202532-92-1Relevant articles and documents
Transition metal complexes with sulfur ligands. Part CXXVII. Azido, halido and nitrido ruthenium complexes with sulfur-rich coordination spheres
Sellmann, Dieter,Gottschalk-Gaudig, Torsten,Heinemann, Frank W.
, p. 63 - 72 (1998)
Ru(II) and Ru(III) azido complexes were synthesized as potential precursors for dinitrogen complexes with sulfur-dominated coordination spheres. NEt4[Ru(N3)(PCy3)('S4')] (1) was obtained from the reaction of [Ru(DMSO)(PCy3)('S4')] with NEt4N3 ('S4'2-=1,2-bis(2-mercaptophenylthio)ethane(2-)). The oxidation of [Ru(DMSO)(PR3)('S4')] with I22 yielded [Ru(I)(PR3)('S4')] (R=Cy 2a, iPr2b). The iodo ligand in 2a and 2b could be exchanged for azide and chloride yielding [Ru(N3)(PR3)('S4')] (R=Cy 3a, iPr 3b) and [Ru(Cl)(PCy3)('S4')] (4). The azido ligand of 1 could not be transformed into a N2 ligand, and the reaction of 3a with HBF4 yielded the nitrido complex [μ-N(Ru(PCy3)('S4')}2](PF 6)([5]PF6) via a labile intermediate exhibiting an IR band at 2070 cm-1 at -40°C. The molecular structures of 2a, 4 and [5]+ as the BPh4- salt were determined by X-ray structure analysis. Crystal data of (a) 2a·C7H8: triclinic space groupP1; a=1087.4(1), b=1089.5(1), c=1988.8(1) pm; α=74.13(1), β=78.66(1), γ=61.22(1)°; Z=2; (b) 4·CH2Cl2: triclinic space group P1; a=1088.7(5), b=1065.6(3), c=1778.4(6) pm; α=80.66(2), β=72.10(4), γ=67.52(3)°; Z=2; (c) [5]BPh4·3THF: orthorhombic space group Pna21; a=1972.9(6), b=2606.3(6), c=1831.1(12) pm; Z=4. The metal centers of all three complexes show pseudo-octahedral coordination and exhibit no anomalies in distances and angles. The two Ru centers in [5] (BPh4)·3THF are linked via a bent nitrido bridge. 1998 Elsevier Science S.A.
