An official website of the United States government
Fourteen Ag( i ), Au( i ), Ni( ii ), Pd( ii ), and Pt( ii ) complexes with macrocyclic tetradentate N-heterocyclic carbene (NHC) ligands were prepared via reactions between three macrocyclic tetrabenzimidazolium salts and metal precursors. All except two Au complexes were characterized using single-crystal X-ray diffraction. Three different structures, including a trinuclear one containing a NHC–Ag–(H 2 O) moiety and a hexanuclear propeller-like supramolecular assembly, are found for Ag–NHC complexes. Nine complexes of group 10 metal ions adopt square-planar geometry, in which the different ring-sizes of the macrocyclic tetracarbene ligands lead to a variation of metal–carbene bond lengths. π–π stackings are observed between the rigid aromatic benzimidazole rings in the nickel group complexes.
more »
« less
Isolation and Characterization of Sulfonium-Ylide-Stabilized Palladium Carbenes
Isolable sulfonium-ylide stabilized palladium carbene complexes were synthesized through palladium(II)-induced cyclization of 1,2-alkynylarylsulfanes. X-ray crystallographic analysis characterized the maintenance of a palladium +2 oxidation state, with carbene-carbon–palladium bond lengths of 1.95 Å, indicating partial double bond character. These endocyclic sulfonium ylide carbenes represent the first characterized and/or isolable examples of this ligand class; such groups were previously proposed as reaction intermediates during cyclization–carbonylation reactions. A variety of palladium(II) complexes bearing sulfonium ylide carbene ligands, with differing substituents, were synthesized and the structure and stability of these complexes in solution were analyzed by 1H and 13C NMR spectroscopy, revealing reversibility and a stability dependence on substituents. The chirality of the sulfur heteroatom and the overall properties these ligands provide a potential electronic and steric alternative to existing carbene ligands, which could facilitate the future development of complementary metal-based reactivity.
more »
« less
- Award ID(s):
- 2102493
- PAR ID:
- 10613947
- Publisher / Repository:
- Organometallics
- Date Published:
- Journal Name:
- Organometallics
- Volume:
- 44
- Issue:
- 1
- ISSN:
- 0276-7333
- Page Range / eLocation ID:
- 169 to 178
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Two‐coordinate carbene Cu(Ι) amide complexes with sterically bulky groups such as the diisopropyl phenyl (dipp) on the carbenes have been shown to have comparable performance to the phosphorescent emitters bearing heavy atoms such as iridium and platinum. These bulky groups enforce a coplanar molecular structure and suppress the nonradiative decay rates. Here, three different two‐coordinate Cu(Ι) complexes were investigated that bear a common thiazole carbene, 3‐(2,6‐diisopropylphenyl)‐4,5‐dimethylthiazol‐2‐ylidene, with only a single dipp group, and carbazolyl ligands with substituents of varying steric bulkorthoto N. These substituents have a negligible impact on luminescence energies of the complexes but serve to modulate the rotation barriers along the metal–ligand coordinate bond. The geometric arrangement of ligands (syn‐ oranti‐conformer) in complexes with alkyl substituents were found to differ, beingsynin the solid state versusantiin solution as revealed by crystallographic analysis and nuclear magnetic resonance spectroscopy. In addition, calculations were performed to determine potential energy surfaces for different conformations of the three complexes to provide a theoretical evaluation of rotation barriers around the metal–ligand bond axis. The relationship between rotation barriers and photophysical properties demonstrate that rates for nonradiative decay decrease with increasing bulk of the substituents on the carbazolyl ligand.more » « less
-
Carbon dioxide hydrogenation with base to generate formate salts can provide a means of storing hydrogen in an energy dense solid. However, this application requires catalytic CO2 hydrogenation, which would ideally use an earth abundant metal catalyst. In this article, six new (CNC)CoIL2 pincer complexes were synthesized and fully characterized, including single crystal X-Ray diffraction analysis on four new complexes. These complexes contain an imidazole-based (1R) N-heterocyclic carbene (NHC) ring or a benzimidazole based NHC ring (2R) in the CNC pincer. The R group is para to N on the pyridine ring and been varied from electron withdrawing (CF3) to donating (Me, OMe) substituents. The L type ligands have included CO and phosphine ligands (in PPh32 and PMe32). Thus, two known Co complexes (1, 1OMe) and six new complexes (1Me, 1CF3, 2, 2OMe, PPh32, PMe32) were studied for the CO2 hydrogenation reaction. In general, the unsubstituted CNC pincer complexes bearing two carbonyl ligands led to the highest activity. The best catalyst, 2, remains active for over 16 h and produces a turnover number of 39,800 with 20 bars of 1:1 CO2 / H2 mixture at 60 °C. A computational study of the mechanism of CO2 hydrogenation is also reported.more » « less
-
Abstract Herein, we report four new chiral 1,4,7‐triazacyclononane (TACN) derivatives and their corresponding nickel(II) chloride complexes. All TACN ligands are bearing one chiral N‐substituent and two alkyl (methyl ortert‐butyl) N‐substituents, and we have developed a new synthetic method for the dimethyl‐substituted TACN derivative, in order to prevent the rotational isomers that hinder the cyclization reaction. The nickel complexes change their coordination geometry significantly depending on the steric bulk of the N‐alkyl substituents, from a dinuclear tris(μ‐chloro)dinickel complex to mononuclear Ni‐dichloride and Ni‐chloride complexes. These complexes were then employed in the alkyl‐alkyl Kumada cross‐coupling reaction and revealed that the more sterically hindered ligands produced more homocoupled product rather than the cross‐coupled product, while the mononuclear Ni‐dichloride complex exhibited significantly lower catalytic activity. These chiral complexes were also employed in enantioconvergent cross‐coupling reactions as well, to afford significant enantioenrichment. Overall, the least sterically hindered Ni complex yields the best yields in the alkyl‐alkyl Kumada cross‐coupling reaction among the four complexes investigated, as well as the highest enantioselectivity.more » « less
-
The 3d transition metal (Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II)) complexes, supported by anions of sterically demanding β-diketones, 1,3-dimesitylpropane-1,3-dione (HLMes) and 1,3-bis(3,5-bis(trifluoromethyl)phenyl)-3-hydroxyprop-2-en-1-one (HLCF3), were synthesized and evaluated for their antitumor activity. To assess the biological effects of substituents on phenyl moieties, we also synthesized and investigated the analogous metal(II) complexes of the anion of the less bulky 1,3-diphenylpropane-1,3-dione (HLPh) ligand. The compounds [Cu(LCF3)2], [Cu(LMes)2] and ([Zn(LMes)2]) were characterized by X-ray crystallography. The [Cu(LCF3)2] crystallizes with an apical molecule of solvent (THF) and features a rare square pyramidal geometry at the Cu(II) center. The copper(II) and zinc(II) complexes of diketonate ligands, derived from the deprotonated 1,3-dimesitylpropane-1,3-dione (HLMes), adopt a square planar or a tetrahedral geometry at the metal, respectively. We evaluated the antitumor properties of the newly synthesized (Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II)) complexes against a series of human tumor cell lines derived from different solid tumors. Except for iron derivatives, cellular studies revealed noteworthy antitumor properties, even towards cancer cells endowed with poor sensitivity to the reference drug cisplatin.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.organomet.4c00418
