Nickel dinuclear

The readily accessible oxalamidine derivative PhN = C(NHBu )C(NHBu ) = NPh provides another useful entry into the coordination chemistry of oxalamidinato ligands. Scheme 195 summarizes the results of an initial study. Mono- and dinuclear complexes of Ti, Zr, and Ta have been isolated and fully characterized. Silylation of both N-H functions was achieved by subsequent treatment with 2 equivalents of n-butyllithium and MesSiCl. The preparation of a nickel(II) complex failed and gave a hydrobromide salt instead. ... 

Other metals can also be used as a catalytic species. For example, Feringa and coworkers <96TET3521> have reported on the epoxidation of unfunctionalized alkenes using dinuclear nickel(II) catalysts (i.e., 16). These slightly distorted square planar complexes show activity in biphasic systems with either sodium hypochlorite or t-butyl hydroperoxide as a terminal oxidant. No enantioselectivity is observed under these conditions, supporting the idea that radical processes are operative. In the case of hypochlorite, Feringa proposed the intermediacy of hypochlorite radical as the active species, which is generated in a catalytic cycle (Scheme 1). 

Quadruply Bridged Dinuclear Complexes of Platinum, PEdladium, and Nickel Keisuke Umakoshi and Yoichi Sasaki... 

Nickel is found in thiolate/sulflde environment in the [NiFe]-hydrogenases and in CODH/ACS.33 In addition, either a mononuclear Ni-thiolate site or a dinuclear cysteine-S bridged structure are assumed plausible for the new class of Ni-containing superoxide dismutases, NiSOD (A).34 [NiFe]-hydrogenase catalyzes the two-electron redox chemistry of dihydrogen. Several crystal structures of [NiFe]-hydrogenases have demonstrated that the active site of the enzyme consists of a heterodinuclear Ni—Fe unit bound to thiolate sulfurs of cysteine residues with a Ni—Fe distance below 3 A (4) 35-39 This heterodinuclear active site has been the target of extensive model studies, which are summarized in Section 6.3.4.12.5. 

Triphos-derived tridentate ligands with mixed donor sets have been developed and subsequently used in Ni coordination chemistry. Nickel(II) complexes include dinuclear compounds (254) and (255) with P2S and P2O ligands, respectively.6... 

Template condensation reactions of the nickel(II) complex of 3,7-bis(2-aminoethyl)-l,3,5,7-tetraazabicyclo[3.3.1]nonane with formaldehyde and the appropriate primary diamines such as ethylenediamine, 1,4-butanediamine, and p-xylenediamine yield dinickel(II) complexes of bis-heptaazamacrocyclic ligands (716)-(718). Similarly, the dinuclear Ni11 complexes (719) and (720) were prepared by using [Ni(2,3,2-tet)](C104)2, formaldehyde, and NH2—(CH2)ra—NH2 ( = 2, 3, 4, 5, 6, 10) or melamine, respectively. 

The orange, air-stable, homoleptic tetrakis( 71-phosphabenzene)nickel (1046) is tetrahedral (point symmetry 54) and can be obtained from phosphabenzene and [Ni(cod)2].2 25 It features a short Ni—P bond length of 2.1274(5) A with considerable N i P 7r-backbonding and a i/(Ni—P) stretch at 168 cm-1. In solution, partial dissociation of one phosphabenzene ligand is observed. 2-Diphenylphosphino-3-methylphosphinine forms with [Ni(cod)2] in the presence of the CO the dinuclear complex (1047) with a W-frame structure.2526... 

Nickel(II) dithiocarbamates, Ni(S2CNRR )2, are monomeric, square planar complexes. A less common dinuclear complex is the thiolato bridged [Ni(S2CNHMe)(p-SMe)]2, in which the dimers are self-assembled into tetra-meric supermolecules through weak axial Ni- S secondary bonds.397... 

Interesting results were reported with dithiocarbamates derived from diamines. Thus, a series of dinuclear zinc(II), cobalt(II), and nickel(II) dithiocarbamate ditopic macrocyclic receptors containing various spacer groups of different sizes has been reported.412,413,414 Spectroscopic investigations and... 

Fig. 36. Structures of the macrocycle H2L35 and its dinuclear nickel complex, [Ni2(L35)]2+ (244).

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... 

The reaction of [Ni(ethene)3] with a hydride donor such as trialkyl(hydrido)-aluminate results in the formation of the dinuclear anionic complex [ Ni(eth-ene)2[2l 11 [22]. The nickel(O) centers in this complex are in a trigonal planar environment of two ethene molecules and a bridging hydride ion, with the ethene carbons in the plane of coordination. The two planes of coordination within the dinuclear complex are almost perpendicular to each other, and the Ni-H-Ni unit is significantly bent, with an angle of 125° and a Ni-Ni distance of 2.6 A [22],... 

Cupr- entries Dinuclear copper complex Nickel-copper alloys Lead-copper alloys Wrought copper alloys... 

Dinuclear nickel models for the active sites of hydrogenases... 

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