Synthesis of selenium bridged metallacycles via oxidative addition of diaryl diselenide across Re-Re bond: Novel one-pot reaction approach

Abstract

One-pot synthesis of novel M(2)E(2)L(2) type metallacycles [L(CO)(3)Re(mu-SeR)(2)Re(CO)(3)L] (1-5) was accomplished by oxidative addition of diaryl diselenide to low-valent transition metal carbonyl with monodentate pyridine ligands. In metallacycles 1-5, where L pyridine ligand, R = C(6)H(5), CH(2)C(6)H(5), the pyridyl groups bonded to metal centres invariably adopted cis conformation due to pi-pi interaction whereas, in compounds 1a and 2a, the pyridyl ligands were oriented in trans conformation. When bulky phenyl groups are introduced at para position of pyridyl rings, as in case of metallacycle 3, the steric hindrance disrupts the soft interaction and resulted into the expansion of space in between two phenylpyridyl groups and created a void. The Metallacycles 1-5 have been characterised by elemental analysis, NMR, IR, absorption and emission spectroscopic techniques. Molecular structures of 1, 1a, 2, 2a, 3 and 4 were determined by single crystal X-ray diffraction analysis and the structural studies of 1, 2, 3 and 4 revealed that the pyridyl groups attached to the metal centres exhibited cis conformation, while 1a, 2a displayed trans conformation. (C) 2011 Elsevier B. V. All rights reserved.