ISSN:
0009-2940
Keywords:
Thioether, benzyl
;
Mercapto amines
;
Nickel complexes
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Addition of two equivalents of benzyl bromide to [N,N′-bis(2-mercaptoethyl)-1,5-diazacyclooctane]nickel(II) (Ni-1) produced the green dibenzyl dithioether complex [Ni-1-Bzl2Br2] structurally characterized by X-ray crystallography as a six-coordinate octahedral complex in a monoclinic crystal system and the P21/c space group. Benzylation of the methyl thioether/thiolate [(Ni-1-Me)+I- yielded the mixed benzyl/methyl dithioether [(Ni-1-BzlMe)Br]I, structurally characterized by X-ray crystallography as a five-coordinate square pyramidal nickel(II) complex with a Ni-Br distance of 2.451 Å. The complex crystallizes in the orthorhombic Cmca space group. The latter is the first nickel(II) pentacoordinate complex isolated for the N,N′-bis(2-mercaptoethyl)-1,5-diazacyclooctane (daco) ligand. Structural comparison of these two complexes with the square-planar dimethyl compound [Ni-1-Me2]I2 found an expansion of the N2S2 plane upon addition of axial ligands. The five-coordinate nickel complex showed a displacement of the Ni ion from the N2S2 plane by 0.43 Å toward the axial bromide ligand, a common observation of pentacoordinate complexes of this ligand with metals such as Zn and Fe. Electrochemical studies as well as the X-ray crystal structures for complex [Ni-1-Bzl2Br2] and [(Ni-1-BzlMe)Br]I are presented and discussed in detail.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19961290708
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