Nickel complexes preparation

Most of the nickel complexes prepared according to reactions (113)—(119) have the general formula [NiL]X2 or [NiL2]X2 (X = C104, ZnCU) and are square planar. The complexes obtained from reaction (118) as dihydrate, NiL(H20)2(C104)2, are six-coordinate cis octahedral. 

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... 

The complex [Ni(2,3-Me2[14]-l,3-diene-l,4,8,lI-N4)] [ZnCU] is square planar and low-spin. The visible spectra show bands near 21.3 kK (characteristic of square planar nickel(II)), near 26.1 kK (due to the imine functions), and near 35.1 kK. The infrared spectra of all of the nickel complexes prepared show absorptions near 3195 and 1595 cm assignable to the N—H stretching vibration and to the symmetric imine vibration, respectively. A strong sharp band also occurs near 1210 cm and is characteristic of the a-diimine function. The NMR spectrum of the perchlorate complex in nitromethane shows a methyl singlet at 2.33 ppm. The ligand can be hydrogenated on nickel(II) with Raney nickel and hydrogen to produce the fully saturated macrocyclic complex [Ni(2,3-Me2[14]-ane-1,4,8,1 1-N4] ... 

Nickel complexes, prepared by the combination of Ni(acac)2 with a chiral P-ami-no alcohol [24,25] or a P-hydroxysulfoximine [26], catalyze the conjugate addition of diethylzinc to chalcone. Some asymmetric ampHfications have been observed. 

Z.-H. Zhou and T. Yamamoto, Research on carbon—carbon coupling reactions of haloaromahc compounds mediated by zerovalent nickel complexes. Preparation of cyclic oligomers of thiophene and benzene and stable anthrylnickel(II) complexes, J. Organomet. Chem., 414, 119-127 (1991). 

The conjugate addition of organoaluminium acetylides to a,)S-unsaturated cyclic ketones takes place in the presence of catalytic amounts of a nickel complex prepared from Ni(acac)2 and di-isobutylaluminium hydride (DIBAH) [equation (12)]. The reaction proceeds for five- or six-membered rings, as well as fused rings in about 70% yield. Other acetylides, those of magnesium and zinc for... 

Nickel-allyl complexes prepared from Ni(CO)4 and allyl bromides are useful for the ole-fination of alkyl bromides and iodides (E.J. Corey, 1967 B A.P. Kozikowski, 1976). The reaction has also been extended to the synthesis of macrocycles (E.J. Corey, 1967 C, 1972A). 

However, with the application in the 19, iOs of crystal held theory to transition-metal ehemistry it was realized that CFSEs were unfavourable to the lormation of tetrahedral d complexes, and previous assignments were re-examined. A typical ca.se was Ni(acac)i. which had often been cited as an example of a tetrahedral nickel complex, but which was shown - in I9. I6 to be trimeric and octahedral. The over-zealous were then inclined to regard tetrahedral d" as non-existent until Hrst L.. M. Venanz.i and then N., S. Gill and R. S. Nyholm" demonstrated the existence of discrete tetrahedral species which in some cases were also rather easily prepared. 

Vinylic copper reagents react with CICN to give vinyl cyanides, though BrCN and ICN give the vinylic halide instead." Vinylic cyanides have also been prepared by the reaction between vinylic lithium compounds and phenyl cyanate PhOCN." Alkyl cyanides (RCN) have been prepared, in varying yields, by treatment of sodium trialkylcyanoborates with NaCN and lead tetraacetate." Vinyl bromides reacted with KCN, in the presence of a nickel complex and zinc metal to give the vinyl nitrile. Vinyl triflates react with LiCN, in the presence of a palladium catalyst, to give the vinyl nitrile." ... 

A useful new method of preparing arylphosphonates (123) involves the reaction of trialkyl phosphites with aryl halides in the presence of a nickel catalyst.The suggested mechanism is via the nickel complex (124), and is non-radical. 

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... 

Macrolactones 77 and/or 78 can be prepared from the reductive cyclisation of ynals 76 in the presence of NHC-nickel complexes (Scheme 5.21) [21], This maaolactonisation occnrs with different selectivity depending on the ligands attached to the nickel. If carbenes snch as IMes or IPr are nsed, the exocyclic olefin 77 is preferentially obtained, however when phosphine ligands are nsed, the endocyclic adducts 78 are preferentially obtained. 

Scheme 5.21 Macrolactones prepared from the reductive cyclisation of ynals in the presence of NHC-nickel complexes...

Kanemasa et al.63 reported that cationic aqua complexes prepared from the /ram-chelating tridentate ligand (i ,f )-dibenzofuran-4,6-diyl-2,2,-Mv(4-phcnyloxazolinc) (DBFOX/Ph) and various metal(II) perchlorates are effective catalysts that induce absolute chiral control in the Diels-Alder reactions of 3-alkenoyl-2-oxazolidinone dienophiles (Eq. 12.20). The nickel(II), cobalt(II), copper(II), and zinc(II) complexes are effective in the presence of six equivalents of water for cobalt and nickel and three equivalents of water for copper and zinc. 

Simple transition metal halides react cleanly with alkali metal boratabenzenes. In this way sandwich-type complexes 32 of V (27), Cr (64), Fe (58), Ru (61), and Os (61) have been made. The corresponding nickel complexes seem to be nonexistent, quite in contrast to NiCp2 in attempted preparations, mixtures of diamagnetic C—C linked dimers were obtained (29). In the manganese case, high sensitivity to air and water has precluded preparative success until now. Some organometallic halides have added further variations to the main theme. The complexes 33 of Rh and 34 of Pt were obtained from [(COD)RhCl]2 and [Me3PtI]4, respectively (61). 

There are few reports of oxidative addition to zerovalent transition metals under mild conditions three reports involving group 10 elements have appeared. Fischer and Burger reported the preparation of aTT -allylpalladium complex by the reaction of palladium sponge with allyl bromide(63). The Grignard-type addition of allyl halides to aldehydes has been carried out by reacting allylic halides with cobalt or nickel metal prepared by reduction of cobalt or nickel halides with manganese/iron alloy-thiourea(64). 

Although the copper mediated Ullmann reaction is a well known method for biaryl synthesis, drastic conditions in the range of 150-280 °C are required. Zerovalent nickel complexes such as bis(l,5-cyclooctadiene)nickel or tetrakis(triphenylphosphine)nickel have been shown to be acceptable coupling reagents under mild conditions however, the complexes are unstable and not easy to prepare. The method using activated metallic nickel eliminates most of these problems and provides an attractive alternative for carrying out aryl coupling reactions(36,38). 

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... 

The S-oxygenation of the hexaamine-dithiophenolate macrocycles should provide a potential entry into the novel class of binucleating polyamine-disulfonate and -disulfinate macrocycles. Indeed, such ligands can be prepared by the oxidation of dinuclear nickel complexes of the parent hexaaza-dithiopheno-late macrocycles followed by the decomposition of the oxidation products in acidic solution. The dinuclear nickel complexes [Nin2(L36)(L )]+ (L = Cr (70) and OAc (71)) of the hexaaza-diphenylsulfonate ligand (L36)2- (Fig. 38) are obtained by... 

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. 

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