Abstract:A novel, efficient and facile protocol for the synthesis of a series of [Ru(NHC)(CO3)(p-cymene)] complexes is reported. This family of Ru-NHC complexes was obtained from imidazol(in)ium tetrafluoroborate or imidazolium hydrogen...
“…Hydrogenation [85], transfer hydrogenation [86], hydrosilylation [87], hydroboration, and hydroamination [88] are the different types of NHC-transition metal catalyzed addition reactions. A brief outline of the various addition reactions catalyzed by NHC-transition metal complexes is summarized in Figure 19.…”
The journey of “carbenes” is more than a century old. It began with a curiosity to understand a then less familiar carbon moiety in its divalent state. It reached an important milestone in the form of 1,3-imidazolium-based N-heterocyclic carbenes (NHCs), where the quest for bottleable carbenes was achieved through simple and elegant synthetic routes. The properties of these carbenes were finely tunable through the steric and electronic factors via chemical modifications. Thus, it became one of the unique and extensively studied ligands for its properties and applications. This chapter first briefs about structural details of NHCs and different synthetic routes for the preparation of imidazolium-based NHC precursors. The later section focuses on various methods for characterizing the steric and electronic properties of these ligands and their metal intermediates, which are crucial for developing efficient catalytic processes. Finally, the chapter concludes with NHC-metal-mediated catalytic applications and its immediate challenges.
“…Hydrogenation [85], transfer hydrogenation [86], hydrosilylation [87], hydroboration, and hydroamination [88] are the different types of NHC-transition metal catalyzed addition reactions. A brief outline of the various addition reactions catalyzed by NHC-transition metal complexes is summarized in Figure 19.…”
The journey of “carbenes” is more than a century old. It began with a curiosity to understand a then less familiar carbon moiety in its divalent state. It reached an important milestone in the form of 1,3-imidazolium-based N-heterocyclic carbenes (NHCs), where the quest for bottleable carbenes was achieved through simple and elegant synthetic routes. The properties of these carbenes were finely tunable through the steric and electronic factors via chemical modifications. Thus, it became one of the unique and extensively studied ligands for its properties and applications. This chapter first briefs about structural details of NHCs and different synthetic routes for the preparation of imidazolium-based NHC precursors. The later section focuses on various methods for characterizing the steric and electronic properties of these ligands and their metal intermediates, which are crucial for developing efficient catalytic processes. Finally, the chapter concludes with NHC-metal-mediated catalytic applications and its immediate challenges.
“…8 These Ru-NHC complexes have found applications from homogeneous catalysis [9][10][11][12][13][14][15] to therapeutic drugs, 16,17 olefin metathesis reactions [18][19][20] and solar cells (DSSCs). [21][22][23] In general, the synthesis of Ru-NHC complexes involves one of the common Ru metal precursors Ru(Cl)2(PPh3)3, 24 [Ru(Cl)2(p-cymene)]2, 25 [Ru(Cl)2(CO)2]n, 26 Ru II (Cl)2(DMSO)4, 27 [Ru(Cl)2(COD)]n, 28 etc., where one or more of the ligands are replaced with the in situ generated NHC ligands. Ru-precursor complexes play a significant role in the development of new Ru-complexes.…”
Section: Introductionmentioning
confidence: 99%
“…[30][31][32] Involvement of base in such reactions has its shortcomings, namely, the limited or no use of aerobic conditions, less scope to employ green solvents, and possibility of forming undesired side products. 33 Nolan and coworkers have recently developed a "weak base" route 25,[33][34][35] for generating NHC-metal complexes. The simple "weak base" route has been described as a cost-effective and environmentally benign approach which can be extended further with various metals for NHC-based complexes.…”
A series of Ru(III)-NHC complexes, identified as [RuIII(PyNHCR)(Cl)3(H2O)] (1a-c), have been prepared, starting from RuCl3·3H2O following a base-free route. The Lewis acidic Ru(III) centre operates via a halide-assisted, electrophilic C-H...
“…8 These Ru-NHC complexes have found applications from homogeneous catalysis [9][10][11][12][13][14][15] to therapeutic drugs, 16,17 olefin metathesis reactions [18][19][20] and solar cells (DSSCs). [21][22][23] In general, the synthesis of Ru-NHC complexes involves one of the common Ru metal precursors Ru(Cl)2(PPh3)3, 24 [Ru(Cl)2(p-cymene)]2, 25 [Ru(Cl)2(CO)2]n, 26 Ru II (Cl)2(DMSO)4, 27 [Ru(Cl)2(COD)]n, 28 etc., where one or more of the ligands are replaced with the in situ generated NHC ligands. Ru-precursor complexes play a significant role in the development of new Ru-complexes.…”
A series of Ru(III)-NHC complexes, identified as [RuIII(PyNHCR)(Cl)3(H2O)] (1a-c), have been prepared, starting from RuCl3·3H2O following a base-free route. The Lewis acidic Ru(III) centre operates via a halide-assisted, electrophilic C-H activation for carbene generation. Best results were obtained with azolium salts having I- anion while ligand precursors with Cl-, BF4-, and PF6- gave no complex formation and those with Br- gave a product with mixed halides. The structurally simple, air and moisture-stable complexes represent rare examples of paramagnetic Ru(III)-NHC complexes. Further, these benchtop stable Ru(III)-NHC complexes were shown to be excellent metal precursors for the synthesis of new [RuII(PyNHCR)(Cl)2(PPh3)2] (2a-c) and [RuII(PyNHCR)(CNCMe)I]PF6 (3a-c) complexes. All the complexes have been characterised using spectroscopic methods, and structures of 1a, 1b, 2c and 3a have been determined using the single-crystal X-ray diffraction technique. This work allows easy access to new Ru-NHC complexes for the study of new properties and novel applications.
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