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TPC-H data (scale factor 10), Customers joined with Orders joined with Lineitems, translated into JSON with the following structure:
Array of Customer with nested `c_orders` which is an array of Orders, each order with nested `o_lineitems` which is an array of Lineitems.
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The coordination chemistry of 2,2′-bis(di-iso-propylphosphino)-trans-stilbene (tPCHCHP) with group 10 metal centers in a variety of oxidation states is reported; different coordination modes were observed depending on the oxidation state of the metal. With metal centers in the 0 or +1 oxidation state ((tPCHCHP)Ni, [(tPCHCHP)Pd]2, (tPCHCHP)NiCl, (tPCHCHP)NiI), η2 coordination of the olefin occurs, whereas, with metals in the +2 oxidation state, C–H activation of the backbone, followed by rapid H–X reductive elimination, was observed, leading to an η1 coordination of the backbone in (tPCCHP)MCl (M = Ni, Pd, Pt). Employing the methyl-substituted analogue, 2,2′-bis(di-iso-propylphosphino)-trans-diphenyl-1,2-dimethylethene (tPCMeCMeP), forced an η2 coordination of the olefin in [(tPCMeCMeP)NiCl]2[NiCl4]. The synthesis of the hydride complex (tPCCHP)NiH was attempted, but, instead, led to the formation of (tPCHCHP)Ni, indicating that the vinyl form of the backbone can function as a hydrogen acceptor. All metal complexes were characterized by multinuclei NMR spectroscopy, X-ray crystallography, and elemental analysis.
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The synthesis and characterization of the two iron chlorin complexes [FeIII(TPC)(NH2CH(CO2CH3)(CH(CH3)2))2]CF3SO3 (1) and FeII(TPC)[(NH2CH(CO2CH3)(CH(CH3)2)]2 (2) are reported. The crystal structure of complex 1 has been determined. The X-ray structure shows that the porphyrinate rings are weakly distorted. The metal−nitrogen distances to the reduced pyrrole N(4), 2.034(4) Å, and to the pyrrole trans to it N(2), 2.012(4) Å, are longer than the distances to the two remaining nitrogens [N(1), 1.996(4) Å, and N(3), 1.984(4) Å], leading to a core−hole expansion of the macrocycle due to the reduced pyrrole. The 1H NMR isotropic shifts at 20 °C of the different pyrrole protons of 1 varied from −0.8 to −48.3 ppm according to bis-ligated complexes of low-spin ferric chlorins. The EPR spectrum of [Fe(TPC)(NH2CH(CO2CH3)(CH(CH3)2))2]CF3SO3 (1) in solution is rhombic and gives the principal g values g1 = 2.70, g2 = 2.33, and g3 = 1.61 (∑g2 = 15.3). These spectroscopic observations are indicative of a metal-based electron in the dπ orbital for the [Fe(TPC)(NH2CH(CO2CH3)(CH(CH3)2))2]CF3SO3 (1) complex with a (dxy)2(dxzdyz)3 ground state at any temperature. The X-ray structure of the ferrous complex 2 also shows that the porphyrinate rings are weakly distorted. The metal−nitrogen distances to the reduced pyrrole N(4), 1.991(5) Å, and to the pyrrole trans to it N(2), 2.005(6) Å, are slightly different from the distances to the two remaining nitrogens [N(1), 1.988(5) Å, and N(3), 2.015(5) Å], leading to a core−hole expansion of the macrocycle due to the reduced pyrrole.
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Proton assignment in 1H-NMR [47,48].
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Attribution 4.0 (CC BY 4.0)https://creativecommons.org/licenses/by/4.0/
License information was derived automatically
TPC-H data (scale factor 10), Customers joined with Orders joined with Lineitems, translated into JSON with the following structure:
Array of Customer with nested `c_orders` which is an array of Orders, each order with nested `o_lineitems` which is an array of Lineitems.