title: Encapsulation of the 4-mercaptobenzoate ligand by macrocyclic metal complexes: conversion of a metallocavitand to a metalloligand.
abstract: Complexation of the ambidentate ligand 4-mercaptobenzoate (4-SH-C6H4CO2H, H2mba) by the macrocyclic complex [Ni2L(μ-Cl)]ClO4 (L(2-) represents a 24-membered macrocyclic hexaazadithiophenolate ligand) has been examined. The monodeprotonated Hmba(-) ligand reacts with the Ni2 complex in a selective manner by substitution of the bridging chlorido ligand to produce μ1,3-carboxylato-bridged complex [Ni2L(Hmba)](+) (2(+)), which can be isolated as an air-sensitive perchlorate (2ClO4) or tetraphenylborate (2BPh4) salt. The reactivity of the new mercaptobenzoate complex is reminiscent of that of a "free" thiophenolate ligand. In the presence of air, 2ClO4 dimerizes via a disulfide bond to generate tetranuclear complex [{Ni2L}2(O2CC6H4S)2](2+) (3(2+)). The auration of 2ClO4 with [AuCl(PPh3)], on the other hand, leads to monoaurated complex [Ni(II)2L(mba)Au(I)PPh3](+) (4(+)). The bridging thiolate functions of the N6S2 macrocycle are deeply buried and are unaffected/unreactive under these conditions. The complexes were fully characterized by electrospray ionization mass spectrometry, IR and UV/vis spectroscopy, density functional theory, cyclic voltammetry, and X-ray crystallography [for 3(BPh4)2 and 4BPh4]. Temperature-dependent magnetization and susceptibility measurements reveal an S = 2 ground state that is attained by ferromagnetic coupling between the spins of the Ni(II) ions in 2ClO4 (J = +22.3 cm(-1)) and 4BPh4 (J = +20.8 cm(-1); H = -2JS1S2). Preliminary contact-angle and X-ray photoelectron spectroscopy measurements indicate that 2ClO4 interacts with gold surfaces.
authors.affiliation: Institut für Anorganische Chemie, Universität Leipzig , D-04103 Leipzig, Germany.
authors.forename: Jochen
authors.initials: J
authors.lastname: Lach
authors.forename: Alexander
authors.initials: A
authors.lastname: Jeremies
authors.forename: Daniel
authors.initials: D
authors.lastname: Breite
authors.forename: Bernd
authors.initials: B
authors.lastname: Abel
authors.forename: Benjamin
authors.initials: B
authors.lastname: Mahns
authors.forename: Martin
authors.initials: M
authors.lastname: Knupfer
authors.forename: Vitaly
authors.initials: V
authors.lastname: Matulis
authors.forename: Oleg A
authors.initials: OA
authors.lastname: Ivashkevich
authors.forename: Berthold
authors.initials: B
authors.lastname: Kersting