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  Ligands Based on Phosphine‐Stabilized Aluminum(I), Boron(I), and Carbon(0)

Vondung, L., Jerabek, P., & Langer, R. (2019). Ligands Based on Phosphine‐Stabilized Aluminum(I), Boron(I), and Carbon(0). Chemistry – A European Journal, 25(12), 3068-3076. doi:10.1002/chem.201805123.

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 Creators:
Vondung, Lisa1, 2, Author
Jerabek, Paul2, 3, Author              
Langer, Robert1, Author
Affiliations:
1Department of Chemistry, Philipps-Universität Marburg, Hans-Meerwein-Str. 4, 35032 Marburg, Germany, ou_persistent22              
2Centre for Theoretical Chemistry and Physics, The New Zealand Institute for Advanced Study and the Institute for Natural and Mathematical Sciences, Massey University, Albany, New Zealand, ou_persistent22              
3Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541710              

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Free keywords: bond theory; computational chemistry; ligand effects; main group elements; transition metals
 Abstract: A systematic quantum chemical study of the bonding in d6‐transition‐metal complexes, containing phosphine‐stabilized, main‐group‐element fragments, (R3P)2E, as ligands (E=AlH, BH, CH+, C), is reported. By using energy decomposition analysis, it is demonstrated that a strong M−E bond is accompanied by weak P−E bonds, and vice versa. Although the Al−M bond is, for example, found to be very strong, the weak Al−P bond suggests that the corresponding metal complexes will not be stable towards phosphine dissociation. The interaction energies for the boron(I)‐based ligand are lower, but still higher than those for two‐carbon‐based ligands. For neutral ligands, electrostatic interactions are the dominating contributions to metal–ligand bonding, whereas for the cationic ligand a significant destabilization, with weak orbital and even weaker electrostatic metal–ligand interactions, is observed. Finally, for iron(II) complexes, it is demonstrated that different reactivity patterns are expected for the four donor groups: the experimentally observed reversible E−H reductive elimination of the borylene‐based ligand (E=BH) exhibits significantly higher barriers for the protonated carbodiphosphorane (CDP) ligand (E=CH) and would proceed through different intermediates and transition states. For aluminum, such reaction pathways are not feasible (E=AlH). Moreover, it is demonstrated that the metal hydrido complexes with CDP ligands might not be stable towards reduction and isomerization to a protonated CDP ligand and a reduced metal center.

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Language(s): eng - English
 Dates: 2018-10-112018-12-192019-02-26
 Publication Status: Published online
 Pages: 9
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/chem.201805123
 Degree: -

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Title: Chemistry – A European Journal
  Other : Chem. – Eur. J.
  Other : Chem. Eur. J.
Source Genre: Journal
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Publ. Info: Weinheim : Wiley-VCH
Pages: - Volume / Issue: 25 (12) Sequence Number: - Start / End Page: 3068 - 3076 Identifier: ISSN: 0947-6539
CoNE: https://pure.mpg.de/cone/journals/resource/954926979058