Synthesis and complexation of nickel(II) and copper(II) by pendant-arm alcohol derivatives of [9]aneNS2 (7-aza-1,4-dithiacyclononane)

Autor: Alexander J. Blake, Ian Andrew Fallis, Jonathan P. Danks, Gavin Whittaker, Martin Schröder, Simon Parsons, Wan-Sheung Li, Steven A. Ross, Andrew Harrison
Rok vydání: 1998
Předmět:
Zdroj: Journal of the Chemical Society, Dalton Transactions. :3969-3976
ISSN: 1364-5447
0300-9246
DOI: 10.1039/a804303e
Popis: A simplified procedure for the preparation of [9]aneNS2 (7-aza-1,4-dithiacyclononane) is described. The structure of the complex [Cu([9]aneNS2)2]2+ confirms that the Cu(II) centre is in a distorted octahedral environment, Cu–S(1) 2.5469(14), Cu–S(4) 2.5386(13), Cu–N(7) 2.016(4) A. Reaction of [9]aneNS2 with isobutylene oxide or 2,2-diphenyloxirane gives the alcohol derivatives, HL1 and HL2, respectively. The 1∶1 metal∶ligand complex [Cu2(L1)2]2+ was found to be binuclear with the alcohol functions deprotonated to form alkoxide bridges between two Cu(II) centres, Cu–N(1) 2.042(4), Cu–S(4) 2.452(2), Cu–S(7) 2.430(2), Cu–O(14) 1.927(4), Cu–O(14′) 1.922(4), Cu–Cu′ 3.0063(9) A, Cu–O–Cu′ 102.7(2)°. Magnetochemical data for this complex confirm antiferromagnetic coupling between the two Cu(II) centres with 2J = –417 ± 2 cm–1. With Ni(II) the complex [Ni(HL1)(CH3CO2)]+ can be isolated, the structure of which shows it to be a monomer with the ligand HL1 acting as a tetradentate ligand to the metal centre, Ni–N(1) 2.064(3), Ni–S(4) 2.3658(12), Ni–S(7) 2.3875(13), Ni–O(14) 2.061(3) A. A chelating acetate ligand completes the distorted octahedral geometry, Ni–O(16) 2.098(3), Ni–O(17) 2.102(3) A.
Databáze: OpenAIRE