期刊
POLYHEDRON
卷 52, 期 -, 页码 524-529出版社
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.poly.2012.08.038
关键词
N-heterocyclic carbene (NHC); PEPPSI; DFT; Saturated six-membered NHC; Palladium
资金
- Department of Science and Technology, New Delhi [SR/S1/IC-15/2011]
- CSIR, New Delhi
- BRNS, Mumbai
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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