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The iridium(III) dihydride complexes [Ir(H)2(L1)(6,6?-bi-2-picoline)]BArF (5; L1 = (S)-1-[2-(2-adamantan-2-yl-4,5-dihydrooxazol-4-yl)-ethyl]-3-(2,6-diisopropylphenyl)-1,2-dihydroimidazol-2-ylidene, BArF = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate) and [Ir(H)2(L2)(6,6?-bi-2-picoline)]BArF (6; L2 = (R)-2-((di-tert-butylphosphanyl)methyl)-4-phenyl-4,5-dihydrooxazole) were prepared from the corresponding [Ir(COD)(L)]BArF precursors by treatment with 6,6?-bi-2-picoline under H2 and characterized by 2D NMR spectroscopy and X-ray diffraction. In solution, the N,P complex 6 exists as two isomeric dihydride species (6a and 6b) that are in rapid equilibrium at room temperature. Furthermore, the X-ray structures for [Ir(COD)(L1)]BArF (1) and [Ir(COD)(L2)]BArF (2) are reported. The structural comparison of the solid-state structures of the iridium(I) precursor 1 and the iridium(III) dihydride complex 5 revealed a significant change in the backbone geometry of the C,N ligand. The original U-shaped conformation of the ligand switches to an S-shaped conformation, and therefore, the substituent in the oxazoline ring occupies different quadrants in the iridium coordination sphere. Notable in this context is the finding that a similar switch in the ligand backbone was observed for the C,N iridium(III) dihydride olefin species 3 ([Ir(H)2[(E)-1-methyl-4-(1-phenylprop-1-en-2-yl)benzene-D5](L1)]BArF), which represents a catalytically competent intermediate.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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We report a NiH-catalyzed migratory defluorinative coupling between two electronically differentiated olefins. A broad range of unactivated donor olefins can be joined directly to acceptor olefins containing an electron-deficient trifluoromethyl substituent in both intra- and intermolecular fashion to form gem-difluoroalkenes. This migratory coupling shows both site- and chemoselectivity under mild conditions, with the formation of a tertiary or quaternary carbon center.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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(matrix presented) Various mono- and disubstituted 2,2?-bipyridines were synthesized in high yields and multigram scales utilizing Stille-type coupling procedures. The corresponding bromo-picoline and tributyltin-picoline building blocks were prepared from commercially available amino-picoline compounds. As first examples of metal complexes, 4,5?-dimethyl-2,2?-bipyridine was reacted with copper(II) and iron(II) ions and investigated as catalyst in ATRP.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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4,4?-Dicarboxy-2,2?-bipyridine was synthesized quantitatively by chromium(VI) oxide-mediated oxidation of 4,4?-dimethyl-2,2?-bipyridine or 4,4?-diethyl-2,2?-bipyridine with periodic acid as the terminal oxidant in sulfuric acid. 5,5?-Dicarboxy-2,2?-bipyridine and 6,6?-dicarboxy-2,2?-bipyridine were also synthesized by the method from the corresponding dimethyl bipyridines in excellent yields. 4,4?,4?-Tricarboxy-2,2?:6?,2?-terpyridine was obtained in 80% yield from 4,4?,4?-triethyl-2,2?:6?,2?-terpyridine, and 4,4?,4?,4??-tetracarboxy-2,2?:6?,2?:6?,2??-quaterpyridine was obtained in 72% yield from 4,4?,4?,4??-tetraethyl-2,2?:6?,2?:6?,2??-quaterpyridine by the same procedure.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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[Problem] various bipyridyl compound, a small number of steps, a relaxed condition by the reaction in a short time. [Solution] a palladium compound in the presence of an oxidant, having the general formula:[In the formula, Y is a hydrogen atom or a nitrogen atom. R1 The, cyano group, halogen atom, alkyl group which may be substituted, alkoxy group which may be substituted, aryl group which may be substituted, aryl group which may be substituted, or substituted silyl group may be. N is an integer of 0 – 4. When n is 2 or more, the same benzene ring bonded to 2 R1 Bonded to each other to form a ring. ]Reacting a compound represented. [Drawing] no (by machine translation)

