Synthesis and co-ordination chemistry of dicobalt-complexed thiacycloalkynes

Funda Demirhan; Andrew Gelling; Sevil Irişli; John C. Jeffery; Spencer N. Salek; Ozan S. Şentürk; Michael J. Went

doi:10.1039/DT9930002765

Synthesis and co-ordination chemistry of dicobalt-complexed thiacycloalkynes

Funda Demirhan, Andrew Gelling, Sevil Irişli, John C. Jeffery, Spencer N. Salek, Ozan S. Şentürk, Michael J. Went^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

18 Citations (Scopus)

Abstract

The reactions of bis(2-mercaptoethyl) sulfide or bis(2-mercaptoethyl) ether with [Co₂(μ-HOCH₂C≡CCH₂OH)(CO) ₆] in the presence of HBF₄·OEt₂ afford [Co₂{μ-C₂(CH₂SCH₂CH ₂)₂X}(CO)₆] (X = S or O) respectively together with dimeric products. The structure of the monomer [Co₂{μ-C ₂(CH₂SCH₂CH₂)₂S}-(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 SCH ₂CH₂S linkages are predominantly anti in solution. The monomers undergo carbonyl substitution by bis(diphenylphosphino)methane (dppm) to afford [Co₂{μ-C₂(CH₂SCH ₂CH₂)₂X}(μ-dppm)(CO)₄] (X = S or O) which react with [Mo(CO)₃(η-C₆H₃Me ₃-1,3,5)] to afford products in which the macrocycles face cap Mo(CO)₃ fragments. Reaction of [Co₂{μ-C ₂(CH₂SCH₂CH₂)₂S}(CO) ₆] with AgBF₄ and PPh₃ yields [Co ₂{μ-C₂(CH₂SCH₂CH ₂)₂S}(CO)₆{Ag(PPh₃)}]BF₄ for which an X-ray crystallographic study revealed that the Ag(PPh ₃)⁺ fragment is co-ordinated by all three sulfur atoms of the ring which adopts an endodentate conformation. Reaction of [Co ₂{μ-C₂(CH₂SCH₂CH ₂)₂S}(CO)₆] with [Cu(MeCN)₄]PF ₆ affords [Co₂{μ-C₂(CH₂SCH ₂CH₂)₂S}(CO)₆{Cu(MeCN)}]PF ₆ containing a labile acetonitrile ligand which undergoes substitution by phosphines. The dimeric compound [(CO)₆Co ₂{μ-(CCH₂SCH₂-CH₂SCH ₂CH₂SCH₂C)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.

Original language	English
Pages (from-to)	2765-2773
Number of pages	9
Journal	Journal of the Chemical Society. Dalton Transactions
Issue number	18
DOIs	https://doi.org/10.1039/DT9930002765
Publication status	Published - 1993
Externally published	Yes

Access to Document

10.1039/DT9930002765

Cite this

@article{11c75ba39e6a40ef9a67a339901c29db,

title = "Synthesis and co-ordination chemistry of dicobalt-complexed thiacycloalkynes",

abstract = "The reactions of bis(2-mercaptoethyl) sulfide or bis(2-mercaptoethyl) ether with [Co2(μ-HOCH2C≡CCH2OH)(CO) 6] in the presence of HBF4·OEt2 afford [Co2{μ-C2(CH2SCH2CH 2)2X}(CO)6] (X = S or O) respectively together with dimeric products. The structure of the monomer [Co2{μ-C 2(CH2SCH2CH2)2S}-(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 SCH 2CH2S linkages are predominantly anti in solution. The monomers undergo carbonyl substitution by bis(diphenylphosphino)methane (dppm) to afford [Co2{μ-C2(CH2SCH 2CH2)2X}(μ-dppm)(CO)4] (X = S or O) which react with [Mo(CO)3(η-C6H3Me 3-1,3,5)] to afford products in which the macrocycles face cap Mo(CO)3 fragments. Reaction of [Co2{μ-C 2(CH2SCH2CH2)2S}(CO) 6] with AgBF4 and PPh3 yields [Co 2{μ-C2(CH2SCH2CH 2)2S}(CO)6{Ag(PPh3)}]BF4 for which an X-ray crystallographic study revealed that the Ag(PPh 3)+ fragment is co-ordinated by all three sulfur atoms of the ring which adopts an endodentate conformation. Reaction of [Co 2{μ-C2(CH2SCH2CH 2)2S}(CO)6] with [Cu(MeCN)4]PF 6 affords [Co2{μ-C2(CH2SCH 2CH2)2S}(CO)6{Cu(MeCN)}]PF 6 containing a labile acetonitrile ligand which undergoes substitution by phosphines. The dimeric compound [(CO)6Co 2{μ-(CCH2SCH2-CH2SCH 2CH2SCH2C)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.",

