistry , quantum mechanics , electron
Density Functional Theory studies of square‐planar Pt II pincer structures, (4‐Z‐NCN)PtCl ([4‐Z‐NCN] − =[4‐Z‐2,6‐(Me 2 NCH 2 ) 2 C 6 H 2 ‐ N,C,N ] − , Z=H, NO 2 , CF 3 , CO 2 H, CHO, Cl, Br, I, F, SMe, SiMe 3 , t Bu, OH, NH 2 , NMe 2 ), enable characterisation of mesomerism for the pincer‐Pt interaction. Relationships between Hammett σ p substituent parameters of Z and DFT data obtained from NBO6 and AOMix computation are used to probe the interaction of the 5d yz orbital of platinum with π‐orbitals of the arene ring. Analogous computation for 2,6‐(Me 2 CH 2 ) 2 C 6 H 3 Z (Z=H, CF 3 , CHO, Cl, Br, I, F, SMe, SiMe 3 , t Bu, OH, NH 2 ) and (4‐H‐NCN)PtZ allows an estimation of the relative substituent effects of “(CH 2 NMe 2 ) 2 PtZ” on π‐delocalisation in the pincer system.