Nickel zero-valent complexes

Low-valent nickel complexes of bpy are also efficient electrocatalysts in the reductive coupling reaction of aromatic halides.207 Detailed investigations are in agreement with a reaction mechanism involving the oxidative addition (Equation (40)) of the organic halide to a zero valent complex.208-210 Starting from [Nin(bpy)2(X)2]0 with excess bpy, or from [Nin(bpy)3]2 +, results in the [Ni°(bpy)2]° complex (Equations (37) and (38)). However, the reactive complex is the... 

Nickel(O) complexes are obtained by substitution of CO molecules in nickel tetracarbonyl, Ni(CO)4. They contain hgands, such as CO, NO, PF3, PCI3 and PlCeHsls and their mixed combinations coordinated to nickel. Some examples of such zero valent complexes are Ni(PF3)4, Ni(PCl3)4, Ni(CEl3PCl4)4, (CO)Ni(PF3)3, (CO) 3Ni(PF3), and (PPh3)2Ni(NO)2. 

The active catalyst is presumably formed through reduction of the Ni species, aided by hydrogen or group VIB metals and their carbonyls, to the nickel carbonyl. Nickel carbonyl is converted to the active catalyst by ligand dissociation. The exact nickel species is the result of complex equilibria, equations 11-17. The zero valent complex adds methyl iodide, after CO dissociation. This is believed to be the rate-determining step and has first order kinetics with respect to both iodide and Ni. It was found that temperature greater than 100 C is needed for the oxidative addition (29). 

Significant advances in organonickel chemistry followed the discovery of frtzws,fraws,fraws-(l,5,9-cyclododecatriene)nickel, Ni(cdt), and bis(l,5-cycloocta-diene)nickel Ni(cod)2 by Wilke et. al.1 In these and related compounds, in which only olefinic ligands are bonded to the nickel, the metal is especially reactive both in the synthesis of other compounds and in catalytic behavior. Extension of this chemistry to palladium and to platinum has hitherto been inhibited by the lack of convenient synthetic routes to zero-valent complexes of these metals in which mono- or diolefins are the only ligands. Here we described the synthesis of bis(l,5-cyclooctadiene)platinum, tris(ethylene)-platinum, and bis(ethylene)(tricyclohexylphosphine)platinum. The compound Pt(cod)2 (cod = 1,5-cyclooctadiene) was first reported by Muller and Goser,2 who prepared it by the following reaction sequence ... 

In summary, it can be seen that the structural chemistry of the zero-valent complexes has to date been dominated by investigations on nickel carbonyl. Preliminary studies on other compounds indicate that the tetrahedral structure may not be the only possibility, and thorough investigation of the unsaturatcd species is likely to develop. Back-donation may be examined by study of force constants, in favorable cases merely of observed frequencies, and it would be interesting to see more cases of competition for back-donation, as in (MeNC)3Ni(CO). 

Finally, we note that Wilke and his coworkers76 have shown that zero-valent complexes, especially of nickel, obtained by reduction with aluminum alkyls can be used in a wide variety of polymerizations such as trimerization of butadiene to trans,trans,trans-cyclododQca.trisn.Q. 

Tetramerization. Methyl propiolate in cyclohexane stirred at 22 in the presence of tetrakis (phosphorus trichloride) nickel (0), and the product isolated after ca. 15 min. crude 1,2,4,6-tetracarbomethoxycyclooctatetraene. Y 83% based on startg. m. consumed.—The reaction, catalyzed by zero valent complexes, is extremely limited in scope. It provides, however, a useful route to a rare class of compounds. F. e. s. J. R. and M. F. Leto, Am. Soc. 83, 2944 (1961). 

Dehalogenation of monochlorotoluenes can be readily effected with hydrogen and noble metal catalysts (34). Conversion of -chlorotoluene to Ncyanotoluene is accompHshed by reaction with tetraethyl ammonium cyanide and zero-valent Group (VIII) metal complexes, such as those of nickel or palladium (35). The reaction proceeds by initial oxidative addition of the aryl haHde to the zerovalent metal complex, followed by attack of cyanide ion on the metal and reductive elimination of the aryl cyanide. Methylstyrene is prepared from -chlorotoluene by a vinylation reaction using ethylene as the reagent and a catalyst derived from zinc, a triarylphosphine, and a nickel salt (36). 

Coordination-catalyzed ethylene oligomerization into n-a-olefins. The synthesis of homologous, even-numbered, linear a-olefins can also be performed by oligomerization of ethylene with the aid of homogeneous transition metal complex catalysts [26]. Such a soluble complex catalyst is formed by reaction of, say, a zero-valent nickel compound with a tertiary phosphine ligand. A typical Ni catalyst for the ethylene oligomerization is manufactured from cyclo-octadienyl nickel(O) and diphenylphosphinoacetic ester ... 

Iron(II), cobalt(II), and nickel(II) monothiocyanato complexes also catalyze evolution of hydrogen in aqueous buffer. The active intermediate is the protonated doubly reduced, zero-valent form of the complex.45... 

