Nickel carbon dioxide complex

When manganese vapour and a mixture of nitric oxide, trifluorophosphine and boron trifluoride are co-condensed the compound Mn(PF3)(NO)3 is produced [280]. Co-condensation of nickel and carbon dioxide results in the formation of some nickel tetracarbonyl [280]. Burdett and Turner [298] showed that co-condensation of nickel and nitrogen at 20°K resulted in a nickel—nitrogen complex. Moskovits and Ozin [299] have recently repeated the experiment and have shown from the infrared spectrum of the matrix that the major product is NiN2, with the nickel atom bonded to the end of the nitrogen molecule. 

Sakaki S, Mine K, Taguchi D, Aral T (1993) Formation of the oxanickelacyclopentene complex from nickel(O), carbon dioxide, and alkyne. An ab initio MO/SD-CI study. Bull Chem Soc Jpn 66 3289-3299... 

The question of the compatibility of metals and alloys with carbon and carbonaceous gases has assumed considerable importance in connection with the development of the gas-cooled nuclear reactor in which graphite is used as a moderator and a constituent of the fuel element, and carbon dioxide as the coolant. Tests of up to 1 000 h on a series of metals and nickel-containing alloys under pressure contact with graphite at 1 010°C" showed that only copper was more resistant than nickel to diffusion of carbon and that the high-nickel alloys were superior to those of lower nickel content. The more complex nickel-chromium alloys containing titanium, niobium and aluminium were better than the basic nickel-chromium materials. 

The [2-I-2-I-2] cycloaddition reaction of diynes 40 and carbon dioxide 41 were successfully catalysed by a NHC-nickel (Scheme 5.12) [15]. The NHC-Ni complex was prepared in situ from [NiCCOD) ] and two equivalents of carbene. Pyrones 42 were obtained in excellent yields at atmospheric pressure of CO and mild reaction conditions. 

Pyridine compounds 45 can also be produced by the NHC-Ni catalysed cycloaddition between nitriles 43 and diynes 44 (Scheme 5.13) [16]. The SIPr carbene was found to be the best ligand for the nickel complex in this reaction. The reaction required mild reaction conditions and low catalyst loadings, as in the case of cycloaddition of carbon dioxide. In addition to tethered aUcynes (i.e. diynes), pyridines were prepared from a 3-component coupling reaction with 43 and 3-hexyne 23 (Scheme 5.13). The reaction of diynes 44 and nitriles 43 was also catalysed by a combination of [Ni(COD)J, NHC salts and "BuLi, which generates the NHC-Ni catalyst in situ. The pyridines 45 were obtained with comparable... 

Insertion of carbon dioxide into olefin oxides gives olefin carbonates, and is an example of basic catalysis with nickel(O) complexes (example 14, Table XI). 

Equations 1 to 3 show some of fixation reactions of carbon dioxide. Equations la and lb present coupling reactions of CO2 with diene, triene, and alkyne affording lactone and similar molecules [2], in a process catalyzed by low valent transition metal compounds such as nickel(O) and palladium(O) complexes. Another interesting CO2 fixation reaction is copolymerization of CO2 and epoxide yielding polycarbonate (equation 2). This reaction is catalyzed by aluminum porphyrin and zinc diphenoxide [3],... 

Brydon and Roberts- added hemolyzed blood to unhemolyzed plasma, analyzed the specimens for a variety of constituents and then compared the values with those in the unhemolyzed plasma (B28). The following procedures were considered unaffected by hemolysis (up to 1 g/100 ml hemoglobin) urea (diacetyl monoxime) carbon dioxide content (phe-nolphthalein complex) iron binding capacity cholesterol (ferric chloride) creatinine (alkaline picrate) uric acid (phosphotungstate reduction) alkaline phosphatase (4-nitrophenyl phosphate) 5 -nucleotidase (adenosine monophosphate-nickel) and tartrate-labile acid phosphatase (phenyl phosphate). In Table 2 are shown those assays where increases were observed. The hemolysis used in these studies was equivalent to that produced by the breakdown of about 15 X 10 erythrocytes. In the bromocresol green albumin method it has been reported that for every 100 mg of hemoglobin/100 ml serum, the apparent albumin concentration is increased by 100 mg/100 ml (D12). Hemolysis releases some amino acids, such as histidine, into the plasma (Alb). 

Carbon dioxide reacts either with alkene and alkyne complexes of nickel(0) or with free alkenes and alkynes in the presence of nickel(O) complexes, giving five-membered cyclic nickel(II) complexes (equations 90 and 91).278... 

Insertion of carbon dioxide into a nickel-carbon bond has recently been demonstrated. The complex Ni(C2H5)2(bpy), (bpy = 2,2 -bipyridine), reacts with C02 in benzene at 40-50°C as shown in (62a) 141a). The intermediate nickel(II) alkyl carboxylate can then react with additional C02 to form either a dicarboxylate or diethyl ketone, as in (62b) and (62c). 

Fisher and Eisenberg (107) have reported on the electrocatalytic reduction of carbon dioxide using macrocycle complexes of nickel and cobalt (e.g., complex 27). An indirect electrochemical reduction of C02 was ac-... 

Tinnemans, A.H.A., Koster, T.P.M., Thewissen, D.H.M.W. and Mackor A. 1984. Tetraaza-macrocyclic cobalt(II) and nickel(II) complexes as electrontransfer agents in the photo( electro )chemical and electrochemical reduction of carbon dioxide. Recl.Trav.Chim. Pavs-Bas 103. 288-295. 

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