Bicyclic N-heterocyclic carbene (NHC) ligand precursors and their palladium complexes

Abstract Eight bicyclic amidinium precursors (3), prepared from R,S-tmcp (R,S-tmcp: (1R,3S)-diamino-1,2,2-trimethylcyclopentane) were described. Only five of the precursors (3a–e) could be converted to palladium complexes, (PdX2(6,7-NHC)PEPPSI) (4) by treatment with PdCl2, K2CO3, and pyridine (additional KBr was used for (PdBr2(6,7-NHC)PEPPSI)). The salts and complexes were fully characterized by spectroscopic methods and X-ray crystallography.

[1]  Lei Wang,et al.  Dinuclear N -heterocyclic carbene palladium(II) complexes as efficient catalysts for the Buchwald–Hartwig amination , 2014 .

[2]  C. Besnard,et al.  Chiral PEPPSI Complexes: Synthesis, Characterization, and Application in Asymmetric Suzuki–Miyaura Coupling Reactions , 2014 .

[3]  H. Inomata,et al.  N-heterocyclic carbene copper(I) complex-catalyzed direct C–H thiolation of benzothiazoles , 2013 .

[4]  P. Ghosh,et al.  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 , 2013 .

[5]  S. Ando,et al.  Syntheses of effectively-shielded N-heterocyclic carbene ligands , 2013 .

[6]  P. D. Newman,et al.  Variable coordination of a chiral diphosphine containing an amidinium/NHC group within its backbone: μ-P,P', κ2-P,P' and κ3-P,C,P' coordination modes. , 2012, Dalton transactions.

[7]  Srinivasa Budagumpi,et al.  Stereochemical and structural characteristics of single- and double-site Pd(II)–N-heterocyclic carbene complexes: Promising catalysts in organic syntheses ranging from CC coupling to olefin polymerizations , 2012 .

[8]  Louis J. Farrugia,et al.  WinGX and ORTEP for Windows: an update , 2012 .

[9]  P. D. Newman,et al.  Monovalent chiral-at-copper complexes: halide-controlled diastereoselectivity. , 2012, Chemical communications.

[10]  Lei Zhu,et al.  Well-defined NHC–Pd(II)–Im (NHC=N-heterocyclic carbene; Im=1-methylimidazole) complex catalyzed C–N coupling of primary amines with aryl chlorides , 2012 .

[11]  V. Dupray Recrystallization of Enantiomers from Conglomerates , 2012 .

[12]  M. Spallek Camphor as Chiral Motif in Ligand Design - Applications in Catalysis and Complexation Gas-Chromatography , 2012 .

[13]  W. Herrmann,et al.  Synthesis and characterization of chiral mono N-heterocyclic carbene-substituted rhodium complexes and their catalytic properties in hydrosilylation reactions , 2011 .

[14]  K. Cavell,et al.  Expanded ring N-heterocyclic carbenes: a comparative study of ring size in palladium (0) catalysed Mizoroki-Heck coupling. , 2011, Dalton transactions.

[15]  P. D. Newman,et al.  Rhodium and iridium complexes of an asymmetric bicyclic NHC bearing secondary pyridyl donors. , 2011, Dalton transactions.

[16]  A. O’Donoghue,et al.  pKas of the conjugate acids of N-heterocyclic carbenes in water. , 2011, Chemical communications.

[17]  A. Trzeciak,et al.  N-Heterocyclic carbene–rhodium complexes as catalysts for hydroformylation and related reactions , 2011 .

[18]  P. D. Newman,et al.  Metal Complexes of Chiral NHCs Containing a Fused Six- and Seven-Membered Central Ring , 2010 .

[19]  S. Tabassum,et al.  New enantiopure NHCs derived from camphor. , 2009, Chemical communications.

[20]  B. Kariuki,et al.  Expanded ring and functionalised expanded ring N-heterocyclic carbenes as ligands in catalysis. , 2009, Dalton transactions.

[21]  S. Nolan,et al.  Carbenes : Synthesis, properties, and organometallic chemistry , 2009 .

[22]  G. Sheldrick A short history of SHELX. , 2008, Acta crystallographica. Section A, Foundations of crystallography.

[23]  K. Cavell,et al.  First examples of diazepanylidene carbenes and their late-transition-metal complexes , 2007 .

[24]  S. Nolan,et al.  Stereoelectronic parameters associated with N-heterocyclic carbene (NHC) ligands: A quest for understanding , 2007 .

[25]  M. Buchmeiser,et al.  Copper (I) 1,3-R2-3,4,5,6-tetrahydropyrimidin-2-ylidenes (R=mesityl, 2-propyl): synthesis, X-ray structures, immobilization and catalytic activity , 2005 .

[26]  C. Crudden,et al.  Stability and reactivity of N-heterocyclic carbene complexes , 2004 .

[27]  R. Grubbs,et al.  A New Ruthenium-Based Olefin Metathesis Catalyst Coordinated with 1,3-Dimesityl-1,4,5,6-tetrahydropyrimidin-2-ylidene: Synthesis, X-ray Structure, and Reactivity , 2004 .

[28]  B. Dalhus,et al.  Non-centrosymmetric racemates: space-group frequencies and conformational similarities between crystallographically independent molecules. , 2000, Acta crystallographica. Section B, Structural science.

[29]  J. Schwartz,et al.  Organometallics , 1987, Science.

[30]  R. Conley,et al.  Schmidt reaction of .alpha.-aralkyl substituted carboxylic acids , 1970 .