M. Schlaf, A. Lough, R. Morris
Oct 15, 1996
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0
Influential Citations
45
Citations
Journal
Organometallics
Abstract
The complexes MH(CO)(quS)(PPh3)2 (M = Ru, Os; quS = quinoline-8-thiolate) are synthesized in a manner analogous to that for the known complexes MH(CO)(pyS)(PPh3)2 (M = Ru, Os; pyS = pyridine-2-thiolate). The isomer distribution in the quinoline-8-thiolate complexes was determined by an nOe experiment. It is inverted relative to the pyridine-2-thiolate complexes. EHMO calculations on the free chelate anions and the complexes OsH(CO)(L)(PPh3)2 (L = pyridine-2-thiol, quinoline-8-thiol) qualitatively show this to be a consequence of the different electronic properties of the chelate ligand. The electrochemistry of the complexes has been investigated. Protonation of the complexes with HBF4 at low temperature results in the formation of mixtures of dihydrogen complexes [M(η2-H2)(CO)(L)(PPh3)2]BF4 (M = Ru, Os; L = pyridine-2-thiolate, quinoline-8-thiolate) and thiol hydride complexes [MH(CO)(LH)(PPh3)2]BF4 (M = Ru, Os; LH = pyridine-2-thiol, quinoline-8-thiol) in varying tautomer ratios. The structure of the thi...