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Transition Metal Complexes with Sulfur Ligands, 123[ [ Synthesis and Reactivity of New Complexes Containing the [Ru(“S 4 ”)] Fragment [S 4 2‐ = 1,2‐Bis(2‐mercaptophenylthio)ethane(2‐)]
Author(s) -
Sellmann Dieter,
GottschalkGaudig Torsten,
Heinemann Frank W.,
Knoch Falk
Publication year - 1997
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19971300507
Subject(s) - chemistry , tetrahydrothiophene , ligand (biochemistry) , reactivity (psychology) , ruthenium , stereochemistry , octahedron , transition metal , yield (engineering) , medicinal chemistry , substitution reaction , coordination complex , metal , crystal structure , crystallography , catalysis , pathology , metallurgy , organic chemistry , medicine , biochemistry , receptor , alternative medicine , materials science
In order to synthesize labile and well‐soluble [Ru(L)(L')(“S 4 ”)] complexes, [Ru(CI) 2 (DMSO) 4 ] was treated With “S 4 ”‐Na 2 (S 4 2‐ = 1,2‐bis(2‐mercaptophenylthio)‐ethane(2–1)] yielding [Ru(DMSO) 2 (“S 4 ”)] ( 1 which contains two labile DMSO ligands. An X‐ray structural analysis of 1 , verifies that both DMSO ligands are coordinated via their S atoms. The reaction of 1 with small ligands such as PR 3 (R = Et, n Pr, n Bu) or tetrahydrothiophene (THT) leads to substitution of both DMSO ligands yielding [Ru(PR 3 ) 2 (“S 4 ”)] (R = Et 3a , n Pr 3b , n Bu 3c ) and [Ru(THT) 2 (“S 4 ”] 2 , respectively, while bulky phosphane ligands such as PCy 3 and P i Pr 3 substitute one DMSO ligand to yield [Ru(DMSO)(PR 3 ])(“S 4 ”] (R = i Pr 4a , Cy 4b ). X‐ray structural analyses of [Ru(PnPr 3 ) 2 (“S 4 ”)] · 0.5 MeOH ( 3b · 0.5 MeOH), [Ru(PnBu 3 ) 2 (S 4 )} ( 3c ), and [Ru(Pme 3 ) 2 (“S 4 ”)] ( 3d ) confirm the pseudo‐octahedral coordination of the Ru centers by four Sdonors and two cis P‐donors and reveal close similarities bet ween the three complexes. Comparision of the structural parameters of 3b · 0.5 MeOH, 3c and 3d with those of [Ru(PPh 3 ) 2 (“MeS, 4 ”)] [MeS 4 “2” = 1,2‐bis(2‐mercaptophenylthio)propane(2–1)] indicates that the inertness towards substitution of 3b · 0.5 MeOH, 3c and 3d as opposed to the substitution lability of [Ru(PPh 3 ) 2 (,MeS 4 “)] is caused by the small cone angles of the alkyl phosphanes. In the DMSO/PCy 3 complex 4b both coligands are labile, and which one is substituted depends on the size of the entering ligand. The reactions of 4b with P n R 3 yield [Ru(DMSO)(PR 3 )('S 4 ”)] (R = n Pr 4c , n Bu 4d ) in contrast to the reaction with CO. PMe 3 , and SMe 2 which give [Ru(CO)(Pcy 3 )(“S 4 ”)] ( 5b ), [Ru(P‐Me 3 )(PCy 3 )(“S 4 ”)] ( 6 , and [Ru(SMe 2 )(PCy 3 )(“S 4 ”)] ( 7 , respectively. In an analogous manner, the CO complexes [Ru(CO(PR 3 )(“S 4 ”)] (R = i Pr 5a , n Bu 5c ) have been obtained by treatement of 4a and 4d with CO. The reactions of 4a and 4b with S 8 yielded the readily soluble μ‐S 2 complexes [μ‐S 2 [Ru(PR 3 )(“S 4 ”)] 2 ] (R ‐ i Pr 8a , Cy 8b ). The spectroscopi9c data of complex 8b and its cyclic voltammogram, which exhibits four quasi‐reversible redox waves, indicate a strong electronic coupling of the two [Ru(PCy 3 )(“S 4 ”)] fragments via the μ‐S 2 bridge.