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Koch F, Berkefeld A, Speiser B, et al. Mechanistic Aspects of Redox-Induced Assembly and Disassembly of S-Bridged [2M-2S] Structures. Chemistry. 2017;23(65):16681-16690doi: 10.1002/chem.201704599.
Koch, F., Berkefeld, A., Speiser, B., & Schubert, H. (2017). Mechanistic Aspects of Redox-Induced Assembly and Disassembly of S-Bridged [2M-2S] Structures. Chemistry (Weinheim an der Bergstrasse, Germany), 23(65), 16681-16690. https://doi.org/10.1002/chem.201704599
Koch, Felix, et al. "Mechanistic Aspects of Redox-Induced Assembly and Disassembly of S-Bridged [2M-2S] Structures." Chemistry (Weinheim an der Bergstrasse, Germany) vol. 23,65 (2017): 16681-16690. doi: https://doi.org/10.1002/chem.201704599
Koch F, Berkefeld A, Speiser B, Schubert H. Mechanistic Aspects of Redox-Induced Assembly and Disassembly of S-Bridged [2M-2S] Structures. Chemistry. 2017 Nov 21;23(65):16681-16690. doi: 10.1002/chem.201704599. Epub 2017 Nov 09. PMID: 28976037.
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Chemistry. 2017 Nov 21;23(65):16681-16690. doi: 10.1002/chem.201704599. Epub 2017 Nov 09.

Mechanistic Aspects of Redox-Induced Assembly and Disassembly of S-Bridged [2M-2S] Structures.

Chemistry (Weinheim an der Bergstrasse, Germany)

Felix Koch, Andreas Berkefeld, Bernd Speiser, Hartmut Schubert

Affiliations

  1. Institut für Anorganische Chemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, Germany.
  2. Institut für Organische Chemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, Germany.

PMID: 28976037 DOI: 10.1002/chem.201704599

Abstract

Sulfur-bridged binuclear structures [2M-2S] play a pivotal role in a variety of chemical processes such as bond breaking and formation and electron transfer. In general, structural persistence is deemed essential to the respective function but owing to the lack of a suitable molecular model system, the current understanding of the factors that control the thermodynamic and kinetic stability of [2M-2S] cores clearly is limited. This work reports a series of binuclear complexes of nickel derived from a 1,4-terphenyldithiophenol ligand platform that is ideally suited for mechanistic work to overcome this limitation. Redox-induced assembly and disassembly of S-bridged [2M-2S] fragments have been investigated at the molecular level. As part of an extended square scheme, metastable binuclear structures that are significant mechanistically have been identified, characterized, and their reactivity studied quantitatively. Electronic properties that are inherent to [2M-2S] structures and determine thermodynamic and kinetic stability are differentiated from steric effects imposed by co-ligands.

© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords: cluster (dis)assembly; nickel; reaction mechanism; sulfur-bridged binuclear clusters; thiolate ligands

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