ISSN:
1434-1948
Keywords:
Ruthenium
;
Sulfur ligands
;
Exchange reactions
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
In a quest for ruthenium complexes having [RuNS4] cores, a non-fluxional configuration, trans-thiolate donors, and exchangeable coligands L, [Ru(L)(‘pyS4’)] complexes have been synthesized [‘pyS4’2- = 2,6-bis(2-mercaptophenylthio)dimethylpyridine(2-)]. Treatment of [RuCl2(PPh3)3] with ‘pyS4’2- gave [Ru(PPh3)(‘pyS4’)] (1). Alkylation of 1 with excess MeI yielded [Ru(PPh3)(‘pyS4’-Me2)]I2 (2). [Ru(DMSO)(‘pyS4’)] (3) was obtained from [RuCl2(DMSO)4] and ‘pyS4’2-. The PPh3 or DMSO coligands in 1, 2, and 3 proved to be very inert to substitution. Only the DMSO could be displaced by CO under drastic conditions yielding [Ru(CO)(‘pyS4’)] (4). Treatment of [RuCl2(CH3CN)4] with ‘pyS4’2- yielded [Ru(‘pyS4’)]2 (5); in the presence of PEt3 or N2H4 mononuclear [Ru(PEt3)(‘pyS4’)] (6) and [Ru(N2H4)(‘pyS4’)] (7) were formed. Template alkylation of NBu4[Ru(NO)(S2C6H4)2] with 2,6-bis(tosyloxymethyl)pyridine gave [Ru(NO)(‘pyS4’)]Tos (8). Complex 8 proved to be the best suited precursor for L exchange reactions. Under reducing conditions, 8 releases its NO ligand and the resulting [Ru(‘pyS4’)] fragments can combine either with each other to give 5, or with PEt3 and N2H4 to yield 6 and 7, respectively. All complexes have been characterized by spectroscopic methods and elemental analysis; 1, 2, 3, and 4 have also been submitted to X-ray structure analysis.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
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