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Three strained Ru(II) metal-organic dyads were prepared and characterized by NMR, mass spectrometry, and analytical HPLC to probe whether these constructs could act as multifunctional photochemotherapy (PCT) agents. The compounds incorporated the crowded 6,6?-dimethyl-2,2?-bipyridine (6,6?-dmb) ligand to impart stoichiometric photocisplatin activity, and imidazo[4,5-f] [1,10]phenanthroline (IP) appended with n thiophene units (nT; n = 1-3) to add capacity for singlet oxygen sensitization. With visible light activation, each complex of the series underwent rapid and selective photoejection of 6,6?-dmb in less than 10 min, with half-lives (t1/2) as short as 46.3 s for [Ru(6,6?-dmb)2(IP-1T)]2 +. Photo-triggered ligand loss slowed with increasing n, and was slowest for [Ru(6,6?-dmb)2(IP-3T)]2 + (t1/2 = 273 s). This trend also held for photoadduct formation with DNA; [Ru(6,6?-dmb)2(IP-1T)]2 + produced relaxed circular DNA at the lowest concentrations. Singlet oxygen yields (PhiDelta) increased with n, whereby PhiDelta for [Ru(6,6?-dmb)2(IP-1T)]2 + was only 3%, but increased to 42% on going to [Ru(6,6?-dmb)2(IP-3T)]2 +. This photosensitization process was reflected by single-strand breaks in the gel-mobility shift assays of [Ru(6,6?-dmb)2(IP-3T)]2 +, but was not discernible for the other compounds. Despite different photochemical and photophysical reactivities, all of the compounds were potent phototoxic agents toward cancer cells (EC50 = 1-2 muM) with relatively short compound-to-light intervals and moderate visible light doses. [Ru(6,6?-dmb)2(IP-3T)]2 + was exceptionally photoactive toward cancer cells at longer intervals (EC50 = 200 nM, PI = 750). Phototherapeutic margins increased with n due to decreased dark cytotoxicity for the more pi-expansive complexes, making metal-organic dyad [Ru(6,6?-dmb)2(IP-3T)]2 + the best multifunctional PCT agent.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Rock ‘n’ roll with gold: Synthesis, structure, and dynamics of a (bipyridine)AuCl3 complex

Our previously reported microwave synthesis of (N-N)AuCl2 + complexes (where N-N = 2,2?-bipyridine (bpy) and sterically unencumbered bpy derivatives) was used to prepare derivatives where the bpy moiety was substituted in the 6,6?-positions. Instead of the square-planar complexes, these reactions produced neutral (N-N)AuCl3 complexes. In these, the tethered N-N ligand is bonded such that one N occupies a regular position in the square coordination plane of the Au(III) center and the other N occupies a pseudoaxial position, interacting with Au through an elongated Au-N bond, as determined by X-ray crystallography of two complexes. Variable-temperature 1H NMR spectroscopy reveals that the two sites of the N-N ligand undergo exchange on the NMR time scale. For N-N = 6,6?-Me2bpy the activation parameters were determined to be DeltaH? = 8.5 ± 0.4 kcal mol-1 and DeltaS? = 0.7 ± 2.0 cal K-1 mol -1. The dynamic behavior of (6,6?-Me2bpy)AuCl 3 was investigated by a DFT computational study, which detailed the in-plane rocking motion seen by NMR as well as decoordination of the axially bonded N with concomitant rolling of half of the bpy moiety by rotation around the central C-C bond of the bidentate ligand.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Several dimeric 1,2-bis(2,2′-bipyridinyl)ethane (1,2,6,7,and 9) and 1,2-bis(1,10-phenanthrolinyl)ethane (3,4, and 5) ligands have been synthesized in high yield by oxidative coupling of the corresponding monomeric methylene carbanions using as oxidating agents Br2, I2, and 1,2-dibromoethane.The structure of the compounds obtained from three tetramethyl-2,2′-bipyridines and one tetramethyl-1,10-phenanthroline have been assigned on the basis of their (1)H-NMR spectra.The electronic absorption and emisson properties of these new ligands are reported.They display intense fluorescence spectra.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Inverse electron demand Diels-Alder reaction of functionalized 5,5?-bi-1,2,4-triazines with bicyclo[2.2.1]hepta-2,5-diene in boiling p-cymene leads to a range of 6,6?-disubstituted-2,2?-bipyridines in good yield.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Chemistry is an experimental science, HPLC of Formula: C12H12N2, and the best way to enjoy it and learn about it is performing experiments.Introducing a new discovery about 4411-80-7, Name is 6,6′-Dimethyl-2,2′-bipyridine

6,6′-Dimethyl-2,2′-bipyridyl

In the solid state, the novel ligand 6,6′-dimethyl-2,2′-bipyridyl (dmbp), C12H12N2, is a planar centrosymmetric molecule in which the pyridyl N atoms have a transoid arrangement, by virtue of the symmetry.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI