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A series of eta3-indenyl molybdenum compounds [(eta3-4,7-Me2C9H5)Mo(CO)2(N,NL)Cl] (N,NL = bpy, phen, pyma), isostructural with well-known eta3-allyl compounds, was synthesized from the recently established halide synthon [{(eta5-4,7-Me2C9H5)Mo(CO)2(mu-Cl)}2]. The low stability of the hexacoordinated eta3-indenyl molybdenum species in solution has been overcome by a modification of the chelating ligand. Hence, the dissociation of the compounds bearing ligands with methyl groups beside nitrogen donor atoms (e.g. 6,6?-Me2-bpy, 2,9-Me2-phen; 2,9-Me2-4,7-Ph2-phen) is strongly disfavored due to the steric requirements of the substituents. The considerable discrimination of the pentacoordinated species enables the use of [(eta5-4,7-Me2C9H5)Mo(CO)2(2,9-Me2-phen)][BF4] for the assembly of derivatives bearing other halides and pseudohalides in the coordination sphere of molybdenum. The current study further describes some other new indenyl complexes accessible from [{(eta5-4,7-Me2C9H5)Mo(CO)2(mu-Cl)}2]. All structural types presented in this experimental study were supported by X-ray crystallographic data.

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Reference:
Metal catalyst and ligand design,
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The invention relates to macrocyclic rare earth complexes which consist of at least one rare earth salt complexed by a macrocyclic compound of formula (I): STR1 in which: the bivalent radicals A, B, C and D, which are identical or different, are hydrocarbon chains optionally containing one or more heteroatoms, at least one of said radicals containing at least one molecular unit or essentially consisting of a molecular unit possessing a triplet energy greater than the energy of the emission level of the complexed rare earth ion, at least one of said radicals consisting of a substituted or unsubstituted nitrogen-containing heterocyclic system in which at least one of the nitrogen atoms carries an oxy group, and it being possible for one of the radicals C or D not to exist; and X1 and X2, which are identical or different, are hydrogen or a hydrocarbon chain (CH2)n optionally interrupted by 1 or more heteroatoms, n being an integer from 1 to 10, with the proviso that if the radicals A and/or B are a nitrogen-containing heterocyclic system in which at least one of the nitrogen atoms carries an oxy group, the radicals C and/or D are selected from biquinolines, biisoquinolines, bipyridines, terpyridines, coumarins, bipyrazines, bipyrimidines and pyridines, and to their use for reducing the perturbations in a fluorescent assay.

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Bidentate ligands 2,2?-biquinoline (biq) and 6,6?-dimethyl-2,2?-bipyridine (dmbpy) with steric hindrance substituents cis to the nitrogen atoms have been used in the synthesis of transition metal complexes. Six new doubly end-on azido-bridged binuclear complexes [M2(biq)2(mu1,1-N3)2(N3)2] (M = Ni (1), M = Co (2)), [M2(biq)2(mu1,1-N3)2Cl2] (M = Ni (3), M = Co (4)), [M2(dmbpy)2(mu1,1-N3)2(N3)2] (M = Ni (5), M = Co (6)) and one end-to-end thiocyanato-bridged polymeric [Ni(dmbpy)(mu1,3-SCN)(NCS)]n (7) have been synthesized and characterized by single crystal X-ray diffraction analysis and magnetic studies. Complexes 1-6 comprise five-coordinate M(II) ions bridged by two end-on azide ligands. The bridging M-N-M bond angles are in the small range 104.1-105.2. Complex 7 consists of a singly thiocyanate-bridged Ni(II) chain in which Ni(II) ions are five-coordinate. This research suggests that the bulky ligands play a key role in the formation of five-coordinate coordination structure. All complexes display intramolecular intermetallic ferromagnetic coupling with JNiNi and JCoCo of ca. 23 or 13 cm-1 based on the Hamiltonian over(H, ^) = – 2 J over(S, ^)1 over(S, ^)2 (S1 = S2 = 1 for Ni2, or 3/2 for Co2). The singly SCN–bridged chainlike complex 7 shows intrachain ferromagnetic interaction with J = 3.96(2) cm-1 and D = -4.55(8) cm-1 (over(H, ^) = – 2 J ?i = 1 (over(S, ?)i over(S, ^)i + 1) – D ?i = 1 [(over(S, ^)iZ)2 – 2 / 3]). Magneto-structural correlationship has been investigated.

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A novel Ni-catalyzed regiodivergent reductive carboxylation of allyl esters with CO2 has been developed. This mild, user-friendly, and operationally simple method is characterized by an exquisite selectivity profile that is dictated by the ligand backbone.

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Metal catalyst and ligand design,
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The Stille-type cross-coupling reaction on mesylate, tosylate, and triflate allowed synthesis of symmetrical but also interesting unsymmetrical monofunctionalized 2?2?-bipyridines in possible multigram scales.

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The stability of a variety of bidentate N-base adducts of MoO 2Cl2 and (CH3)ReO3 (MTO) was investigated in thf and CH2C12 as solvents. The formation constants were determined from the spectrophotometric data based on 1:1 adduct formation. The adduct formation constants for [MoO2Cl 2L2](L2 = bidentate nitrogen ligand) are 104-106 times higher than those for [(CH 3)ReO3L2] with the same ligands under the same conditions. The adduct stability of both systems is very sensitive to the electronic nature of the ligands and increases with their donor ability. Hammett correlations of the formation constants against sigmagive relatively large negative values for the reaction constants (pRe = -5.9, p Mo = -6.6). The stability is also governed by steric and strain factors. Thus, sterically hindered 6,6′-disubstituted 2,2′ -bipyridines do not form ad ducts with MTO, and only 6,6′-dimethyl- and 6,6′-diphenyl- 2,2′-bipyridines form adducts with MoO2Cl2. However, these adducts are much less stable than other methyl derivatives of 2,2′-bipridine adducts. The steric strain between the two methyl groups in 3,3-dimethy 1-2,2′-bipyridine influences the bipyridine planarity upon complexation and reduces the adduct stability. The thermodynamic parameters (enthalpy and entropy) were determined from temperature-dependence studies. The adduct stability is mainly due to the strongly exothermic binding of the nitrogen-bidentate ligand. The entropy change is small and has little effect on adduct stability.Wiley-VCH Verlag GmbH & Co, KGaA.

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Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In a article, 4411-80-7, molcular formula is C12H12N2, introducing its new discovery. HPLC of Formula: C12H12N2

A number of nitrogen, sulfur or oxygen containing bis-heteroaromatic or bis-heterocyclic derivatives have been synthesized in good to excellent yields by homocoupling of the corresponding halogenated compounds in the presence of liganded (triphenylphosphine or 2,2′-bipyridine) nickel Complex Reducing Agents in THF or DME at 63 deg C.

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The influence of various solvents on the electronic absorption spectra in the visible region of complexes of the general type (M = Cr, Mo, W; n = 3, 4, 5, 6; X = CH3, CN, CO2CH3; bipy = 2,2′-bipyridine) has been measured.Molar absorption coefficients are reported.Attempts to correlate this information with the solvent polarity parameter proposed by Manuta and Less indicate that the effects of geometric distortion in the substrate complex preclude a simple explanation of the observations in terms of a single parameter.Keywords: Chromium; Molybdenum; Tungsten; Solvatochromism; Bipyridine; Carbonyl

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Metal catalyst and ligand design,
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The syntheses of 6-(chloromethyl)- (3), 6-(chloromethyl)-6′-methyl- (2), and 6,6′-bis(chloromethyl)-2,2′-bipyridine (1) are reported.Complete spectral analyses including 1H and 13C NMR data are given for each compound.Experimental results and appropriate comparisons justify the reassignment of the 13C NMR spectral data for the bipyridine derivatives.Description of the synthetic techniques with the new, critical modifications utilized to prepare these key starting materials are presented.Bipyridine N-oxides have been shown to undergo intra-ring rearrangements; no N-oxide migration occurs under thermolysis at 200 deg C.

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Metal catalyst and ligand design,
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The presently-disclosed subject matter includes light-activated ruthenium compounds. In some embodiments the compounds release one or more ligands when exposed to light, and in specific embodiments the light includes a wavelength of about 500 nm to about 1000 nm. The present compounds can also comprise an overall charge, wherein the overall charge can be a positive overall charge or a negative overall charge. Further still, embodiments include methods of treating cancer in a subject by administering a compound and then exposing a site of the subject to light.

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