Universität zu Köln

Neugebauer, Michael, Schmitz, Simon, Bruenink, Dana, Doltsinis, Nikos L. and Klein, Axel ORCID: 0000-0003-0093-9619 (2020). Dynamics of the efficient cyclometalation of the undercoordinated organoplatinum complex [Pt(COD)(neoPh)](+) (neoPh=2-methyl-2-phenylpropyl). New J. Chem., 44 (44). S. 19238 - 19250. CAMBRIDGE: ROYAL SOC CHEMISTRY. ISSN 1369-9261

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Abstract

Reaction of the organoplatinum complex [Pt(COD)(neoPh)Cl] (neoPh = (2-methyl-2-phenylpropyl)) with Ag(PF6) leads to the undercoordinated cationic complex [Pt(COD)(neoPh)](+) which rapidly and quantitatively rearranges to the complex [Pt(COD)(kappa(2)-neoPh)] through intramolecular cyclometalation. Detailed NMR spectroscopy and single crystal XRD reveal a doubly metalated neoPh ligand. In line with experimental observations, ab initio molecular dynamics simulations confirm that the cyclometalation reaction is exothermic and has a relatively low free energy barrier. In addition, the simulations provide detailed insight into the reaction mechanism, showing that an intermediate species exists in which the newly formed Pt-C bond coexists with a covalent Pt-H bond involving the leaving proton. The latter is found to eventually transfer onto an acetone solvent molecule.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Neugebauer, Michael UNSPECIFIED UNSPECIFIED UNSPECIFIED Schmitz, Simon UNSPECIFIED UNSPECIFIED UNSPECIFIED Bruenink, Dana UNSPECIFIED UNSPECIFIED UNSPECIFIED Doltsinis, Nikos L. UNSPECIFIED UNSPECIFIED UNSPECIFIED Klein, Axel UNSPECIFIED orcid.org/0000-0003-0093-9619 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-310674
DOI:	10.1039/d0nj04811a
Journal or Publication Title:	New J. Chem.
Volume:	44
Number:	44
Page Range:	S. 19238 - 19250
Date:	2020
Publisher:	ROYAL SOC CHEMISTRY
Place of Publication:	CAMBRIDGE
ISSN:	1369-9261
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Inorganic Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language C-H ACTIVATION; RAY CRYSTAL-STRUCTURE; PLATINUM COMPLEXES; BOND FORMATION; DINEOPHYLPLATINUM(II) COMPLEXES; ORGANOMETALLIC PALLADIUM; THERMAL-DECOMPOSITION; MECHANISTIC INSIGHT; FORCE-FIELD; REACTIVITY Multiple languages Chemistry, Multidisciplinary Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/31067