Trigonal-Bipyramidal Nickel(II) Complexes Containing Sulfur Ligand Atoms

Abstract

A new tetradentate ligand, tris( o-methylthiophenyl (phosphine, P(o-C6H4SCHs)3 (TSP, I), forms a series of crystalline, intensely-colored, trigonal-bipyramidal nickel(II) complexes containing the species [Ni(TSP)X] + (X = I, Br, Cl, or NTCS) or [Ni(TSP)L]2 + (L = thiourea, triphenylphosphine, or methyldiphenylphosphine). The two lowest energy electronic absorption bands in the visible and ultraviolet spectra have been assigned to the two 4A4 -2E(D) transitions. Under similar conditions, the analogous arsine compound, tris( o-methylthiophenyl (arsine, As^-CePUSCHsh (TSA), did not react with nickel(II) salts.

Synthesis and characterization of a new thiohydrazone ligand, 3-carboxy-2-hydroxybenzaldehydemorpholine N-thiohydrazone and its metal complexes

“…The tetrahedral and high spin octahedral Co(II) complexes each possess three unpaired electrons but may be distinguished by the magnitude of the deviation of effective magnetic moment value from the spin only value. The magnetic moments of tetrahedral Co(II) complexes with an orbitally degenerate ground term are higher than the spin only value and occur in the range 4.2-4.7 BM [39,40]. Octahedral Co(II) complexes have a large contribution from the 4 T 1g term and have effective magnetic moment values in the range of 4.8-5.6 BM [40].…”

“…The magnetic moments of tetrahedral Co(II) complexes with an orbitally degenerate ground term are higher than the spin only value and occur in the range 4.2-4.7 BM [39,40]. Octahedral Co(II) complexes have a large contribution from the 4 T 1g term and have effective magnetic moment values in the range of 4.8-5.6 BM [40]. The Co(II) complexes 10, 12 and 14 display a broad band in the region 580 nm.…”

“…4 T 1 (P) transition in the tetrahedral environment of the Co(II) (i.e. 3 in Td) [40]. The 2 [ 4 A 2 !…”

“…4 T 1 (F)] of the tetrahedral Co(II) complexes are generally observed in the near infrared, which could not be measured on our instrument. The low spin square-planar Co(II) complexes may be readily distinguished by eff in the range 2.1-2.9 BM, arising from one unpaired electron with large orbital contribution [40][41][42][43][44]. The observed magnetic moment values for 11 and 13 are 2.48 and 2.30 BM, respectively, which are in the range of square-planar Co(II) species.…”

The development of transition metal chemistry in the United States of America

“…In some cases, the metal may also lose electrons to the newly added group, and thus increase its own oxidation number as weil as its coordination number. For example, the iridium(I) complex shown above adds a mole of hydrogen to give the iridium (111) 35 .…”