Nickel complexes amines

Activated aryl chlorides, which are close in reactivity to unactivated aryl bromides, underwent reaction with the original P(o-tol)3-ligated catalyst.58 Nickel complexes, which catalyze classic C—C bond-forming cross-couplings of aryl chlorides, 9-64 also catalyzed aminations of aryl chlorides under mild conditions.65,66 However, the nickel-catalyzed chemistry generally occurred with lower turnover numbers and with a narrower substrate scope than the most efficient palladium-catalyzed reactions. 

Alkylnickel amido complexes ligated by bipyridine have been prepared that undergo reductive elimination of V-alkyl amines (Equation (54)).207,208 Unlike the phosphine-ligated palladium arylamides, these complexes underwent reductive elimination only after oxidation to nickel(III). Thermally induced reductive elimination of alkylamines from phosphine-ligated nickel complexes appears to occur after consumption of phosphine by arylazides 209... 

These telomerization reactions of butadiene with nucleophiles are also catalyzed by nickel complexes. For example, amines (18-23), active methylene compounds (23, 24), alcohols (25, 26), and phenol (27) react with butadiene. However, the selectivity and catalytic activity of nickel catalysts are lower than those of palladium catalysts. In addition, a mixture of monomeric and dimeric telomers is usually formed with nickel catalysts ... 

Allylation of amines with allyiic alcohols in the presence of reducible nickel complexes easily occurs at 80°C (example 4, Table X). 

Macrocyclic Fi-donor ligands and vitamin Bj, analogues. The free amine [(97) tet] can be prepared from the previously reported nickel complex. Cobalt-fin) complexes have been prepared with both planar (bcde octahedral) and folded (abed octahedral) co-ordination. Derivatives of the three ligand configurations arising from restricted inversion at the four chiral co-ordinated secondary amino-groups have been prepared (see Scheme 2) and their stabilities and configurations discussed. ... 

Two other refining processes are also frequently employed. One involves hydrometallurgical refining in which sulfide concentrates are leached with ammonia solution to convert the copper, nickel, and cobalt sulfides into their complex amines. Copper is precipitated from this solution upon heating. Under such conditions, the sulfide-amine mixture of nickel and cobalt are oxidized to their sulfates. The sulfates then are reduced to metalhc nickel and cobalt by heating with hydrogen at elevated temperatures under pressure. The metals are obtained in their powder form. 

Using standard anaerobic techniques, a 100-mL Schlenk flask equipped with a stir bar is charged with 50 mL dry benzene and 2 mL (1.96 g, 0.0172 mol) distilled free amine. If crude daco is used, the product will be less pure and of lower yields. The mixture is warmed to 50-60°C under N2. Three 1-mL (0.05 mol) portions of ethylene sulfide are added, allowing 20 min reaction time between additions. The mixture is then heated under N2 for 1 h. Complete reaction is indicated by the formation of a finely divided white precipitate after the final addition. The reaction mixture is filtered anaerobically through a bed of celite in a glass-fritted funnel. Solvent is removed under vacuum while continuing to heat at 50-60°C. The H2-bme-daco is obtained as a colorless to pale yellow oil. Irrespective of color, this material is of suitable quality to be converted to the nickel complex. If distilled daco is used, the product is quite pure. Attempts at vacuum distillation (bpo.immHg = 135°C) resulted in partial decomposition. Yield 3.21 g (80%). 

Ni(04C2)(tet-a)-3H20 (tet = 5,7,7,12,14,14-hexamethyl-l,4,8,ll-tetraazacyclotetradecane a = meso isomer b = racemic isomer) were prepared by the reaction of a concentrated solution of sodium oxalate with an aqueous solution of the appropriate nickel(II) amine complex.1780,1781 In the dinuclear complex [Ni2(04C2)(en)4](N03)2 (234)1740-1741 the bridging oxalato group is planar and symmetrically bonded to the two nickel atoms. The same structure occurs in the complex Ni2(04C2)(0N0)2(py)6 which was obtained as a by-product in a very low yield when a pyridine solution of methanenitrosolic acid and nickel(II) were allowed to stand for several months.1741... 

The reaction of the appropriate amine with the nickel complexes formed by isonitroacetyl-acetone in refluxing EtOH-CHCl3 mixture affords the complexes (331).2412... 

The higher valent nickel complexes with saturated amine donors have little more than a transient existence as independent species in solution and consequently have a limited chemistry. Complexes with stronger donor ligands have a more extensive chemistry. 

A number of nickel complexes have been shown to possess fungicidal activity. Salicylic acid complexes of the type Ni(salicylate)2(amine)2 have been tested on a range of fungi. They were active quite generally and in many cases the amine complexes were more active than... 

Bis(phosphoranimine) ligands, chromium complexes, 5, 359 Bis(pinacolato)diboranes activated alkene additions, 10, 731—732 for alkyl group functionalization, 10, 110 alkyne additions, 10, 728 allene additions, 10, 730 carbenoid additions, 10, 733 diazoalkane additions, 10, 733 imine additions, 10, 733 methylenecyclopropane additions, 10, 733 Bisporphyrins, in organometallic synthesis, 1, 71 Bis(pyrazol-l-yl)borane acetyl complexes, with iron, 6, 88 Bis(pyrazolyl)borates, in platinum(II) complexes, 8, 503 Bispyrazolyl-methane rhodium complex, preparation, 7, 185 Bis(pyrazolyl)methanes, in platinum(II) complexes, 8, 503 Bis(3-pyrazolyl)nickel complexes, preparation, 8, 80-81 Bis(2-pyridyl)amines... 

Copper Complexes. The preparation of copper and nickel complexes of tridentate metallizable azo and azomethine dyes is easily carried out in aqueous media with copper and nickel salts at pH 4-7 in the presence of buffering agents such as sodium acetate or amines. Sparingly water soluble precursors can be metallized in alkaline medium at up to pH 10 by using an alkali-soluble copper tetram(m)ine solution as coppering reagent, which is available by treating copper sulfate or chloride with an excess of ammonia or alkanolamines [3],... 

An alternative procedure starts from a metal complex of o-phenylenedi-amine. For example, the bis(o-phenylenediamine) complex of nickel(II) chloride reacts with acetylacetone to give a mixture of a nickel complex of the diamine and diketone together with 2,4-dimethylbenzodiazepinium chloride (76CPB1934 91JPR327). Chromium complexes have been used in the same way [91JCS(D)2045]. 

Schwoegler and Adkins (93) reacted alcohols with primary and secondary amines over Raney nickel to form secondary and tertiary amines, respectively. Since tertiary alcohols do not undergo the reaction, it is assumed that the catalyst dehydrogenates the alcohol to a carbonyl compound which reacts with an amine to give a product that can be readily hydrogenated to a more complex amine. Piperidine was reacted with ethyl, n-butyl, and n-dodecyl alcohols to give 82, 70, and 69% yields, respectively, of the corresponding alkylpiperidines. 

Successful development of the asymmetric hydrocyanation reaction may provide a versatile route to chiral nitriles, amines, and acids. As we have seen, the mechanistic details of the hydrocyanation reaction of butadiene with zero-valent nickel complexes are well established. By using a nickel complex of a chiral bidentate phosphinite ligand, 9.53, good conversion and enantioselectiv-ity (>85% e.e.) for the hydrocyanation of 6-methoxy 2-vinyl naphthalene have been obtained. 

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