Reactions of [H₂Os₃(CO)₁₀] with Conjugated Diynes (RC₂C₂R‘) Containing Nucleophilic Oxygen in β Position of a Substituent (R = Ph, R‘ = CH₂OH, C(O)Ph; R = R‘ = CMe₂(OH))

Abstract

Reactions of [H2Os3(CO)10] with a series of diynes, RC2C2R‘ (1: R = Ph, R‘ = CH2OH; 2: R = Ph, R‘ = C(O)Ph; 3: R = R‘ = C(OH)Me2), have been studied. It was found that upon coordination to the triosmium cluster, the nucleophilic oxygens of the R‘ substituents of 1 and 2 take part in intramolecular cyclization reactions to give [HOs3(CO)10{μ-η1:η2-PhCH2(CCH−CCH−O)}] (5) and [HOs3(CO)10{μ-η1:η1-Ph(CCH−CC−O)CPh}] (6), respectively, both of which contain furan rings coordinated to the cluster core. On heating of the latter compound, the furan moiety remains intact, but a carbonyl group dissociates from the cluster, leading to the formation of [HOs3(CO)9(μ3-η1:η3:η1-Ph(CCH−CC−O)CPh)] (7) with a closed “C3Os3” pentagonal pyramidal structure. Reaction of [H2Os3(CO)10] with 3 does not lead to cyclization of the diyne; instead, the clusters [Os3(CO)10{μ3-η2-(RCHCH−C2R)}] (8) and [Os3(CO)10{μ3-η2-(RC2C2R)}] (9) are formed. Deuterium labeling of the starting compounds has been used in the reaction of [H2Os3(CO)10] with HOCH2C2C2CH2OH in order to investigate possible mechanisms of the cyclization reaction. The crystal and molecular structures of clusters 5, 7, and 9 are presented.

Formation of multifunctional ligands by nucleophilic addition of alcohols and thiols to the alkyne groups in compound C5H5FeC5H4CCSCCH: Reactivity studies

“…This fact seems to be as a result of the contribution of the electron lone pairs on the sulfur and oxygen atoms. Similar values are found in compound trans-[Pt{(E)-C(SMe)@CHPh}Cl(PEt 3 ) 2 ]ÁCHCl 3 [1.766(6) Å] [11] and [HOs 3 (CO) 10 (l-g 1 :g 2 -PhCH 2 C@CH-C@CH-O)] [1.400 (12) Å] [12]. The C(2)-S(2)-C(3) angle [101.1(2)] is comparable to those found for the compounds FcC"CSC"CSiMe 3 [99.…”

“…According to the mechanisms described for these authors, we agree that once the complex [{Co 2 (CO) 6 } 2 (l-g 2 :g 2 -FcCCSCCH)] is formed, it can react with a molecule of the alkyne [{Co 2 (CO) 6 }(l-g 2 -FcCCSC"CH)] followed by another molecule of the ferrocenyl alkyne [{Co 2 (CO) 6 }(l-g 2 -FcC"CSCCH)] to give the trimerization product [{Co 2 (CO) 6 } 3 -(l-g 2 -FcCCS) 2 (l-g 2 -HCCS)]C 6 H 2 Fc after demetallation. Its spectroscopic and spectrometric data are the following: IR (m CO 2092m, 2061 s, 2030 vs), 1 H NMR {7.19 (s, 2H, C 6 H 2 ), 6.77 (s, 1H, HC"C), 4.54-4.36 (m, 12H, C 5 H 4 ), 4.34 (s, 5H, C 5 H 5 ), 4.31 (s, 5H, C 5 H 5 ), 4.20 (s, 5H, C 5 H 5 }, MS(ESI + ) m/z: 1488-1152 (M + ÀnCO, n = [6][7][8][9][10][11][12][13][14][15][16][17][18].…”

Bis[1,3-bis(pentafluorophenyl)triazenido]tricarbonylosmium(II)

“…The axial Os1-C2 bond length is 1.934 (5) Å , longer than the above two. The C-O bond lengths and the Os-C-O angles are similar to those observed in other osmium-carbonyl compounds (Akther et al, 2003;Canal et al, 2003;Fink et al, 1999;Kiriakidou-Kazemifar et al, 2001;Kramer et al, 2002;Pomogailo et al, 2002;Sun et al, 2005;Tunik et al, 2003). Selected bond angles and lengths are listed in Table 1.…”

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.…”