Nickel phenyl complexes

In the presence of 6-iodo-l-phenyl-l-hexyne, the current increases in the cathodic (negative potential going) direction because the hexyne catalyticaHy regenerates the nickel(II) complex. The absence of the nickel(I) complex precludes an anodic wave upon reversal of the sweep direction there is nothing to reduce. If the catalytic process were slow enough it would be possible to recover the anodic wave by increasing the sweep rate to a value so fast that the reduced species (the nickel(I) complex) would be reoxidized before it could react with the hexyne. A quantitative treatment of the data, collected at several sweep rates, could then be used to calculate the rate constant for the catalytic reaction at the electrode surface. Such rate constants may be substantially different from those measured in the bulk of the solution. The chemical and electrochemical reactions involved are... 

Diastereoselective preparation of a-alkyl-a-amino acids is also possible using chiral Schiff base nickel(II) complexes of a-amino acids as Michael donors. The synthetic route to glutamic acid derivatives consists of the addition of the nickel(II) complex of the imine derived from (.S )-,V-[2-(phenylcarbonyl)phenyl]-l-benzyl-2-pyrrolidinecarboxamide and glycine to various activated olefins, i.e., 2-propenal, 3-phenyl-2-propenal and a,(f-unsaturated esters93- A... 

Phenylurefbanes, 58, 10 Phosgene, 57, 46 Phosphine, diphenyl-, 56,45 Phosphine-mckcl catalyst, 58, 129 PHOSPHINE-NICKEL CATALYZED COMPLEX CROSS-COUPLING OF GRIG-NARD REAGENTS WITH ARYL AND ALKENYL HALIDES, 58, 127 Phosphine, phenyl-, bis(3-dimethylamino-piopyl)-, 55, 128 Phosphine, triphenyl-, 56, 81 Phosphomum, [ 4-(4-rne thoxy phenyl)-2-butenyl) triphenyl, iodide, 56, 81 Phosphomum, 2-octadecenyltnphenyl-, iodide, 56, 81... 

Both compounds being colorless and volatile, the liquid methyl derivative could be distilled in vacuo (b.p. 66-68° at 3.5 mm.), while the phenyl compound is a crystalline solid melting at 66°, which is sublimable in vacuo. The fluorination reactions occur somewhat less vigorously than in the case of the phosphorus trichloride nickel-(0) complex, and gentle heating was normally required to initiate the reaction. Benzene was used as a solvent. 

Effects of Different Metal Salicylaldimine Chelates. Varying the central metal profoundly affected catalytic and inhibitory properties. There were only small quantitative variations, however, between N-phenyl- and V-butylsalicylaldimines having the same central metal atom. The only other salicylaldimines where catalyst-inhibitor conversion could be demonstrated were those of copper (II). With copper (II) both the catalytic and the inhibitory effects are much less pronounced than for cobalt (II). Surprisingly nickel (II) complexes behaved like conventional catalysts for hydrocarbon autoxidation—i.e., the rate is proportional to... 

Selected nickel(II) complexes with C-substituted diamines are listed in Table 41. In solution the square planar coordination is favoured,700 while both square planar and six-coordinate complexes have been isolated in the solid state. Complexes with l,2-diphenyl-l,2-diaminoethane (stilbendiamine, stien) and l-phenyl-l,2-diaminoethane have been widely studied.701-706 Using CI2CHCO2 as counterion, two complexes have been obtained with the former ligand, one blue, monoclinic, P2Jc ( Ueif = 3.16BM), the other yellow-green, triclinic,... 

With a view to preparing polymerizable complexes, thiophene-substituted nickel-dithiolene complexes [Ni(L)(L )] have been synthesized and used to prepare films by electrochemical polymerization. The features of the complexes and of the polymers depend on the number of thiophene substituents. In particular, the complex with four thiophene substituents (L = L = thpdt, 12) shows a narrower HOMO-LUMO gap as compared to complexes with two thiophene and two phenyl groups or four phenyl groups [Xmax, nm (e, M- cm- ) 976 (38800) L = L = 12 931 (37700) L = 12, L = 9, R = Ph 866 (30900) L = L = 9, R = Ph] and gave a polymer whose electrochemical features are similar to those of poly[l,2-di(2,5-thienylene)ethane], suggesting that similar extended chains are formed"". 

Some iron and nickel cyanide and carbonyl complexes have been reported as models of the [FeNi]-hydrogenase enzymes. The preparation and structures of the trigonal bipyramidal nickel and iron complexes with the tetradentate ligands tris(2-phenylthiol)phosphine (PS3) and tris(3-phenyl-2-thiophenyl)phosphine (PS3 ) have been reported [70, 71]. The nickel carbonyl complex [Ni(PS3 )(CO)] exhibits vco at 2029 cm compared with the value of 1940 em" for the iron earbonyl complex [Fe(PS3 )(CO)]. Both of these complexes lose CO upon oxidation. The use of cyanide in place of carbon monoxide allows for the preparation of both [Fe (PS3)(CN)] and [Fe (PS3 )(CN)] eomplexes. The IR properties of... 

A tripod-type Schiff-base ligand, (127), was prepared by a 3 1 condensation reaction of 2-phenyl-4-formylimidazole in methanol.204 In two nickel(II) complexes, the screw coordination arrangement of the tripod ligand (127) around the metal ion induces chirality, resulting in a A (clockwise) or a A (anticlockwise) enantiomer.204 A multifunctional tripodal ligand possessing two different functionalities, such as pyridine and cyano moieties, (128), has been prepared by the reaction of 2-aminomethylpyridine, excess acrylonitrile, and glacial acetic acid. 

The general catalytic performance of these metal complexes in polymerization of olefins was screened by the following standard procedure The complexes (50 or 100 pmol) were activated with 100 mole equivalents of methylalumoxane (MAO) in toluene solution. The polymerization reaction was carried out at a temperature of 30°C, during which ethene was added with a flow of 40 L h"t After 4.5 h, the mixture was quenched with methanol, the solid polymer isolated, washed and dried. For benchmarking a nickel diimine complex [12a] with 2,6-(di-isopropyl) phenyl substituents at the imine nitrogen atoms (133) was also included. Tab. 3.2 shows the activity and polymer data. 

Polymerizations with nickel salicylaldimine complexes 87-101 were performed in a 1 L steel autoclave at 40 bar and 30 °C. The nickel complexes (0.09 mmol) were activated with equimolar amounts of Ni(COD)2 in toluene solutions for 30 min after which the autoclave was pressurized with ethene. The reaction was terminated after 1.5 h by venting the ethene and the formed polymer powder was isolated. Details are summarized in Tab. 3.9. For comparison, complex 134, a nickel salicylaldimine complex with a 2,6-(diisopropyl)phenyl imine substituent, was screened under the same conditions. 

Other applications of the technique include examination of the nickel(II) complex with imidazole. <86JA6470>, and mechanistic studies of the dehydrogenation of 1,2,3-trimethyl-2-phenyl-benzimidazoline <84CHE817,87CHE525). 

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