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Synthesis and Co-ordination Chemistry of Dicobaltcomplexed Thiacycloalkynes

DOI: 10.1039/DT9930002765

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2765 - 2774 (1993)

Update date:2022-09-26

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Authors:

Demirhan, FundaDemirhan, Funda

Gelling, AndrewGelling, Andrew

Irisli, SevilIrisli, Sevil

Jeffery, John C.Jeffery, John C.

Salek, Spencer N.Salek, Spencer N.

et al.et al.

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Article abstract of DOI:10.1039/DT9930002765

The reactions of bis(2-mercaptoethyl) sulfide or bis(2-mercaptoethyl) ether with CCH2OH)(CO)6> in the presence of HBF4*OEt2 afford (CO)6> (X = S or O) respectively together with dimeric products.The structure of the monomer (CO)6> has been established by X-ray crystallography and comprises a hexacarbonyldicobalt unit transversely bridged via the alkyne functionality of 1,4,7-trithiacycloundec-9-yne which has an exodentate conformation.Proton NMR studies of the bis(2-mercaptoethyl) sulfide derivatives reveal that the SCH2CH2S linkages are predominantly anti in solution.The monomers undergo carbonyl substitution by bis(diphenylphosphino)methane (dppm) to afford (μ-dppm)(CO)4> (X = S or O) which react with to afford products in which the macrocycles face cap Mo(CO)3 fragments.Reaction of (CO)6> with AgBF4 and PPh3 yields (CO)6>BF4 for which an X-ray crystallographic study revealed that the Ag(PPh3)(1+) fragment is co-ordinated by all three sulfur atoms of the ring which adopts an endodentate conformation.Reaction of (CO)6> with PF6 affords (CO)6>PF6 containing a labile acetonitrile ligand which undergoes substitution by phosphines.The dimeric compound <(OC)6Co2<μ-(CCH2SCH2CH2SCH2CH2SCH2C)2>Co2(CO)6> produces a 1:1 adduct when treated with AgBF4.X-Ray crystallography reveals that the silver ion is co-ordinated by four of the six available thioether groups.

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Product name:{Co2(μ-C2(CH2SCH2CH2)2S)(CO)6}

Cas No:134097-34-0

134097-34-0

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