Nickel trigonal complexes

Scheme 1 Electronic states involved in the absorbtion bands in the region of the first singlet—triplet intersection for octahedral, tetragonal and trigonal complexes of nickel(II).336 Solid arrows denote spin-allowed absorbtion transitions, dotted arrows connect pairs of interacting levels. (reprinted with permission from ref. 336 1998, American Chemical Society).

Low-spin nickel(II) complexes are numerous and many studies of their spectra have appeared in the literature. The most common stereochemistry is trigonal bipyramidal mainly because of the frequent use of tripod-hke hgands. 

When nickel(II) salts containing a coordinating anion (halide and pseudohalide) are reacted with NaBH4 in the presence of np3, trigonal bipyramidal nickel(I) complexes of the type [NiXnp3], in which the coordinating anion occupies die axial position, 39,340 are obtained. When nickel(II) salts with poorly coordinating anions are used, non-stoichiometric hydrido complexes of nickel(II) are obtained (equations 108 and 109). 

Table 31 Magnetic Moments and Spectral Parameters for some High-spin Five-coordinate Nickel II) Complexes with Nearly Trigonal Bipyramidal... 

The Ni3S2 fragments in the two complexes (263) and (265) have a trigonal bipyramidal geometry with the two S atoms in the apical positions and the three nickel atoms in the equatorial plane, as found in other organometaUic compounds which contain the same Ni unit.1939 The formation of the enneanuclear complex (264), on the contrary, is exceptional and no other complex of this stoichiometry was isolated with analogous tertiary phosphines, with selenium, or with metals other than nickel. It is not possible to assign any definite oxidation number to nickel in complex (264). The lack of two electrons with respect to the situation of nine nickel(II) ions was reported to be essential for the existence of complex (264) because the oxidation is spontaneous and its reduction invariably leads to the decomposition of the cluster compound.19 ... 

Both nickel(III) and nickel(IV) complexes are usually found in octahedral environments. Less common geometries are the square planar and the trigonal bipyramidal ones. 

Kinetics and Mechanisms of Ligand Replacement Reactions in Trigonal Bipyramidal Nickel(II) Complexes of a Tetradentate Ligand Containing an Apical Phosphorus Donor Atom... 

Some iron and nickel cyanide and carbonyl complexes have been reported as models of the [FeNi]-hydrogenase enzymes. The preparation and structures of the trigonal bipyramidal nickel and iron complexes with the tetradentate ligands tris(2-phenylthiol)phosphine (PS3) and tris(3-phenyl-2-thiophenyl)phosphine (PS3 ) have been reported [70, 71]. The nickel carbonyl complex [Ni(PS3 )(CO)] exhibits vco at 2029 cm compared with the value of 1940 em" for the iron earbonyl complex [Fe(PS3 )(CO)]. Both of these complexes lose CO upon oxidation. The use of cyanide in place of carbon monoxide allows for the preparation of both [Fe (PS3)(CN)] and [Fe (PS3 )(CN)] eomplexes. The IR properties of... 

This is particularly true now with the recent discovery of trigonal prismatic structures for some 6-coordinated metal complexes (21). Surely the proper metal-ligand combination should give a system in which the difference in energy between an octahedral and a trigonal prismatic structure is small. As a result, racemization may take place by a trigonal twist mechanism. Twisting processes of the square-planar-tetrahedral type are known to occur readily in certain nickel(II) complexes (20). 

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