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Study of Donor–Acceptor Bonds on the N ‐Coordinated Sn/Pb(II) Atoms in peri ‐Substituted Naphthalenes: Evidence of Pb→B Interaction
Author(s) -
Aman Michal,
Dostál Libor,
Mikysek Tomáš,
Růžičková Zdenka,
Mebs Stefan,
Beckmann Jens,
Jambor Roman
Publication year - 2020
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202000696
Subject(s) - chemistry , lewis acids and bases , tin , medicinal chemistry , ligand (biochemistry) , acceptor , stereochemistry , redox , catalysis , inorganic chemistry , organic chemistry , biochemistry , receptor , physics , condensed matter physics
Peri ‐substituted naphthalene derivatives, namely, N ‐coordinated plumbylenes 1‐PPh 2 ‐8‐PbL‐C 10 H 6 ( 4 ) and 1‐BCy 2 ‐8‐PbL‐C 10 H 6 ( 5 ) (L = 2,6‐(Me 2 NCH 2 ) 2 C 6 H 3 ) were prepared. Compounds 4 and 5 allowed studying interactions between the Pb atoms with the either Lewis acidic (BCy 2 ) or Lewis basic sites (PPh 2 ). Addition of an external Lewis acid (BH 3 · SMe 2 ) to 5 provided the complex 1‐BCy 2 ‐8‐[(BH 3 ) 2 L]Pb‐C 10 H 6 ( 7 ), in which both NMe 2 groups of the ligand L were coordinated by BH 3 . This reaction has also been used for the synthesis of a tin analogue 1‐BCy 2 ‐8‐[(BH 3 ) 2 L]Sn‐C 10 H 6 ( 6 ). New complexes 4–7 were also compared with the previously known, tin(II) analogues 1‐PPh 2 ‐8‐SnL‐C 10 H 6 ( 1 ), 1‐PPh 2 ‐8‐[(BH 3 ) 2 L]Sn‐C 10 H 6 ( 2 ), 1‐BCy 2 ‐8‐SnL‐C 10 H 6 ( 3 ). This set of compounds allowed us to study influence of the P→E and E→B peri ‐contacts upon the redox potentials E 1/2 (ox1) by the cyclic voltammetry. As the result, the selective oxidation of E(II) atom was also studied and the new organotin(IV) sulfide [1‐PPh 2 ‐8‐LSn(C 10 H 6 )(µ‐S)] 2 ( 9 ) was prepared, the product of exclusive oxidation of the tin(II) atom in 1 . Beside this, the evaluation of the P→E and E→B peri ‐contacts in the neutral molecules, the first and second ionization energies (IE) were calculated. For this reason, electronic properties, full structural optimizations were conducted with density functional theory (DFT) for all possible combinations of metal atom (Sn vs. Pb), Lewis acid (N→Sn/Pb vs. N(BH 3 )Sn/Pb), peri ‐substituents (BCy 2 vs. PPh 2 ), and for three molecular charges (0 vs. 1 + vs. 2 + ) on the B3PW91/6‐311+g(2df,p) level of theory.