Nickel with phosphorus

Another readily glass-forming system involves metal-metalloid alloys. The most common ones use iron or nickel with phosphorus or boron. Their frequent use results from the catalytic properties of the metals for the widely studied hydrogenation of CO. Alloys prepared with all possible combinations of these four elements in different compositions have been studied. Additionally, some of these alloys, Ni-B, Ni-P, and Fe-Ni-(Cr)-P-B, as well as Pd-Si and Pd-Ge alloys, have been studied in the hydrogenation of hydrocarbons containing multiple bonds. 

Electrochemical corrosion characteristics of nickel were carried out by potentiodynamic polarization and impedance spectroscopy methods. Corrosion tests of nickel produced by electrocrystallization were ap>plied to its micrometric (Nim) and nanometric (Ni ) crystalline structures and for NiP amorphous alloy of nickel with phosphorus at content of 10.7% by weight (Eftekhari, 2008), (Kowalewska Trzaska, 2006). 

The grades with the 410 or 420 numerals are the basic 13% chromium type with varied carbon content. The additions of sulphur or selenium (possibly with phosphorus) to some grades (416 group) is to improve machinability. 431S29 has increased chromium content to improve corrosion resistance, but reference to Fig. 3.11 shows that such addition alone would lead to a mixed martensite-5-ferrite structure with certain disadvantages to mechanical properties. The nickel addition is to limit ferrite content. 

Resistance to corrosion Most authors who compare resistance to corrosion of electroless nickel with that of electrodeposited nickel conclude that the electroless deposit is the superior material when assessed by salt spray testing, seaside exposure or subjection to nitric acid. Also, resistance to corrosion of electroless nickel is said to increase with increasing phosphorus level. However, unpublished results from International Nickel s Birmingham research laboratory showed that electroless nickel-phosphorus and electrolytic nickel deposits were not significantly different on roof exposure or when compared by polarisation data. 

Arbusov reaction of thienyl halides with phosphites in the presence of nickel catalyst [41, 42], or palladium catalyzed phosphorylation of thienyl halides [43], and some of them are commercially available (Scheme 22). 2,5-Diphosphorylthiophenes were synthesized by Arbusov reaction of thienyl halides with phosphites in the presence of nickel catalyst [44] or reaction of 2,5-dilithiothiophene with phosphorus halides followed by oxidation [45] (Scheme 23). 

The JV-oxide of (l,4-benzodiazepin-2-ylidene)malonate (503, R = H, n = 1) was deoxygenated by catalytic hydrogenation over Raney Nickel in a mixture of methanol and THF at atmospheric pressure for 5 hr (83USP4401597) and by treatment with phosphorus trichloride in methylene chloride at ambient temperature overnight (75JOC153 83USP-4401597). 

Schrauzer, Mayweg and Heinrich have reported the preparation of the complex 5 from the reaction of aqueous nickel(ll) chloride with a reaction mixture of benzoin in dioxane and phosphorus(V) sulfide. The parent acid and its salts have not been characterized. The only other closed ring complex, 6, was isolated in low yield (3%) subsequent to the reaction of nickel (II) acetate with the mixture resulting from the reaction of 1,3-propanediol with phosphorus(V) sulfide. As for 5, the parent acid and its salts were not... 

Knowing all these facts, especially the difficult access to fluorophosphines and the poor donating abilities of phosphorus trifluoride (5, 6), we decided to use another approach, which readily led to a number of coordination compounds with fluorophosphine ligands—namely, the fluorination of chlorophosphines already coordinated to the transition metal, where the 3s electrons of phosphorus are blocked by the complex formation. There was no reaction between elemental nickel and phosphorus trifluoride, even under extreme conditions, whereas the exchange of carbon monoxide in nickel carbonyl upon interaction with phosphorus trifluoride proceeded very slowly and even after 100 hours interaction did not lead to a well defined product (5,6). 

Thiane oxides have been shown to be reduced cleanly back to the thiane with phosphorus pentasulfide under conditions to which sulfones, sulfinates, ketones, esters and amides are inert (78CJC1423) the potential of this reaction, though not yet applied, is obviously considerable, especially when coupled with the old-established Raney nickel desulfurization technique. Thiane itself is desulfurized to pentane (with traces of cyclopentane) but the opportunity to construct alkyl chains of great complexity regio- and stereo-specifically is there. At the very least, the reduction to tetrahydrothiopyrans presents a very useful entree into a wide range of 2-substituted thianes (Scheme 2). 

In all the complexes shown in Table 9 (with one exception) the nickel atom is four-coordinated by two phosphorus atoms and by two carbon atoms in a distorted planar arrangement (24a). The plane containing the nickel and phosphorus atoms and the plane containing the nickel and the coordinated carbon atoms form a dihedral angle which varies between 4° and 27° (24b), depending on the coordinated alkene. In the [Ni(p3)(C2F4)2] complex (25) the nickel atom is five-coordinated by three phosphorus atoms of the tridentate ligand and two carbon atoms of tetrafluoroethylene. 

Phosphorus unites with most of the metals, forming phosphides. Phosphorus is electronegative towards hydrogen, and its affinity for the metals is rather less than that of sulphur. The phosphides are made by the direct union of the two elements usually assisted by heat, and in an atmosphere of an inert gas to prevent undue oxidation. In this way, at a dull red-heat, the metals iron, nickel, cobalt, copper, manganese, palladium, platinum, and iridium united with phosphorus with incandescence and gold, silver, tin, and zinc without incandescence. Phosphides VOL. VIII. 3 B... 

Tetrakis[phosphorus(III) chloride] nickel has been prepared by the reaction of nickel carbonyl with phosphorus-(III) chloride at room temperature.1 The synthesis of this compound as described below is based on this method. 

Nickel (0) complex compounds, non-electrolytes, with phosphorus-(III) chloride, Ni(PCI3)4, 6 201 Nickel(I) complex compounds,... 

Complexes of nickel constitute a distinct group of homogeneous alkylalumi-nium-free catalysts for olefin polymerisation. An efficient catalyst for ethylene polymerisation is formed in the reaction of bis(cycloocta-l,5-diene)nickel(0) [Ni(Cod)2] with phosphorus-ylid and triphenylphosphine in toluene solvent [181] ... 

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