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Special Issue "Scorpionate Ligands: Ever-Young Chemistry Tools"

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Inorganic Chemistry".

Deadline for manuscript submissions: closed (31 May 2018)

Special Issue Editors

Guest Editor
Prof. Dr. Carlo Santini

School of Science and Technology, Chemistry Division, University of Camerino, via Sant’Agostino 1, 62032 Camerino (MC), Italy
Website | E-Mail
Interests: coordination chemistry; functional metal complexes; hybrid materials; inorganic and organometallic chemistry; scorpionate ligands; phosphanes; N-heterocyclic carbenes; metal-based drugs
Guest Editor
Prof. Dr. Maura Pellei

School of Science and Technology, Chemistry Division, University of Camerino, via Sant’Agostino 1, 62032 Camerino (MC), Italy
Website | E-Mail
Phone: 0737402213
Interests: bioinorganic chemistry; coordination chemistry; inorganic materials; organometalllic chemistry; copper; scorpionate ligands; phosphanes; metal-based drugs

Special Issue Information

Dear Colleagues,

Since the introduction of tris(pyrazolyl)borates by Trofimenko, in the 1960s, in a pivotal paper on “Boron-Pyrazole Chemistry”, scorpionate ligands are some of the most widely-used ligands in chemistry. They readily coordinate a wide variety of metal ions, affording stable metal complexes: the term scorpionate derives from the interchange between their bi- and tri-dentate coordination modes. In the last 50 years, the success of poly(azolyl)borates has inspired the development of a new generation Scorpionates, including the analogous poly(azolyl)alkanes, which are excellent supporting ligands for most metals of the Periodic Table. Even if this shows that, in this field, a great deal of research has been done, Scorpionates chemistry and their applications have not been fully explored yet.

The purpose of this Special Issue is to present the latest advances in the field of scorpionate ligands, highlighting their stimulating and innovative applications in coordination chemistry, organometallics, catalysis, supramolecular assembly, materials science, medicinal inorganic chemistry or enzymes modeling.

Prof. Dr. Carlo Santini
Prof. Dr. Maura Pellei
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1800 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • poly(azolyl)borates
  • poly(azolyl)alkanes
  • coordination chemistry
  • metals
  • complexes
  • organometallics
  • catalysis
  • medicinal inorganic chemistry

Published Papers (1 paper)

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Research

Open AccessArticle Cobalt(II) Complexes with N,N,N-Scorpionates and Bidentate Ligands: Comparison of Hydrotris(3,5-dimethylpyrazol-1-yl)borate Tp* vs. Phenyltris(4,4-dimethyloxazolin-2-yl)borate ToM to Control the Structural Properties and Reactivities of Cobalt Centers
Molecules 2018, 23(6), 1466; https://doi.org/10.3390/molecules23061466
Received: 25 May 2018 / Revised: 13 June 2018 / Accepted: 15 June 2018 / Published: 16 June 2018
PDF Full-text (4437 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Scorpionate ligands Tp* (hydrotris(3,5-dimethylpyrazol-1-yl)borate) and ToM (tris(4,4-dimethyloxazolin-2-yl)phenylborate) complexes of cobalt(II) with bidentate ligands were synthesized. Both Tp* and ToM coordinate to cobalt(II) in a tridentate fashion when the bidentate ligand is the less hindered acetylacetonate. In crystal structures, the geometry of
[...] Read more.
Scorpionate ligands Tp* (hydrotris(3,5-dimethylpyrazol-1-yl)borate) and ToM (tris(4,4-dimethyloxazolin-2-yl)phenylborate) complexes of cobalt(II) with bidentate ligands were synthesized. Both Tp* and ToM coordinate to cobalt(II) in a tridentate fashion when the bidentate ligand is the less hindered acetylacetonate. In crystal structures, the geometry of cobalt(II) supported by the N3O2 donor set in the Tp* complex is a square-pyramid, whereas that in the ToM complex is close to a trigonal-bipyramid. Both Tp*- and ToM-acac complexes exhibit solvatochromic behavior, although the changing structural equilibria of these complexes in MeCN are quite different. In the bis(1-methylimidazol-2-yl)methylphenylborate (LPh) complexes, Tp* retains the tridentate (к3) mode, whereas ToM functions as the bidentate (к2) ligand, giving the tetrahedral cobalt(II) complex. The bowl-shaped cavity derived from the six methyl groups on ToM lead to susceptibility to the bulkiness of the opposite bidentate ligand. The entitled scorpionate compounds mediate hydrocarbon oxidation with organic peroxides. Allylic oxidation of cyclohexene occurs mainly on the reaction with tert-butyl hydroperoxide (TBHP), although the catalytic efficiency of the scorpionate ligand complexes is lower than that of Co(OAc)2 and Co(acac)2. On cyclohexane oxidation with meta-chloroperbenzoic acid (mCPBA), both ToM and Tp* complexes function as catalysts for hydroxylation. The higher electron-donating ToM complexes show faster initial reaction rates compared to the corresponding Tp* complexes. Full article
(This article belongs to the Special Issue Scorpionate Ligands: Ever-Young Chemistry Tools)
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