RESUMO
Inspired by natural photosynthesis, features such as proton relays have been integrated into water reduction catalysts (WRC) for effective production of hydrogen. Research by DuBois et al. showed the crucial influence of these relays, largely in the form of pendant amine functions. In this work catalysts are presented containing innovative diphosphinoamine ligands: [M(ii)Cl2(PNP-C1)], [M(ii)(MeCN)2(PNP-C1)]2+, [M(ii)(PNP-C1)2]2+, and [M(ii)Cl(PNP-C2)]+ (M = Pt2+, Pd2+, Ni2+, Co2+; PNP-C1 = N,N-bis{(di(2-methoxyphenyl)phosphino)methyl}-N-alkylamine, PNP-C2 = N,N-bis{(di(2-methoxyphenyl)phosphino)ethyl}-N-alkylamine and alkyl = Me, Et, iso-Pr, Bz). Synthetic strategies and detailed characterisation are covered, including 1H-, 13C-, and 31P-NMR analysis, mass spectroscopy and single crystal X-ray diffractometry (XRD). The catalytic properties have been explored by changing the pendant amines and auxiliary methoxy coordination sites, as well as enlarging the ligand backbone. Moreover, confirmed by density functional theory (DFT) calculations based on XRD data in vacuo and solvent environment, two very different catalytic cycles are proposed. PNP-C1 shows a classical proton relay, whereas PNP-C2 allows an additional coordination of nitrogen, acting optionally like a pincer. Through new insights into efficiency and stability-increasing influences of proton relays in general, their number per metal centre, an enlarged ligand backbone and the use of solvato instead of halogenido complexes, substantial improvements have been made in catalytic performance over the DuBois et al. catalysts and recently self-made WRCs. The turnover number (TON) related to the single site of cost-efficient nickel WRCs is increased from 11.4 to 637, whereas a corresponding palladium catalyst gives TON as high as 2289.
RESUMO
The bis(bidentate) phosphine cis,trans,cis-1,2,3,4-tetrakis(diphenylphosphino)cyclobutane (dppcb) has been regioselectively oxidized leading to novel, hemilabile ligands. [Co2Cl4(dppcb)] (1a) is transformed via cobalt(II) mediated dioxygen activation into [Co2Cl4(2,3-trans-dppcbO2)] (2a) in excellent yield, where 2,3-trans-dppcbO2 is cis,trans,cis-2,3-bis(diphenylphosphinoyl)-1,4-bis(diphenylphosphino)-cyclobutane. By contrast, the in situ presence of dioxygen during the synthesis of Co2Br4(dppcb)] (1b) produces both [Co2Br4(2,3-trans-dppcbO2)] (2b) and [Co2Br4(1,3-trans-dppcbO2)] (3), where 1,3-trans-dppcbO2 is cis,trans,cis-1,3-bis(diphenylphosphinoyl)-2,4-bis(diphenylphosphino)-cyclobutane. The new compounds 2a, 2b and 3 have been obtained as pure, crystalline solids and all three X-ray structure analyses have been performed showing folded cyclobutane rings. Interestingly, the corresponding reaction using [Co2I4(dppcb)] (1c) proceeds chemoselectively. Thus, [Co2I4(dppcbO3)] (4), where dppcbO3 is cis,trans,cis-1,2,3-tris(diphenylphosphinoyl)-4-diphenylphosphinocyclobutane, is formed in excellent yield and also fully characterized by an X-ray structure analysis showing two different conformations of 4. However, [Co2(NO3)4(dppcb)] (1d) shows no dioxygen activation at all. Therefore, in order to reveal the mechanism of this oxidation [Co2I4(DMF)2(dppcb)] (5) has been prepared and its X-ray structure is presented. The synthesis of [Co2I4(PMe2Ph)2(dppcb)] (6) proves that this is a common reaction pathway. Furthermore, because the product distribution of the oxidation strongly depends on the kind of halides present, the whole series Co2X4(dppcbO4)] (X = Cl, 7a; Br, 7b; I, 7c) has been prepared, where dppcbO4 is cis,trans,cis-1,2,3,4-tetrakis(diphenylphosphinoyl)-cyclobutane, and all three X-ray structures are given, also showing folded cyclobutane rings. It seems likely that coordination of dppcb to cobalt(II) is essential to form the regio- and chemoselectively oxygenated molecules.
RESUMO
The structure of the title compound, C23H32O4, an arylalkanone isolated from the petroleum ether fraction of the ethanol extract of the bark of Virola venosa, has been established by NMR spectroscopy and, for the first time, by X-ray structure analysis. Two independent molecules of the same enantiomer are present in the unit cell. Both molecules exhibit an intramolecular hydrogen bond, which can be correlated with a rare signal observed at 18.28 p.p.m. in the 1H NMR spectrum. The packing, in space group P1, is determined by a pseudo-center of symmetry leading to a short intermolecular contact, which is present in one molecule but does not occur in the other. As a consequence, the O-C-C-O torsion angles [-16.9 (3) and -12.7 (3) degrees ] through the ketone and its adjacent hydroxy group are significantly different in the two molecules.