Biological pincer complexes.
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ABSTRACT:
SUBMITTER: Nevarez J
PROVIDER: S-EPMC7561051 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:The synthesis of two well-defined rhodium(I) complexes of nitrous oxide (N2 O) is reported. These normally elusive adducts are stable in the solid state and persist in solution at ambient temperature, enabling comprehensive structural interrogation by 15 N NMR and IR spectroscopy, and single-crystal X-ray diffraction. These methods evidence coordination of N2 O through the terminal nitrogen atom in a linear fashion and are supplemented by a computational energy decomposition analysis, which provides further insights into the nature of the Rh-N2 O interaction.
| S-EPMC6856677 | biostudies-literature
Project description:A unique chain-rupturing transformation that converts an ether functionality into two hydrocarbyl units and carbon monoxide is reported, mediated by iridium(i) complexes supported by aminophenylphosphinite (NCOP) pincer ligands. The decarbonylation, which involves the cleavage of one C-C bond, one C-O bond, and two C-H bonds, along with formation of two new C-H bonds, was serendipitously discovered upon dehydrochlorination of an iridium(iii) complex containing an aza-18-crown-6 ether macrocycle. Intramolecular cleavage of macrocyclic and acyclic ethers was also found in analogous complexes featuring aza-15-crown-5 ether or bis(2-methoxyethyl)amino groups. Intermolecular decarbonylation of cyclic and linear ethers was observed when diethylaminophenylphosphinite iridium(i) dinitrogen or norbornene complexes were employed. Mechanistic studies reveal the nature of key intermediates along a pathway involving initial iridium(i)-mediated double C-H bond activation.
| S-EPMC8162749 | biostudies-literature
Project description:The mechanism for the borylation of an aromatic substrate by a cobalt pincer complex was investigated by density functional theory calculations. Experimental observations identified trans-(iPrPNP)CoH2(BPin) as the resting state in the borylation of five-membered heteroarenes, and 4-BPin-(iPrPNP)Co(N2)BPin as the resting state in the catalytic borylation of arene substrates. The active species, 4-R-(iPrPNP)CoBPin (R=H, BPin), were generated by reductive elimination of H2 in the former, through Berry pseudorotation to the cis isomer, and N2 loss in the latter. The catalytic mechanism of the resulting Co(I) complex was computed to involve three main steps: C-H oxidative addition of the aromatic substrate (C6H6), reductive elimination of PhBPin, and regeneration of the active complex. The oxidative addition product formed through the most favorable pathway, where the breaking C-H bond of C6H6 is parallel to a line between the two phosphine atoms, leaves the complex with a distorted PNP ligand, which rearranges to a more stable complex via dissociation and re-association of HBPin. Alternative pathways, ?-bond metathesis and the oxidative addition in which the breaking C-H bond is parallel to the Co-B bond, are predicted to be unlikely for this Co(I) complex. The thermodynamically favorable formation of the product PhBPin via reductive elimination drives the reaction forward. The active species regenerates through the oxidative addition of B2Pin2 and reductive elimination of HBPin. In the overall reaction, the flipping (refolding) of the five-membered phosphine rings, which connects the species with two phosphine rings folded in the same direction and that with them folded in different directions, is found to play an important role in the catalytic process, as it relieves steric crowding within the PNP ligand and opens Co coordination space. Metal-ligand cooperation based on the ligand's aromatization/dearomatization, a common mechanism for heavy-metal pincer complexes, and the dissociation of one phosphine ligand, do not apply in this system. This study provides guidance for understanding important features of pincer ligands with first-transition-row metals that differ from those in heavier metal complexes.
