Understanding the lability of a trans bound pyridine ligand in a saturated six-membered N-heterocyclic carbene based (NHC)PdCl2(pyridine) type complex: A case study
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Title |
Understanding the lability of a trans bound pyridine ligand in a saturated six-membered N-heterocyclic carbene based (NHC)PdCl2(pyridine) type complex: A case study
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Creator |
KUMAR, A
KATARI, M GHOSH, P |
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Subject |
N-heterocyclic carbene (NHC)
PEPPSI DFT Saturated six-membered NHC Palladium CROSS-COUPLING REACTIONS CHARGE DECOMPOSITION ANALYSIS MIXED AQUEOUS-MEDIUM PALLADIUM COMPLEXES ELECTRONIC-STRUCTURE PEPPSI COMPLEXES PD METAL PRECATALYST NHC |
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Description |
The lability of a trans "throwaway" pyridine ligand in a PEPPSI (Pyridine Enhanced Precatalyst Preparation, Stabilization and Initiation) themed saturated six-membered N-heterocyclic carbene complex namely, (1,3-difurfuryl tetrahydropyrimidin-2-ylidene)PdCl2(pyridine) (2), was investigated with the aid of a combined experimental and computational studies. In this regard, a new saturated six-membered N-heterocyclic carbene complex 2 was synthesized from the reaction of 1,3-difurfuryl tetrahydropyrimidin-1-ium chloride (I) with PdCl2 in the presence of KN(SiMe3)(2) as a base in pyridine. Significantly enough, the complex 2 represents the first structurally characterized example of a PEPPSI themed trans-(NHC)PdX2(pyridine) (X = halide) type of a complex supported over a saturated six-membered N-heterocyclic carbene ligand. The lability of a trans "throwaway" pyridine ligand in 2 was probed by a displacement reaction with PPh3 to yield the corresponding phosphine analog, (1,3-difurfuryl tetrahydropyrimidin-2-ylidene)PdCl2(PPh3) (3), at room temperature under ambient condition. Detailed density functional theory (DFT) studies aimed at understanding the lability of the trans "throwaway" pyridine ligand in 2, against a PPh3 ligand yielding 3, points towards a kinetic factor rather than a thermodynamic one as a reason for the lability of the pyridine in 2. (C) 2012 Elsevier Ltd. All rights reserved.
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Publisher |
PERGAMON-ELSEVIER SCIENCE LTD
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Date |
2014-10-16T05:52:07Z
2014-10-16T05:52:07Z 2013 |
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Type |
Article
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Identifier |
POLYHEDRON, 52524-529
http://dx.doi.org/10.1016/j.poly.2012.08.038 http://dspace.library.iitb.ac.in/jspui/handle/100/15384 |
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Language |
en
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