pyS Ligand Research Articles

Synthesis and structures of two isomers of [Re 3Ru(S)(C 5H 4N)(C 5H 4NS) 2(CO) 11] which differ in the distribution of pyridine-2-thionato ligands between doubly- and triply-bridging positions

The pyridine-2-thionato (pyS) bridged compound [Re 2(pyS) 2(CO) 6] reacts with [Ru 3(CO) 12] to give various tetranuclear compounds built from Re(pyS)(CO) 3 and Ru(CO) x ( x = 2, 3 or 4) units: [ReRu 3(S)(C 5H 4N)(CO) 14], [Re 2Ru 2(S)(C 5H 4N)(pyS)(CO) 13], and [Re 3Ru(S)(C 5H 4N)(pyS) 2(CO) 11] as two isomers. X-ray structures of these isomers show that one contains two doubly-bridging pyS ligands and the other one doubly- and one triply-bridging pyS ligands.

Notes. [RhPd2(pyS)4(η3-C4H7)2][BF4]: synthesis and X-ray structure of a mixed-metal trinuclear complex containing two µ3-pyridine-2-thionato (pyS) ligands

The complex [RhIII(pyS)3(pySH)], containing two chelating pyridine-2-thionato (pyS) ligands, one monodentate S-bonded pyridine-2-thionato ligand, and one monodentate S-bonded 1H-pyridine-2-thione (pySH) ligand, reacts with triethylamine and two equivalents of the 2-methylallyl complex [Pd(η3-C4H7)S2][BF4](S = solvent = H2O or acetone) to yield the trinuclear compound [RhIII(pyS)2(µ3-pyS)2{PdII(η3-C4H7)}2][BF4], (1). The structure of (1), determined by single-crystal X-ray diffraction, contains two chelating pyridine-2-thionato ligands at rhodium and two which bridge all three metal atoms as part of a bicyclic cage. None of the metal atoms is within bonding distance. The structure may be regarded as containing the cyclic bidentate ligand [Pd2(µ-pyS)2(η3-C4H7)2] chelated to the group [RhIII(pyS)2]+ through two sulphur atoms.

Di- and tri-nuclear complexes of palladium(II) containing doubly- and triply-bridging pyridine-2-thionato (pyS) ligands: crystal structure of [Pd3(C6H4CH2NMe2)3(pyS)2][BF4

The complex [Pd2Cl2(dmp)2][dmp = 2-(dimethylaminomethyl)phenyl] reacts with 1H-pyridine-2-thione (pySH) or with the 6-methyl substituted derivative (mpySH) in the presence of triethylamine to generate the dinuclear complexes [Pd2(dmp)2(pyS)2] and [Pd2(dmp)2(mpyS)2]. These exist as head-to-tail isomers with folded conformations so that the palladium co-ordination planes are approximately parallel. Fluxional enantiomerisation of the mpyS-bridged compound leading to N-methyl group exchange has been studied. These bridged dimers behave as cyclic bidentate sulphur ligands. [Pd2(dmp)2(pyS)2] reacts with [Pd(dmp)(solvent)2]+ to give [Pd3(dmp)3(pyS)2]+; the X-ray structure of [Pd3(dmp)3(pyS)2][BF4] is reported. The cation contains a cage of three palladium atoms linked by two triply-bridging pyS ligands. Related η3-2-methylallyl trimers and mixed-ligand trimers have also been synthesised by the same method.