Synthesis and Coordination Chemistry of Novel Binucleating Macrocyclic Ligands with Amine-thioether and Amine-thiophenolate Donor Functions

Abstract

The ability of the aromatic tetraaldehyde l,2-bis(4-rm-butyl-2,6-diformylphenylsulfanyl)ethane (1 ) to function as a precursor in the preparation of binucleating hexaamine-dithiolate lig ands has been investigated. Reductive amination of compound 1 with bis(aminoethyl)amine un der medium-dilution conditions affords the macrobicyclic hexaamine-dithioether compound L 1. Deprotection of the [1+2] condensation product gives the corresponding 24-membered hexaamine-dithiophenol ligand H2L2. The formulation of L 1 as a macrobicyclic amine-thioether was confirmed by an X-ray crystal structure determination of the tetranuclear nickel(II) complex of L 1, [{ (L jN iiC lili^-C l^K B P h ;) (2b). The formulation of the doubly deprotonated form (L2)2-of H2L2 as a 24-membered amine-thiophenolate ligand was confirmed by an X-ray crystal structure determination of the dinuclear cobalt(III) complex, [(L2)Com(^-OH)](C1 0 4 ) 2 • Cl (3). The preparation and the crystal structures of the new compounds are described.

Preparation and Characterization of Dinuclear NiII Amine‐Thiophenolate Complexes Coligated by EO4– (E = Cl, Re) and EO42– Oxoanions (E = S, Cr, Mo, W)

“…The perchlorato (2) and perrhenato (3) complexes were found to be inaccessible by direct reactions of the chloro complex 1 and the respective EO 4 -ligand. In order to achieve their coordination, a Cl -abstraction was necessary.…”

“…[2] These complexes have a rich coordination chemistry since the [(L Me )M 2 ] 2+ fragments are able to coordinate a large variety of coligands LЈ. These include Cl -, [3] OH -, [4] NO 2 -, NO 3 -, N 3 -, [5] BH 4 -, [6] various carboxylates, [7][8][9] N 2 H 4 , pyrazolate, and pyridazine, [5] and some biologically relevant molecules such as HCO 3 -, (p-NO 2 C 6 H 4 O) 2 PO 2 -, and proline. [10] In earlier work, we have also described the synthesis of a few [ + have been reported.…”

Dinuclear Complexes as Building Blocks for Tetra-Nuclear Macrocyclic Complexes with Dithiolate Macrocyclic Ligand

“…Mold. 2013, 8 (1), [58][59][60][61][62][63][64][65][66][67][68][69][70][71][72][73][74][75][76][77] ) at 0.71 V, and iii) the oxidation of the thiophenolate sulfur atoms yielding a nickel bound thiyl radical at 1.59 V. Anodic shifts in the second and third redox waves are clearly discernible, confi rming the above fi ndings that the electron transfer events of the ferrocenyl moiety and the binuclear subunit infl uence one another. The fact that the potential shifts are not so pronounced than in 9 is in good agreement with the smaller positive charges of the participating species.…”

“…Reaction of [65,67]. These are assigned to the antisymmetric and symmetric carboxylate stretching modes, respectively, of a μ 1,3 -bridging carboxylate function.…”

Dinuclear Amine–Thiophenolate Complexes Coligated by Ferrocenemonocarboxylate and 1,1′‐Ferrocenedicarboxylate Anions: Preparation, Characterization and Structures of Trinuclear [LMII2(O2CC5H4FeCp)]+ and Pentanuclear [(LMII2)2(O2CC5H4)2Fe]2+ Complexes (M=Co, Ni, Zn)

“…Keywords: binuclear complexes · ferrocene · magnetic properties · polynuclear complexes · redox chemistry Cl À , [18] OH À , [19] NO 2 À , NO 3 À , N 3 À , [20] BH 4 À , [21] and various carboxylates. [22][23][24] The extensive redox chemistry exhibited by these dinuclear amine-thiolate complexes [25] and the possibility of coupling these units into polynuclear arrays, led us to synthesize derivatives bearing ferrocenemono-and ferrocenedicarboxylate anions ( complexes.…”