New Method for Intramolecular Cyclization of Osmium-Coordinated Diynes Avoiding Os3(μ-H)2(CO)10 as Starting Material

A new method of synthesis was carried out for the preparation of the hydride clusters [Os3(μ-H)(CO)9{μ3,η1:η3:η1-RC2COHC≡CR}] (R = C4H3S (1a), BrC4H2S (1b), Ph (1c)) by reaction between RC≡CC≡CR (R = C4H3S (a), BrC4H2S (b), Ph (c)) and the “non-hydride” [Os3(CO)11(CH3CN)] in dichloromethane at room temperature and in the presence of water, avoiding the starting material [Os3(μ-H)2(CO)10]. The complexes [Os3(μ-CO)(CO)9{μ3,η1:η2:η1-RC4R}] (R = C4H3S (2a), BrC4H2S (2b), Ph (2c)) were also obtained as byproducts. 1a−c and 2a−c contain a “closed” Os3 triangular core in μ3,η1:η3:η1-allylic and μ3,η1:η2:η1-alkyne coordination modes, respectively. When the reaction is carried out in wet polar and donor solvents [Os3(μ-H)(CO)9{μ3,η1:η3:η1-RC2CH═COCR}] (R = C4H3S (3a), BrC4H2S (3b), Ph (3c)) are obtained, where the organic ligand turns into a furan ring by an intramolecular cyclization process. These reactions proceed through 1a−c as intermediates, identified by 1H NMR. Therefore, 3a−c have also been obtained as th...

[1]  M. Marcos,et al.  Electronic communication through a poly-yne carbonyldicobalt complex containing an open linear triosmium cluster. , 2009, Dalton transactions.

[2]  M. Marcos,et al.  Synthesis, Characterization, Structures and Comparative Electrochemical Study of 2,4-Bis(trimethylsilylethynyl)thiophene Coordinated Carbonylcobalt Units , 2007 .

[3]  R. Gracia,et al.  Synthesis, Characterization, and Redox Behavior of Mixed 1,3-Diyne Dicobalt/Triosmium and Dicobalt/Triruthenium Carbonyl Clusters , 2007 .

[4]  A. Poë,et al.  Electronic and steric effects in fragmentation reactions of Os3(CO)9(mu-C4Ph4). , 2005, Dalton transactions.

[5]  J. Davies,et al.  Molecular rearrangements of diynes coordinated to triosmium carbonyl clusters: reactions of [Os3(μ-H)2(CO)10] and [Os3(CO)10(MeCN)2] with 1,4-dipyridylbuta-1,3-diyne , 2005 .

[6]  T. Pakkanen,et al.  Reactions of 2,4-hexadiyne-1,6-diol with [H2Os3(CO)9(PR3)] clusters. Cyclization of the diyne and reversible exchange of the phosphine ligands between different positions of the "Os3C3" framework. , 2004, Dalton transactions.

[7]  J. Davies,et al.  Molecular rearrangements of diynes coordinated to triosmium carbonyl clusters: the synthesis and structural characterisation of [Os-3(mu-H)(CO)(10){mu(3)-eta(1):eta(3):eta(1)-Ph(C)C9H6)}], [Os-3(mu-H)(CO)(9){mu(3)- eta(1):eta(3):eta(1)-Ph(C)C9H6)}] and [Os-3(mu-H)(CO)(8)(MeCN){mu(3)-eta(1):eta(3):et , 2003 .

[8]  T. Pakkanen,et al.  Reactions of [H2OS3(CO)(10)] with conjugated diynes (RC2C2R ') containing nucleophilic oxygen in beta position of a substituent (R = Ph, R ' = CH2OH, C(O)Ph; R = R ' = CMe2(OH)) , 2003 .

[9]  Mark D. Smith,et al.  Reactions of Os3(CO)10(μ-H)2 with 1,8-Bis(ferrocenyl)octatetrayne Yield Products Involving Cyclizations and Trans-Hydrogenation of Alkyne Groups , 2002 .

