Abstract
A novel platinum complex with 1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidenyl ligand has been synthesized and characterized on the basis of elemental analysis, MS, 1H and 13C NMR spectroscopy, X-ray Absorption Spectroscopy and single crystal X-ray diffraction studies. The XRD determination of the complex (monoclinic, C2/c) revealed a structure in which the platinum (II) centre coordinates two chlorides, a carbon atom of the N-heterocyclic carbene (NHC) and is stabilized by coordinating the nitrogen atom of a 3-chloropyridine molecule, forming an over-all square planar geometry. By prolonging the time of the reaction, it was possible to obtain the trans-dichloridobis(3-chloropyridine) platinum(II) complex under the same reaction conditions. The electronic and molecular properties of both complexes were investigated and compared by means of Near Edge X-ray Absorption Fine Structure spectroscopy (NEXAFS), supported by numerical simulations. The platinum carbene complex obtained was tested in a series of C–H activation and hydrosilylation reactions.
Highlights
Over the last decade N-heterocyclic carbene complexes of late transition metals have gained significant attention in modern chemistry due to their truly unique features [1,2,3,4,5]
The platinum carbene complex obtained was tested in a series of C–H activation and hydrosilylation reactions
PtCl2 was reacted with the IPr imidazolium precursor in the presence of potassium carbonate in an excess of 3-chloropyridine. While both Pt(II) and Pd(II) metal ions readily form square planar complexes, reactions on Pt(II) centres typically proceed many orders of magnitude slower compared to Pd(II) [49]
Summary
Over the last decade N-heterocyclic carbene complexes of late transition metals have gained significant attention in modern chemistry due to their truly unique features [1,2,3,4,5] These compounds are widely utilized across the chemical field including the use in materials [6,7], as metallopharmaceuticals [8,9,10] and extensively as both homogeneous and heterogeneous catalysts [11,12,13,14,15]. Despite the many benefits of such method, the main drawback arises from the lack of analytical techniques for characterization of the obtained materials For such hybrids, it is important to monitor closely the initial stability, the changes in oxidation state, and the nature of the chemical bonding during the activation step in order to optimize these systems. This gives a convenient reference material when using such compounds in the study of catalysis mechanisms
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