Ubergangsmetallkomplexe mit Schwefelliganden, 145 [1]. ¨ [Ru(NO)('py
buS
4')]Br, ein Komplex mit [Ru(NO)(NS
4)]-Ger ¨ust, aktivierten CH
2-Gruppen und interionischen Wechselwirkungen im Festk¨orper ['py
buS
4'
2-= 2,6-Bis(2-mercapto-3,5-di-tert-butyl- phenylthio)dimethylpyridin(2–)]
Transition Metal Complexes with Sulfur Ligands, 145 [1]. [Ru(NO)('py
buS
4')]Br, a Complex with [Ru(NO)(NS
4)] Core, Activated CH
2Groups, and Interionic Interactions in the Solid State ('py
buS
4'
2= 2,6-Bis(2-mercapto-3,5-di-tert-butylphenylthio)dimethylpyridine(2-)) Dieter Sellmann, Daniel H¨außinger, Torsten Gottschalk-Gaudig
und Frank W. Heinemann
Institut f¨ur Anorganische Chemie der Universit¨at Erlangen-N¨urnberg, Egerlandstraße 1, D-91058 Erlangen, Germany
Sonderdruckanforderungen an Prof. Dr. D. Sellmann.
E-mail: sellmann@anorganik.chemie.uni-erlangen.de
Z. Naturforsch.55 b,723–729 (2000); eingegangen am 5. April 2000 Ruthenium Nitrosyl Complexes, Sulfur Ligands, Interionic Interaction
In the search for soluble and reactive ruthenium nitrosyl complexes, [Ru(NO)('pybuS4')]Br ([2]Br) was synthesized by template alkylation of NBu4[Ru(NO)('buS2')2] with py(CH2Br)2 ['pybuS4'2 = 2,6-bis(2-mercapto-3,5-di-tert-butyl-phenylthio)dimethylpyridine(2-); 'buS2'2 = 2-mercapto-3,5-di-tert-butylphenylthiolate(2-); py(CH2Br)2= 2,6-bis(bromomethyl)pyridine].
The solid state structure of2has been determined by X-ray diffraction, which reveals a head- to-head O-O interaction between the linear Ru-NO entities. The ligand CH2protons of [2]+are activated and exchange with D+under ambient conditions. The(NO) band of [2]Br appears at 1841 cm 1 in the solid state (KBr or hostaflon mull) and is significantly blue-shifted in solution (1879 cm 1 in MeOH, 1886 cm 1 in DMF). A similar blue-shift (1866 cm 1 in KBr vs. 1888 cm 1in MeOH) has been found for [Ru(NO)('pyS4')]Br ([1]Br) which contains the parent [Ru(NO)('pyS4')]+ cation ['pyS4'2 = 2,6-bis(2-mercaptophenylthio)dimethylpyr- idine(2-)]. These(NO) shifts can be explained either by an interionic charge-transfer between the bromide anions and the nitrosyl complex cation or by O-O interactions between two NO ligands as found for solid-state [2]Br. These interactions are not found for [1]OTs which exhibits a(NO) band at ca. 1890 cm 1in the solid state (KBr, hostaflon) as well as in MeOH solution.