Scheme 6. Interplay of the C8- and C -production channels for the cyclo-oligomerization of 1,3-butadiene with zero valent PR3/P(OR)3-stabilized nickel complexes as the catalyst. Free energies (AG, AGJ in kcalmol-1) are given relative to the favorable rf-synrfiC A-cis isomer of 2a for catalysts bearing strong a-donor ligands namely I (L = PMe3), III (L = PPrj), VI (L = PBU3), and -acceptor ligands namely V (L = P(OMe)3), IV...

Cj) Treatment of zero-valent nickel complexes with Br0nsted acids. 

C2) Treatment of zero-valent nickel complexes with Lewis acids, whereby the Lewis acid can also be an organometallic species. 

There can be little doubt that the active species involved in most or even all of the various combinations described in Section II is HNi(L)Y (see below), because the different catalysts prepared by activating the nickel with Lewis acids have been shown to produce, under comparable conditions, dimers and codimers which have not only identical structures but identical compositions. On modification of these catalysts by phosphines, the composition of dimers and codimers changes in a characteristic manner independent of both the method of preparation and the nickel compound (2, 4, 7, 16, 17, 26, 29, 42, 47, 76). Similar catalysts are formed when organometallic or zero-valent nickel complexes are activated with strong Lewis acids other than aluminum halides or alkylaluminum halides, e.g., BFS. 

The formation of cationic nickel hydride complexes by the oxidative addition of Brdnsted acids (HY) to zero-valent nickel phosphine or phosphite complexes (method C,) has already been discussed in Section II. Interesting in this connection is a recent H NMR study of the reaction of bis[tri(o-tolyl)phosphite]nickelethylene and trifluoroacetic acid which leads to the formation of a square-planar bis[tri(o-tolyl)phosphite] hydridonickel trifluoroacetate (30) (see below) having a cis arrangement of the phosphite ligands (82). 

Less clear is the sequence which leads to the formation of the active species in the case of catalysts prepared from zero-valent nickel complexes and aluminum halides or alkylaluminum halides (method C2). The catalytic properties of these systems, however—in particular, the influence of phosphines (76)—leaves no doubt that the active species is also of the HNiY type discussed above. In this connection, a recent electron spin resonance report that nickel(I) species are formed in the reaction of COD2Ni with AlBr3 (83 ), and the disproportionation of Ni(I) to Ni(II) and Ni(0) in the presence of Lewis acids (69) should be mentioned. 

Scheme 3 refers to oxidative addition of organic halides or derivatives thereof to zero-valent nickel, and to replacement reactions on Ni(II) complexes. 

Some of these coupling reactions can be made catalytic if hydrogen is eliminated and combines with the anion, thus leaving the nickel complex in the zero-valent state. Allylation of alkynes or of strained olefins with allylic acetates and nickel complexes with phosphites has been achieved (example 38, Table III). 

Baker has also reported the reaction of butadiene with phenylhydra-zones leading to azoalkenes (example 14, Table IV). This is also a Grig-nard-type reaction which is catalytic. Analogous results were obtained with methylhydrazones (136). A wider scope was recently attained by causing allylic esters to react with phenylhydrazones in the presence of zero-valent nickel complexes having trialkyl phosphites (example 15, Table IV). 

An intermediate acylnickel halide is first formed by oxidative addition of acyl halides to zero-valent nickel. This intermediate can attack unsaturated ligands with subsequent proton attack from water. It can give rise to benzyl- or benzoin-type coupling products, partially decarbonylate to give ketones, or react with organic halides to give ketones as well. Protonation of certain complexes can give aldehydes. Nickel chloride also acts as catalyst for Friedel-Crafts-type reactions. 

Zero-valent nickel-chelating phosphine complexes are used at 120°C under C02 pressure. 

Oxidative addition of the silyl species to nickel is followed by insertion of unsaturated substrates. Zero-valent nickel complexes, and complexes prepared by reducing nickel acetylacetonate with aluminum trialkyls or ethoxydialkyls, and in general Ziegler-Natta-type systems, are effective as catalysts (244, 260-262). Ni(CO)4 is specific for terminal attack of SiHCl3 on styrene (261). 

Harrison, K.N., Hoye, P.A.T., Orpen, A.G., Pringle, P.G., and Smith, M.B., Water-soluble, zero-valent, platinum-, palladium,- and nickel-P(CH2OH)3 complexes catlaysts for the addition of phosphine to formaldehyde, J. Chem. Soc., Chem. Commun., 1096, 1989. 

A large number of (mostly zero-valent) nickel-alkene complexes has been reported. Although these complexes have not been recently reviewed, their general properties and structures were expertly described in 1982 [21]. A complete overview of the reported nickel-alkene and nickel-alkyl complexes is beyond the scope of this section, in which a selection of nickel-alkene and nickel-alkyl complexes is described, mostly related to possible intermediates in hydrogenation catalysis. 

Nickel forms a large number of complexes with various anions (monoden-tate, bidentate, and polydentate) and many neutral ligands. The most common coordination numbers of the metal in these complexes are six and four while the metal is usually in +2 oxidation state, Ni2+. Also, some complexes of three and five coordinations exist. Several zero valent nickel complexes, such as nickel tetracarbonyl, and a number of substituted carbonyl complexes are well known. 

---