Reactions of diacetylene ligands with trinuclear clusters. I Reactions of 2,4-hexadiyne-1,6-diol and its dicobalthexacarbonyl derivatives with H2Os3(CO)10

A comparison between the reaction of P2Ph4 with [{Co2(CO)6}2(μ-η2:μ-η2-HOCH2CCCCCH2OH)] and the reaction of [Co2(μ-PPh2)2(CO)6] with HOCH2CCCCCH2OH

“…A related dehydration of 2,4-hexadiyne-1,6-diol on reaction with H 2 Os 3 (CO) 10 has been reported. No CO insertion was observed in this dehydration, however, and furan ring formation occurred yielding [Os 3 (µ-H)(µ 2 ,-η 3 -OCH=CHC=CCCH 3 )(CO) 10 ] [32,33]. Dehydration-cyclocarbonylation of a diynediol to give a 2(5H)-furanone, as observed here, has not been previously reported.…”

“…Reaction of [Co 2 (l-PPh 2 ) 2 (CO) 6 ] with HOCH 2 C" CAC"CCH 2 OH at 80°C in toluene produced a range of products (Scheme 3), in moderate yields (see Section 4): Unreacted [Co 2 (l-PPh 2 ) 2 (CO) 6 ], [13] [Co 3 (l-PPh 2 ) 3 (CO) 6 ], [13] [Co 2 (CO) 6 (l-g 2 -HOCH 2 C"CACCCH 2 OH)] [32] and [Co 2 {l-g 4 -PPh 2 C(CCCH 2 OH)C(CH 2 OH)CO} (l-PPh 2 )(CO) 4 ] (4) were isolated. The identity of these complexes (except 4) was confirmed by comparison of their 1 H, 31 P NMR and IR spectra with the literature values.…”

“…Unless otherwise stated, all reagents were obtained from commercial suppliers and used without Table 4 Selected bond distances (Å ) and angles (°) for complex 4 further purification. [{Co 2 (CO) 6 } 2 (l-g 2 :l-g 2 -HOCH 2 C"CAC"CCH 2 OH)] was prepared by the literature method [32,82]. [Co 2 (l-PPh 2 ) 2 (CO) 6 ] was generated in situ from [Co 2 (CO) 8 ] and PPh 2 H using our previously reported modification of GeoffroyÕs procedure [2,13].…”

A new synthetic route for the preparation of [Os3(CO)10(μ-OH)(μ-H)] and its reaction with bis(diphenylphosphino)methane (dppm): syntheses and X-ray structures of two isomers of [Os3(CO)8(μ-OH)(μ-H)(μ-dppm)] and [Os3(CO)7(μ3-CO)(μ3-O)(μ-dppm)]

“…26,27 The geometry-optimized structures presented here have been drawn with the JIMP2 molecular visualization and manipulation program. 28 The rst structural reports on [Os 3 (CO) 10 (m-OH)(m-H)] appeared in 1995, [31][32][33] and all three structures contained hydrogens that were placed in xed positions. The hydroxyl hydrogen in [Os 3 (CO) 10 (m-OH)(m-H)] is diastereotopic and can exist as a mixture of cis and trans stereoisomers depending on the disposition of the hydrogen with respect to an appropriate reference point, which we will dene here as the axial CO in the Os(CO) 4 moiety that is located on the same face of the Os 3 plane as the bridging hydroxyl group.…”

Reactions of linked tetrahedron clusters [Co2(CO)6(μ-HC2CH2O)–]2R with Rh2(CO)4Cl2 to give mixed-metal linked alkyne-bridged butterfly clusters containing C2Co2Rh2 unit

“…The linked clusters have been receiving considerable attention in recent years because of their potential application as polymeric materials and their unusual structures and reactions [1][2][3][4][5][6]. The chemistry of transition metal complexes bridged by unsaturated hydrocarbons developed rapidly and extensively in recent years resulting from the relevance to the chemistry of metal-catalyst surfaces [7,8].…”