Spontaneous formation of trinickel clusters containing mu(3)-imido bridgesfrom 2-nitrophenols and Ni(PMe3)(4)

2-Nitrophenols ArOH (1: 4-Me, 6-CMe3; 2: 4-CMe3, 6-CMe3; 3: 4-OMe, 6-H) are reduced stepwise by Ni(PMe3)(4) to form cluster compounds (4-6) in which f our trimethylphosphines and two chelating mu 3-imidato-2-phenolato ligands are coordinated to a triangulo-Ni-3 core. Initially mononuclear trans-octah edral complexes Ni(OAr)(2)(OPMe3)(2) (7-9) containing O:O-coordinated nitro phenolato ligands are formed and eventually converted to (4-6). Crystal and molecular structures for 4 and 7 are discussed. Cluster degradation of 4 w ith HCl/ether yields the 2-aminophenol. (C) 1999 Elsevier Science S.A. All rights reserved.