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Iminophosphorano‐Substituted Bispyridinylidenes: Redox Potentials and Substituent Constants from Tolman Electronic Parameters
Author(s) -
Richard Nicholas A.,
Khor Chun Keat,
Hetherington Sydney M.,
Mills Scott L.,
Decken Andreas,
Dyker C. Adam
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.202004153
Subject(s) - substituent , redox , chemistry , phosphine , computational chemistry , stereochemistry , organic chemistry , catalysis
Abstract Bispyridinylidenes (BPYs) have emerged as an important class of neutral organic electron donors, with redox potentials that vary widely with choice of substituent. Methods to predict the effect of substitution on the redox potential are therefore highly desirable. Here we show that the redox potential of BPYs featuring iminophosphorano substituents (R 3 P=N‐), which represent the most reducing class of BPYs, can be predicted based on the well‐known Tolman electronic parameter (TEP) for the respective phosphine fragment (R 3 P). Moreover, building on earlier work relating redox potentials to Hammett‐type substituent constants, it is now possible to quantitatively predict σ p + values for iminophosphorano substituents from TEP values. These results provide a path for precisely tailoring redox potentials of iminophosphorano‐substituted BPYs, but also give quantitative descriptors for how these highly versatile iminophosphorano substituents can impact the properties of any molecular scaffold.