Intramolecular Dynamics of Tetranuclear Iridium Carbonyl Cluster Compounds. Part IV. Derivatives with monodentate ligands and edge-bridging bidentate ligands

✍ Scribed by Andrès Strawczynski; Gianfranco Suardi; Renzo Ros; Raymond Roulet

• Publisher: John Wiley and Sons
• Year: 1993
• Tongue: German
• Weight: 802 KB
• Volume: 76
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/hlca.19930760605

✦ Synopsis

Decacarbonyl/~,-bis(methylthio)methane]tetrairidium

([Ir4(C0)

,,(p2-CH3SCH2SCH3)], 14). A soln. of 2 (272 mg, 0.204 mmol) and bis(methy1thio)methane (259 pl, 2.54 mmol) in CH2C1, (130 ml) was stirred with AgBF, (51 mg, 0.26 mmol) for 1 h at 258 K under Ar, then passed through a column of silica gel at 258 K using CH,C12.

The soln. was evaporated to dryness at 263 K, and the residue was dissolved in THF and heated in THF for 25 h a t 333 K. Chromatography on a plate of silica gel using CH2C12/hexane 1 : 1 gave two fractions. Recrystallisation from CH,Cl,/heptane gave 14 (55%) and [IT~(CO)~ I(ql-CH3SCH2SCH3)] (18%). The latter compound can be obtained in 64% yield, if chromatography is not preceded by heating the residue in THF. IR (CH,CI,, 298 K) of 14: 2085, 2045vs, 2024vs, 1990 (sh), 1963 (sh), 1864vw, 1829w, 1 7 8 7 ~. IR (nujol): 2086s, 2081s, 2049s, 2033vs, 2027vs, 2012vs, 2006vs, 1999s, 1989s. 'H-NMR (CD2CI2, 168 K): 2.73 (s, 2 CH,); 7.98,3.98 (2d, 1 H each, ,J(H,H) = 7.3, CH,). I3C-NMR: see text. Cross-peaks in a 2D-COSY spectrum at 170 K confirmed the pseudo-trans-positions of b and d, and of c and e. Anal. calc. for C,3H,Ir401,S, (1 157.20): C 13.49, H 0.70; found: C 13.60, H 0.69.