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Bart M. J. M. Suijkerbuijk Duncan M. Tooke Anthony L. Spek Gerard van Koten Robertus J. M. Klein Gebbink Prof. Dr. 《无机化学与普通化学杂志》2007,633(15):2649-2653
A tin(IV) porphyrin was combined with two axial NCN‐pincer platinum(II) fragments by utilizing the oxophilicity of the apical positions on the tin atom and the acidic nature of the NCN‐pincer platinum derived benzoic acid. The solid‐state structure determined by X‐ray crystallography revealed some close contacts between the pincer complexes and the meso‐p‐tolyl subsitutents of the porphyrin. It was shown by 1H NMR spectroscopy that these close contacts were not present in solution and that this compound can potentially act as a novel building block for supramolecular architectures. 相似文献
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Poverenov E Gandelman M Shimon LJ Rozenberg H Ben-David Y Milstein D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(19):4673-4684
Novel anionic dialkyl, diaryl, and dihydride platinum(II) complexes based on the new "long-arm" hemilabile PCN-type ligand C6H4[CH2P(tBu)2](CH2)2N(CH3)2 with the general formula Li+[Pt(PCN)(R)2]- (R=Me (4), Ph (6) and H (9)) were prepared by reaction of [Pt(PCN)(R)] complexes (obtained from the corresponding chlorides) with an equivalent of RLi, as a result of the opening of the chelate ring. Alkylating agents based on other metals produce less stable products. These anionic d8 complexes are thermally stable although they bear no stabilizing pi acceptors. They were characterized by 1H, 31P[1H], 13C, and 7Li NMR spectroscopy; complex 9 was also characterized by single crystal X-ray crystallography, showing that the Li+ ion is coordinated to the nitrogen atom of the open amine arm and to the hydride ligand (trans to the P atom) of a neighboring molecule (H--Li=2.15 A), resulting in a dimeric structure. Complexes 4 and 9 exhibit high nucleophilic reactivity, upon which the pincer complex is regenerated. Reaction of 4 with water, methyl iodide, and iodobenzene resulted in the neutral complex [Pt(PCN)(CH3)] (3) and methane, ethane, or toluene, respectively. Labeling studies indicate that the reaction proceeds by direct electrophilic attack on the metal center, rather than attack on the alkyl ligand. The anionic dihydride complex 9 reacted with water and methyl iodide to yield [Pt(PCN)(H)] (8) and H2 or methane, respectively. 相似文献
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Prof. Dr. Javier A. Cabeza Dr. Israel Fernández Dr. José M. Fernández-Colinas Dr. Pablo García-Álvarez Carlos J. Laglera-Gándara 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(53):12423-12430
An efficient synthesis of 2-di-tert-butylphosphanylmethylpyrrole (HpyrmPtBu2), by treating 2-dimethylaminomethylpyrrole (HpyrmNMe2) with tBu2PH at 135 °C in the absence of any solvent, has allowed the preparation of the new PGeP germylene Ge(pyrmPtBu2)2 ( 1 ), by treating [GeCl2(dioxane)] with LipyrmPtBu2, in which the Ge atom is stabilized by intramolecular interactions with one (solid state) or both (solution) of its phosphane groups. Reactions of germylene 1 with Group 10 metal dichlorido complexes containing easily displaceable ligands have led to [MCl{κ3P,Ge,P-GeCl(pyrmPtBu2)2}] [M=Ni ( 2 ), Pd ( 3 ), Pt ( 4 )], which have an unflawed square-planar metal environment. Treatment of germylene 1 with [AuCl(tht)] (tht=tetrahydrothiophene) rendered [Au{κ3P,Ge,P-GeCl(pyrmPtBu2)2}] ( 5 ), which is a rare case of a T-shaped gold(I) complex. The hydrolysis of 5 gave the linear gold(I) derivative [Au(κP-HpyrmPtBu2)2]Cl ( 6 ). Complexes 2 – 5 contain a PGeP pincer chloridogermyl ligand that arises from the insertion of the Ge atom of germylene 1 into a M−Cl bond of the corresponding metal reagent. The bonding in these molecules has been studied by DFT/NBO/QTAIM calculations. These results demonstrate that the great flexibility of germylene 1 makes it a better precursor to PGeP pincer complexes than the previously known germylenes of this type. 相似文献
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Design of pincer complexes based on (methylsulfanyl)acetic/propionic acid amides with ancillary S‐ and N‐donors as potential catalysts and cytotoxic agents