| S-EPMC6358283 | biostudies-literature
Project description:Pincer-type [Cnaphthyl, Npyridine, Namido]HfMe2 complex is a flagship among the post-metallocene catalysts. In this work, various pincer-type Hf-complexes were prepared for olefin polymerization. Pincer-type [Namido, Npyridine, Namido]HfMe2 complexes were prepared by reacting in situ generated HfMe4 with the corresponding ligand precursors, and the structure of a complex bearing 2,6-Et2C6H3Namido moieties was confirmed by X-ray crystallography. When the ligand precursors of [(CH3)R2Si-C5H3N-C(H)PhN(H)Ar (R = Me or Ph, Ar = 2,6-diisopropylphenyl) were treated with in situ generated HfMe4, pincer-type [Csilylmethyl, Npyridine, Namido]HfMe2 complexes were afforded by formation of Hf-CH2Si bond. Pincer-type [Cnaphthyl, Sthiophene, Namido]HfMe2 complex, where the pyridine moiety in the flagship catalyst was replaced with a thiophene unit, was not generated when the corresponding ligand precursor was treated with HfMe4. Instead, the [Sthiophene, Namido]HfMe3-type complex was obtained with no formation of the Hf-Cnaphthyl bond. A series of pincer-type [Cnaphthyl, Npyridine, Nalkylamido]HfMe2 complexes was prepared where the arylamido moiety in the flagship catalyst was replaced with alkylamido moieties (alkyl = iPr, cyclohexyl, tBu, adamantyl). Structures of the complexes bearing isopropylamido and adamantylamido moieties were confirmed by X-ray crystallography. Most of the complexes cleanly generated the desired ion-pair complexes when treated with an equivalent amount of [(C18H37)2N(H)Me]+[B(C6F5)4]-, which showed negligible activity in olefin polymerization. Some complexes bearing bulky substituents showed moderate activities, even though the desired ion-pair complexes were not cleanly afforded.
| S-EPMC6540127 | biostudies-literature
Project description:A series of cobalt complexes, stabilized by a monoanionic tridentate NCN pincer ligand, was synthetized and characterized. Preparation of the paramagnetic 15 VE complex [Co(NCNCH2-Et)Br] (1) was accomplished by transmetalation of Li[2,6-(Et2NCH2)2C6H3] with CoBr2 in THF. Treatment of this air-sensitive compound with NO gas resulted in the formation of the diamagnetic Co(III) species [Co(NCNCH2-Et)(NO)Br] (2) as confirmed by X-ray diffraction. This complex features a strongly bent NO ligand (Co-N-O∠135.0°). The νNO is observed at 1609 cm-1 which is typical for a bent metal-N-O arrangement. Coordinatively unsaturated 1 could further be treated with pyridine, isocyanides, phosphines and CO to form five-coordinate 17 VE complexes. Oxidation of 1 with CuBr2 led to the formation of the Co(III) complex [Co(NCNCH2-Et)Br2]. Treatment of [Co(NCNCH2-Et)Br2] with TlBF4 as halide scavenger in acetonitrile led to the formation of the cationic octahedral complex [Co(NCNCH2-Et)(MeCN)3](BF4)2. A combination of X-ray crystallography, IR-, NMR- and EPR-spectroscopy as well as DFT/CAS-SCF calculations were used to characterize all compounds.
| S-EPMC8596404 | biostudies-literature
Project description:Based on previous work related to the design and application of rigid tridentate phosphine-pyridine-phenyl coordination offered by a PNC-pincer ligand upon cyclometalation to nickel, the synthesis, spectroscopic and solid state characterization and redox-reactivity of two NiII(PNC) complexes featuring either a methyl (2CH3 ) or CF3 co-ligand (2CF3 ) are described. One-electron oxidation is proposed to furnish C-C reductive elimination, as deduced from a combined chemical, electrochemical, spectroscopic and computational study. One-electron reduction results in a ligand-centered radical anion, as supported by electrochemistry, UV spectroelectrochemistry, EPR spectroscopy, and DFT calculations. This further attenuates the breadth of chemical reactivity offered by such PNC-pincer ligands.
