Donor‐Acceptor Couples and Late Transition Metal Complexes of Oxidation‐Labile 1,4,5,8‐Tetrakis(guanidino)naphthalene Superbases

Abstract

In this manuscript the reactivity of the two oxidation‐labile superbases 1,4,5,8‐tetrakis(N,N,N′,N′‐tetramethylguanidino)naphthalene and the newly synthesized 1,4,5,8‐tetrakis(N,N′‐dimethyl‐N,N′‐ethylene‐guanidino)naphthalene(tdmegn) are discussed and compared with that of related organic electron donors. The work includes oxidation with inorganic and organic oxidation reagents, as well as the preparation and characterization of dinuclear CoII, NiII and CuI complexes. Magnetic coupling in the dinuclear CoII and NiII complexes is studied on the basis of SQUID measurements. Finally, the results of experiments on the oxidation of the dinuclear CuI complexes are presented.

Guanidinyl‐Functionalized Aromatic Compounds (GFAs) – Charge and Spin Density Studies as Starting Points for the Development of a New Class of Redox‐active Ligands

“…It also represents the most intensively studied GFA compound up to date. Another example is 1, 4, 5, 8‐tetrakis(tetramethylguanidinyl)naphthalene (ttmgn), which also is shown in Scheme 20,21. There are several points that make the GFA compounds attractive.…”

Redox Chemistry and Group 10 Metal Complexes of Aromatic Compounds with Bulky Bicyclic Guanidino Groups

“…Guanidino-functionalized naphthalene species such as 1,8-bis(tetramethylguanidino)naphthalene [35] and 1,4,5,8-tetrakis(tetramethylguanidino)naphthalene [21,36] have been shown to be proton sponges. Hence the monoprotonated form of these species features the proton in an unsymmetric bridging position between both imino N atoms.…”

Bisguanidines with Biphenyl, Binaphthyl, and Bipyridyl Cores: Proton‐Sponge Properties and Coordination Chemistry

“…[13] Recently, we developed guanidinyl-functionalized aromatic compounds (GFAs) as a new class of organic electron donor. Two examples, namely 1,2,4,5-tetrakis(tetramethylguanidinyl)benzene (ttmgb) [12,14] and 1,4,5,8-tetrakis(tetramethylguanidinyl)naphthalene (ttmgn), [15,16] are shown in Scheme 1. These compounds feature guanidinyl groups in [ (2)], [NiBr 2 (2)], [NiCl 2 (3)], and [NiBr 2 (3)]; magnetic curves of [NiBr 2 (2)], [Ni(5) 3 ]Cl 2 and [Ni (6) 3 ]Cl 2 ; calculated structures of the protonated ligands and their hypothetical isomers; 13 C-1 H-coupled and HETCOR NMR spectra of [NiCl 2 (2)], [NiBr 2 (2)], [NiCl 2 (3)], and [NiBr 2 (3)]; Curie plots from the VT-NMR spectroscopic experiments; NMR spectra at different temperatures for [{PdClA C H T U N G T R E N N U N G (h 3 Abstract: Herein, we report on the synthesis, protonation, and coordination chemistry of chelating guanidine ligands with biphenyl, binaphthyl, and bipyridyl backbones.…”