[10]  J. Davies,et al.  Reactions of [Os3(CO)10(NCMe)2] with symmetric diynes and their reactivity towards [Co2(CO)8] , 2001 .

[11]  T. Pakkanen,et al.  Reactions of Diacetylene Ligands with Trinuclear Clusters; Cyclization of Diynes with beta-amino moieties on the surface of H2Os3(CO)10 , 2001 .

[12]  J. Davies,et al.  Reaction of [Os3H2(CO)10] with the diyne Me3SiC2C2SiMe3 and the reactivity of the products towards [Co2(CO)8]: the X-ray structures of [Os3(μ-H)(CO)10{μ-η1-η2-HC2(SiMe3)C2(SiMe3)}], [Os3(μ-CO)(CO)9{μ3-η2-Me3SiC2C2SiMe3}] and [Os3(μ-H)(CO)9{μ3-η1:η2-;μ-η2-Me3SiC2C2[Co2(CO)6]}] , 2000 .

[13]  B. Qu,et al.  Effect of Metals on the Electronic Communication through a Molecular Wire Model , 2000 .

[14]  C. Adams,et al.  A new two-strand chain cluster: the synthesis and characterisation of [Os3(CO)11{μ3-η4-(C4H3S)C2C2(C4H3S)}] , 2000 .

[15]  G. Enright,et al.  Synthesis and structure of metallocarbon clusters bearing pendant ethynyl ligands. X-ray crystal structures of Os3(CO)9(μ-CO)(μ3-η1,η1,η2-Me3SiCCC2CCSiMe3), Os3Ru(CO)12(μ4-η1,η2,η1,η2-Me3SiCCC2CCSiMe3), Ru4(CO)12(μ4-η1,η2,η1,η2-Me3SiCCC2CCSiMe3) and {Ru4(CO)12}{Co2(CO)6}(μ4-η1,η2,η1,η2:μ-η2,η2-Me3Si , 1999 .

[16]  R. Giordano,et al.  Metal–Carbonyl Clusters with Alkynes Bound in “Parallel” or “Perpendicular” Fashion , 1997 .

[17]  G. Starova,et al.  Reactions of diacetylene ligands with trinuclear clusters II. Reactions of hexa-2,4-diyne-1,6-diol and 1,4-diphenyl-1,3-butadiyne with Ru3(CO)12 , 1997 .

[18]  B. Skelton,et al.  Preparation and thermolysis of complexes derived from some trinuclear ruthenium clusters and 1,4-diphenylbuta-1,3-diyne , 1997 .

[19]  Scott R. Wilson,et al.  Reaction of (μ-H)2Os3(CO)9(PPh3) with Acetylene and Ethylene. Structures, Dynamics, and Interconversion of Two Isomers of the Vinyl Complex (μ-H)Os3(CO)9(PPh3)(μ-CHCH2) , 1996 .

[20]  B. Skelton,et al.  Reactions between ruthenium cluster carbonyls and 1,4-diphenylbuta-1,3-diyne , 1996 .

[21]  P. Low,et al.  Some transition-metal complexes derived from silylated 1,3-diynes , 1996 .

[22]  M. G. Karpov,et al.  Reactions of diacetylene ligands with trinuclear clusters. I Reactions of 2,4-hexadiyne-1,6-diol and its dicobalthexacarbonyl derivatives with H2Os3(CO)10 , 1995 .

[23]  A. Deeming,et al.  Conversion of the clusters [Os3(1,3-diyne)(CO)10] into bis(alkynyl) clusters by carboncarbon bond cleavage , 1993 .