| S-EPMC6001697 | biostudies-literature
Project description:Different synthetic methods have been developed to prepare eight new redox-active pincer-type ligands, H(X,Y), that have pyrazol-1-yl flanking donors attached to an ortho-position of each ring of a diarylamine anchor and that have different groups, X and Y, at the para-aryl positions. Together with four previously known H(X,Y) ligands, a series of 12 Ni(X,Y)2 complexes were prepared in high yields by a simple one-pot reaction. Six of the 12 derivatives were characterized by single-crystal X-ray diffraction, which showed tetragonally distorted hexacoordinate nickel(II) centers. The nickel(II) complexes exhibit two quasi-reversible one-electron oxidation waves in their cyclic voltammograms, with half-wave potentials that varied over a remarkable 700 mV range with the average of the Hammett ?(p) parameters of the para-aryl X, Y groups. The one- and two-electron oxidized derivatives [Ni(Me,Me)2](BF4)n (n = 1, 2) were prepared synthetically, were characterized by X-band EPR, electronic spectroscopy, and single-crystal X-ray diffraction (for n = 2), and were studied computationally by DFT methods. The dioxidized complex, [Ni(Me,Me)2](BF4)2, is an S = 2 species, with nickel(II) bound to two ligand radicals. The mono-oxidized complex [Ni(Me,Me)2](BF4), prepared by comproportionation, is best described as nickel(II) with one ligand centered radical. Neither the mono- nor the dioxidized derivative shows any substantial electronic coupling between the metal and their bound ligand radicals because of the orthogonal nature of their magnetic orbitals. On the other hand, weak electronic communication occurs between ligands in the mono-oxidized complex as evident from the intervalence charge transfer (IVCT) transition found in the near-IR absorption spectrum. Band shape analysis of the IVCT transition allowed comparisons of the strength of the electronic interaction with that in the related, previously known, Robin-Day class II mixed valence complex, [Ga(Me,Me)2](2+).
| S-EPMC5047063 | biostudies-literature
Project description:The synthesis, characterization, and catalytic activity of low-spin {CoNO}8 pincer complexes of the type [Co(PCP)(NO)(H)] are described. These compounds are obtained either by reacting [Co(PCP)(?2-BH4)] with NO and Et3N or, alternatively, by reacting [Co(PCP)(NO)]+ with boranes, such as NH3·BH3 in solution. The five-coordinate, diamagnetic Co(III) complex [Co(PCPNMe-iPr)(NO)(H)] was found to be the active species in the hydroboration of alkenes with anti-Markovnikov selectivity. A range of aromatic and aliphatic alkenes were efficiently converted with pinacolborane (HBpin) under mild conditions in good to excellent yield. Mechanistic insight into the catalytic reaction is provided by means of isotope labeling, NMR spectroscopy, and APCI/ESI-MS as well as DFT calculations.
| S-EPMC7842137 | biostudies-literature
Project description:A C-H bond activation strategy based on electrochemical activation of a metal hydride is introduced. Electrochemical oxidation of ( tBu4 PCP)IrH4 ( tBu4 PCP is [1,3-( t Bu2PCH2)-C6H3]-) in the presence of pyridine derivatives generates cationic Ir hydride complexes of the type [( tBu4 PCP)IrH(L)]+ (where L = pyridine, 2,6-lutidine, or 2-phenylpyridine). Facile deprotonation of [( tBu4 PCP)IrH(2,6-lutidine)]+ with the phosphazene base tert-butylimino-tris(pyrrolidino)phosphorane, t BuP1(pyrr), results in selective C-H activation of 1,2-difluorobenzene (1,2-DFB) solvent to generate ( tBu4 PCP)Ir(H)(2,3-C6F2H3). The overall electrochemical C-H activation reaction proceeds at room temperature without need for chemical activation by a sacrificial alkene hydrogen acceptor. This rare example of undirected electrochemical C-H activation holds promise for the development of future catalytic processes.
| S-EPMC7017868 | biostudies-literature
Project description:A series of gold(III) complexes supported by pyridine-based bis(amidate), bis(carboxylate), and bis(iminothiolate) substituents is reported. These compounds represent rare examples of pincer-ligated gold(III) centers with multiple anionic heteroaom donors. Reactivity and electrochemical studies demonstrate the stability of these compounds and the marked difference in reduction potentials with varying ligand scaffolds.
| S-EPMC4146325 | biostudies-literature