Twists and turns of platinum-allene complexes: NMR techniques for the study of the dynamic behaviour in solution

Quirós, M. Teresa and Paz Muñoz, María and Christensen, Jeppe and Coles, Simon J. (2016) Twists and turns of platinum-allene complexes: NMR techniques for the study of the dynamic behaviour in solution. Organometallics, 36 (2). 318–330. ISSN 0276-7333

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Abstract

Classic (dynamic exchange lineshape analysis) and novel (SSTD NMR) NMR techniques have been applied in order to obtain the kinetic and thermo-dynamic parameters of the three main processes occurring in the fluxional behaviour of Pt-allene complexes with N-containing ligands, in four and five coordination mode, in solution. Our results show intramolecular helical and rotational movements, closely related to each other confirming η1 -staggered structures as possible intermediates. The ligand exchange in these complexes seems to occur via a ligand-independent dissociative mechanism, where coordinating solvents might be involved in the stabilisation of the intermediates. The differences observed in the interaction of allenes with other metals could be the basis to explain the divergent reactivity observed in platinum catalysed processes.

Item Type:
Journal Article
Journal or Publication Title:
Organometallics
Uncontrolled Keywords:
Research Output Funding/yes_externally_funded
Subjects:
?? yes - externally fundednoorganic chemistryphysical and theoretical chemistryinorganic chemistry ??
ID Code:
185716
Deposited By:
Deposited On:
03 Feb 2023 16:00
Refereed?:
Yes
Published?:
Published
Last Modified:
15 Jul 2024 23:31