[24]  D. Osella,et al.  Reactions of the co-ordinatively unsaturated cluster [Os3(µ-H)(CO)8{Ph2PCH2P(Ph)C6H4}] with alkynes RCCR (R = Ph, C6H4Me, Me or CF3); crystal structures of [Os3(CO)8{µ3–η2(∥)–RC2R}(Ph2PCH2PPh2)](R = Me or CF3) and electrochemical behaviour of triosmium–alkyne clusters , 1993 .

[25]  A. Deeming,et al.  Structural aspects of the osmium and ruthenium clusters [M3(CO)10(alkyne)] and related substituted compounds , 1992 .

[26]  François Diederich,et al.  Synthetic approaches toward molecular and polymeric carbon allotropes , 1992 .

[27]  L. Farrugia,et al.  Reappraisal of the fluxional behavior of Ru3(.mu.-H)(.mu.3-.eta.2-C.tplbond.CBu-tert)(CO)9 and evidence for the concerted rotation of the Ru(CO)2(PMe2Ph) group in the enantiomerization of Ru3(.mu.-H)(.mu.3-.eta.2-C.tplbond.CBu-tert)(CO)8(PMe2Ph) , 1992 .

[28]  L. Brandsma,et al.  An Alternative Synthysis of Thieno[3,4-b]Thiophene , 1990 .

[29]  A. Poë,et al.  Kinetics of reactions of hydrogen with [Os3(CO)11(NCMe)] and [Os3(CO)10(NCMe)2] , 1989 .

[30]  P. Bates,et al.  Oxidative addition of 1,3-diynes at triosmium clusters with cleavage of the central carbon–carbon bond: X-ray crystal structure of [Os3(µ3,η2-C2Ph)(µ-C2Ph)(CO)9] derived from 1,4-diphenylbuta-1,3-diyne , 1987 .

[31]  L. Lian,et al.  Two-dimensional nuclear magnetic resonance for the quantitative analysis of three-site exchange in the ruthenium cluster [Ru3(μ-H)(CO)9(MeCCHCme)] , 1985 .

[32]  P. Raithby,et al.  Alkyne-Substituted Transition Metal Clusters , 1985 .

[33]  P. Braunstein,et al.  Alkyne-substituted homo- and heterometallic carbonyl clusters of the iron, cobalt and nickel triads , 1983 .

[34]  D. Osella,et al.  Relationships between structure and ligand dynamics in Organometal Clusters , 1982 .

[35]  B. Hanson,et al.  Reactions of alkynes with [Os3(CO)11(NCCH3)]: the crystal structures of [Os3(CO)9(C3H2OH)H] and [Os3(CO)9(C3H2OCH3)H] , 1980 .

[36]  B. Deboer,et al.  Structural studies on polynuclear osmium carbonyl hydrides. 1. Crystal structures of the isomorphous species undecacarbonyldihydrotriosmium and dodecacarbonyltriosmium. Role of an equatorial .mu.2-bridging hydride ligand in perturbing the arrangement of carbonyl ligands in a triangular cluster , 1977 .

[37]  H. Kaesz,et al.  Synthesis of hydrido- and deuterio-carbonyl cluster complexes of ruthenium, iron--ruthenium, and osmium from metal carbonyls and hydrogen at atmospheric pressure , 1975 .

[38]  R. Dickson,et al.  Compounds Derived from Alkynes and Carbonyl Complexes of Cobalt , 1974 .

[39]  D. Shriver,et al.  Carbon- and oxygen-coordinated carbon monoxide. Fe2(.pi.-C5H5)2(CO)2(COAl(C2H5)3)2 and Fe4(.pi.-C5H5)4(COAl(C2H5)3)4 , 1969 .

[40]  G. Eglinton,et al.  722. Macrocyclic acetylenic compounds. Part II. 1,2:7,8-Dibenzocyclododeca-1,7-diene-3,5,9,11-tetrayne , 1960 .

[41]  G. Eglinton,et al.  182. Macrocyclic acetylenic compounds. Part I. Cyclotetradeca-1 :3-diyne and related compounds , 1959 .