Coupling of methylidyne and carbonyl ligands on the triosmium cluster framework. Crystal structure of (.mu.-H)2Os3(CO)9(.mu.3-.eta.1-CCO)

Synthesis and asymmetric reactivity of enantiomerically pure cyclopentadienylmetal complexes derived from the chiral pool

“…Unfortunately, attempts to form the (neophenylmenthyl)cyclopentadiene (6) proved to be unsuccessful. Both the 4-methylbenzenesulfonate 12 and the methanesulfonate 13 of phenylmenthol (11) were readily formed, but both failed to alkylate cyclopentadienylsodium under a variety of conditions involving changes in temperature (20 or 66 °C) and solvent (THE or THF/DMPU12).…”

“…At 0 °C 10 (0.990 g, 3.00 mmol) in THF (10 mL) was introduced dropwise into the reaction solution. This mixture was stirred at this temperature for 30 min and for 12 h at room temperature and then heated at reflux for 2 h. Acidic (HC1) aqueous workup yielded a yellow oil (0.947 g) that was purified by flash chromatography (hexanes) to provide 3 as a colorless oil (0.386 g, 45.9%) as a mixture of cyclopentadiene double-bond isomers: IR (thin film) 3060, 2952, 2915,1603,1497,1456,1370,1034,900,765,702 cm-1; MS, m/z (relative intensity) 280 (M+, 7), 154 (8), 119 (100), 105 (14), 91 (59), 79 (25), 67 (14); NMR (250 MHz, CDClg) 7.05-7.40 (m, 5 H), 6.38 (br s, 0.3 H), 6.34 (br s, 0.6 ), 6.19 (br s, 1.4 ), 5.91 (br s, 0.7 H), 2.79 (br s, 1.4 H), 2.35-2.75 (m, 1.6 ), 1.86 (m, 1 ), 1.35-1.75 (m, 4 ), 1.30 (m, 1 ), 1.27 (s, 3 ), 1.16 (s, 3 ), 0.90-1.15 (m, 2 ), 0.86 (d, J = 6.4 Hz, 3 H). Anal.…”

“…(Iff,7S)- 1,10,6]deca-2,5-diene ( 4) and (lff,4S,10,6]dec- 2-en-4-ol (20). To LiAlH4 (0.190 g, 5.00 mmol) in ether (20 mL) was added 19 (0.951 g, 5.00 mmol) in ether (5 mL) dropwise under nitrogen.…”

Hydrolytic trimer of chromium(III). Synthesis through chromite cleavage and use in the preparation of the "active" trimer hydroxide

“…Cr(OH2)63+ ;==: Cr(OH)3(OH2)3(s) (4) octahedra are linked solely through H-bonding between OH" and H20 ligands of adjacent metal centers. As a foreseeable consequence of this structure, acidification of this hydroxide leads to…”

[(μ2-H)Ru3(CO)9{μ3-NS(O)MePh}]: An Electron-Deficient Trinuclear Cluster Containing a Chiral Sulfoximido Cap

“…Most of the trinuclear organometallic clusters, however, are electron-precise systems which satisfy the effective atomic number rule with 48 electrons. , Trinuclear 46e clusters are rare; in the iron triad only osmium representatives are known. Apart from [(μ 2 -H)Os 3 (CO) 8 (μ 3 -η 2 -PPh 2 CH 2 PPhC 6 H 4 )], only the famous cluster [(μ 2 -H) 2 Os 3 (CO) 10 ] and its derivatives [(μ 2 -H) 2 Os 3 (CO) 9 L] (L = PMe 2 Ph, PPr i ), [(μ 2 -H)Os 3 (CO) 10 (μ 2 -AuPh)], and [Os 3 (CO) 10 (μ 2 -AuPh) 2 ] 9 have been reported so far. No Ru 3 cluster with an electron count of 46 is mentioned in Deeming's review of 1995 …”