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1.
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The synthesis of a number of nickel(II) complexes containing the didentate phosphane ligand 1,2-bis(di(o-methoxyphenyl)phosphino)ethane (o-MeO-dppe) is reported. Two types of complexes have been synthesized, i.e., the mono(chelate) complex (1) of the general formula [Ni(o-MeO-dppe)X2] (where X = Cl, Br or I) and the bis(chelate) complex (2) of the general formula [Ni(o-MeO-dppe)2]Y2 (where Y = PF6 or trifluoroacetate (TFA)). These complexes have been characterized using electronic absorption and NMR spectroscopy. The structures of the mono(chelate) complex [Ni(o-MeO-dppe)I2] (1c) and of the bis(chelate) complex [Ni(o-MeO-dppe)2](PF6)2 (2e) have been determined by X-ray crystallography. [Ni(o-MeO-dppe)I2] crystallizes in the monoclinic space group P2(1)/c with Z = 4, a = 12.1309(1) A, b = 16.5759(3) A, c = 17.6474(2) A, beta = 119.3250(10) degrees. [Ni(o-MeO-dppe)2](PF6)2 crystallizes in the monoclinic space group C2/c with Z = 4, a = 22.5326(3) A, b = 13.6794(2) A, c = 21.7134(3) A, beta = 107.1745(7) degrees. In both structures the nickel ion is in a square-planar geometry with a NiP2I2 and NiP4 chromophore, respectively. Using 1H and 31P[1H] NMR spectroscopy the behavior of the complexes in various solvents has been studied. It appears that in solution these nickel complexes are involved in an autoionization equilibrium: 2[Ni(o-MeO-dppe)X2] <==>[Ni(o-MeO-dppe)2](2+) + ["NiX(4)"](2-). The ionized complex (3) consists of a cationic unit in which a nickel atom is surrounded by two didentate phosphane ligands, and an anionic unit that stoichiometrically consists of a nickel atom and four anions. The position of the autoionization equilibrium is highly dependent on the anion and the solvent used. In a polar solvent in combination with weakly coordinating anions only the ionized complex is observed, whereas in an apolar solvent in combination with coordinating anions only the mono(chelate) complex occurs. A comparison of the behavior of o-MeO-dppe with its unsubstituted analogue dppe in combination with nickel(II) acetate using 31P[1H] NMR spectroscopy shows that the latter is more readily oxidized. 相似文献
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Godbole MD Roubeau O Clérac R Kooijman H Spek AL Bouwman E 《Chemical communications (Cambridge, England)》2005,(29):3715-3717
The novel octanuclear cluster [Mn8O2(OH)2(OMe)12(OAc)2(Mesalim)4] (1) presents SMM behaviour with a relatively high experimental energy barrier (eff/kB= 36.0 K) as shown by its dc and ac magnetic properties. 相似文献
5.
W. Bouwman 《Mathematische Annalen》1897,49(1):24-38
Ohne Zusammenfassung 相似文献
6.
Mooibroek TJ Lutz M Spek AL Bouwman E 《Dalton transactions (Cambridge, England : 2003)》2010,39(45):11027-11034
Complexes of the type [Pd(ligand)(2)](anion)(2) were prepared with a series of bidentate di(o-methoxyphenyl)phosphine ligands with increasing steric bulk on the meta position of the phenyl groups: m-H (L1); m-MeO (L2); and m-Me (L3). The solid-state structure of [Pd(L2)(2)](OTs)(2) revealed that the two ligands are symmetrically coordinated to Pd(2+). In the solid state structure of [Pd(L3)(2)](OTs)(2) however, the two ligands are unsymmetrically coordinated to Pd(2+), yielding an unprecedented conformation of this bis-chelate P(4)Pd(2+) complex. (1)H-(1)H-COSY and NOESY analysis and a (31)P-NMR simulation showed that the asymmetric structure of [Pd(L3)(2)](OTs)(2) is retained in solution. 相似文献
7.
C.P. Duif S.N. GeurtsW.G. Bouwman M.Th. RekveldtJ. Plomp 《Physica B: Condensed Matter》2011,406(12):2467-2469
A prototype instrument with an inclined ferromagnetic foil was built which was capable of π-flipping over a broad wavelength range of polarised thermal neutrons in a time-of-flight beam. It was found that, for a single foil, polarised neutrons could be flipped in a wavelength range of 0.2-0.5 nm with an efficiency of 93%. With improved mechanical setup this range probably can even be extended to 0.1-1.0 nm. Foil flippers can have some major advantages for polychromatic SESANS over resonance flippers, but the technical realisation with four foils in series will be challenging. 相似文献
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Vinyl polymerized norbornene has some useful properties such as good mechanical strength, optical transparency and heat resistance. Several transition metal complexes have been described in the literature as active catalysts for the vinyl polymerization of norbornene. We now report the use of three types of nickel(II) complexes with N‐heterocyclic carbene (NHC) ligands in the catalytic vinyl polymerization of norbornene under a range of conditions. Specifically, two nickel complexes bearing a chelating bis(NHC) ligand, two nickel complexes bearing two chelating anionic N‐donor functionalized NHC ligands as well as one diiodidonickel(II) complex with two monodentate NHC ligands were tested. The solid‐state structure of bis(1,3‐dimethylimidazol‐2‐ylidene)diiodidonickel(II), as determined by X‐ray crystallography, is presented. The highest polymerization activity of 2.6 × 107 g (mol cat)?1 h?1 was observed using the latter nickel complex as catalyst, activated by methylaluminoxane. The norbornene polymers thus obtained are of high molecular weight but with rather low polydispersity. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
10.
Mooibroek TJ Schoon L Bouwman E Drent E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(47):13318-13333
The reactivity of palladium complexes of bidentate diaryl phosphane ligands (P2) was studied in the reaction of nitrobenzene with CO in methanol. Careful analysis of the reaction mixtures revealed that, besides the frequently reported reduction products of nitrobenzene [methyl phenyl carbamate (MPC), N,N′‐diphenylurea (DPU), aniline, azobenzene (Azo) and azoxybenzene (Azoxy)], large quantities of oxidation products of methanol were co‐produced (dimethyl carbonate (DMC), dimethyl oxalate (DMO), methyl formate (MF), H2O, and CO). From these observations, it is concluded that several catalytic processes operate simultaneously, and are coupled via common catalytic intermediates. Starting from a P2Pd0 compound formed in situ, oxidation to a palladium imido compound P2PdII?NPh, can be achieved by de‐oxygenation of nitrobenzene 1) with two molecules of CO, 2) with two molecules of CO and the acidic protons of two methanol molecules, or 3) with all four hydrogen atoms of one methanol molecule. Reduction of P2PdII?NPh to P2Pd0 makes the overall process catalytic, while at the same time forming Azo(xy), MPC, DPU and aniline. It is proposed that the Pd–imido species is the central key intermediate that can link together all reduction products of nitrobenzene and all oxidation products of methanol in one unified mechanistic scheme. The relative occurrence of the various catalytic processes is shown to be dependent on the characteristics of the catalysts, as imposed by the ligand structure. 相似文献