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Svetlana G. Churusova Diana V. Aleksanyan Andrei A. Vasil'ev Ekaterina Yu. Rybalkina Olga Yu. Susova Zinaida S. Klemenkova Rinat R. Aysin Yulia V. Nelyubina Vladimir A. Kozlov 《应用有机金属化学》2018,32(6)
Pincer complexes featuring readily tunable tridentate ligand frameworks comprise one of the most actively studied classes of organometallic and metal–organic compounds and find extensive use in catalysis, organic synthesis, materials science, and other fields of chemistry and allied disciplines. Currently growing attention is devoted to non‐classical ligand scaffolds, such as functionalized carboxamides, which offer multiple options for directed structural modifications. In this study, the reactions of (methylsulfanyl)acetyl and propanoyl chlorides with 2‐(aminomethyl)pyridine, 2‐(2‐aminoethyl)pyridine, 8‐aminoquinoline and 2‐(diphenylthiophosphoryl)aniline afford a series of new pincer‐type ligands based on functionalized carboxamides. The ligands obtained readily undergo direct cyclopalladation under the action of PdCl2(NCPh)2 in dichloromethane at room temperature, resulting in Pd(II) pincer complexes with N,N,S‐ and S,N,S‐donor sets. Importantly, some of the cyclopalladated derivatives can also be produced efficiently under solvent‐free conditions according to the approach recently developed by our group. The complexes obtained have been tested for cytotoxicity against several human cancer cell lines and catalytic activity in the model Suzuki reaction. The results have been compared to those for the related Pd(II) pincer complexes to define the main structure–activity relationships and to outline the most promising structures for further investigations. 相似文献
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Prof. Dr. Miguel A. Esteruelas Antonio Martínez Dr. Montserrat Oliván Dr. Enrique Oñate 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(55):12632-12644
The saturated trihydride IrH3{κ3-P,O,P-[xant(PiPr2)2]} ( 1 ; xant(PiPr2)2=9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) activates the B−H bond of two molecules of pinacolborane (HBpin) to give H2, the hydride-boryl derivatives IrH2(Bpin){κ3-P,O,P-[xant(PiPr2)2]} ( 2 ) and IrH(Bpin)2{κ3-P,O,P-[xant(PiPr2)2]} ( 3 ) in a sequential manner. Complex 3 activates a C−H bond of two molecules of benzene to form PhBpin and regenerates 2 and 1 , also in a sequential manner. Thus, complexes 1 , 2 , and 3 define two cycles for the catalytic direct C−H borylation of arenes with HBpin, which have dihydride 2 as a common intermediate. C−H bond activation of the arenes is the rate-determining step of both cycles, as the C−H oxidative addition to 3 is faster than to 2 . The results from a kinetic study of the reactions of 1 and 2 with HBpin support a cooperative function of the hydride ligands in the B−H bond activation. The addition of the boron atom of the borane to a hydride facilitates the coordination of the B−H bond through the formation of κ1- and κ2-dihydrideborate intermediates. 相似文献
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Dr. Jun‐ichi Ito Kohei Fujii Prof. Dr. Hisao Nishiyama 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(2):601-605
NCN‐pincer Ru‐complexes containing bis(oxazolinyl)phenyl ligands serve as suitable catalysts in the direct conjugate additions of α,β‐unsaturated carbonyl compounds, including ketones, esters, and amides, as well as vinylphosphonates, giving various β‐alkynyl carbonyl and phosphonate compounds. A bis(oxazolinyl)phenyl (phebox)–Ru complex also catalyzes the asymmetric conjugate addition of an alkyne with a β‐substituted, α,β‐unsaturated ketone to produce a chiral β‐alkynyl ketone. 相似文献
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<正>1 General methods Unless otherwise noted, all reactions and manipulations involving air- or moisture-sensitive compounds were performed using standard Schlenk techniques or in a glovebox. All solvents were purified and dried using standard procedures. Melting points were measured on a RY-I apparatus and uncorrected. 1H, 13 C, 31 P and 19 F NMR spectra were recorded on Varian Mercury 300 or 400 MHz spectrometers. Chemical shifts(δ values) were reported in ppm downfield from internal TMS(1H NMR), CDCl3(13C NMR), external 85% H3PO4(31P NMR), and external CF3CO2H(19F NMR), respectively. Optical rotations were determined using a Perkin Elmer 341 MC polarimeter. The IR spectra were measured on a BRUKER TENSOR 27 相似文献