author = "Funda Demirhan and Andrew Gelling and Sevil Iri{\c s}li and Jeffery, {John C.} and Salek, {Spencer N.} and {\c S}ent{\"u}rk, {Ozan S.} and Went, {Michael J.}",

year = "1993",

doi = "10.1039/DT9930002765",

language = "English",

pages = "2765--2773",

journal = "Journal of the Chemical Society. Dalton Transactions",

issn = "1472-7773",

publisher = "Royal Society of Chemistry",

number = "18",

}

TY - JOUR

T1 - Synthesis and co-ordination chemistry of dicobalt-complexed thiacycloalkynes

AU - Demirhan, Funda

AU - Gelling, Andrew

AU - Irişli, Sevil

AU - Jeffery, John C.

AU - Salek, Spencer N.

AU - Şentürk, Ozan S.

AU - Went, Michael J.

PY - 1993

Y1 - 1993

N2 - The reactions of bis(2-mercaptoethyl) sulfide or bis(2-mercaptoethyl) ether with [Co2(μ-HOCH2C≡CCH2OH)(CO) 6] in the presence of HBF4·OEt2 afford [Co2{μ-C2(CH2SCH2CH 2)2X}(CO)6] (X = S or O) respectively together with dimeric products. The structure of the monomer [Co2{μ-C 2(CH2SCH2CH2)2S}-(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 SCH 2CH2S linkages are predominantly anti in solution. The monomers undergo carbonyl substitution by bis(diphenylphosphino)methane (dppm) to afford [Co2{μ-C2(CH2SCH 2CH2)2X}(μ-dppm)(CO)4] (X = S or O) which react with [Mo(CO)3(η-C6H3Me 3-1,3,5)] to afford products in which the macrocycles face cap Mo(CO)3 fragments. Reaction of [Co2{μ-C 2(CH2SCH2CH2)2S}(CO) 6] with AgBF4 and PPh3 yields [Co 2{μ-C2(CH2SCH2CH 2)2S}(CO)6{Ag(PPh3)}]BF4 for which an X-ray crystallographic study revealed that the Ag(PPh 3)+ fragment is co-ordinated by all three sulfur atoms of the ring which adopts an endodentate conformation. Reaction of [Co 2{μ-C2(CH2SCH2CH 2)2S}(CO)6] with [Cu(MeCN)4]PF 6 affords [Co2{μ-C2(CH2SCH 2CH2)2S}(CO)6{Cu(MeCN)}]PF 6 containing a labile acetonitrile ligand which undergoes substitution by phosphines. The dimeric compound [(CO)6Co 2{μ-(CCH2SCH2-CH2SCH 2CH2SCH2C)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.

AB - The reactions of bis(2-mercaptoethyl) sulfide or bis(2-mercaptoethyl) ether with [Co2(μ-HOCH2C≡CCH2OH)(CO) 6] in the presence of HBF4·OEt2 afford [Co2{μ-C2(CH2SCH2CH 2)2X}(CO)6] (X = S or O) respectively together with dimeric products. The structure of the monomer [Co2{μ-C 2(CH2SCH2CH2)2S}-(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 SCH 2CH2S linkages are predominantly anti in solution. The monomers undergo carbonyl substitution by bis(diphenylphosphino)methane (dppm) to afford [Co2{μ-C2(CH2SCH 2CH2)2X}(μ-dppm)(CO)4] (X = S or O) which react with [Mo(CO)3(η-C6H3Me 3-1,3,5)] to afford products in which the macrocycles face cap Mo(CO)3 fragments. Reaction of [Co2{μ-C 2(CH2SCH2CH2)2S}(CO) 6] with AgBF4 and PPh3 yields [Co 2{μ-C2(CH2SCH2CH 2)2S}(CO)6{Ag(PPh3)}]BF4 for which an X-ray crystallographic study revealed that the Ag(PPh 3)+ fragment is co-ordinated by all three sulfur atoms of the ring which adopts an endodentate conformation. Reaction of [Co 2{μ-C2(CH2SCH2CH 2)2S}(CO)6] with [Cu(MeCN)4]PF 6 affords [Co2{μ-C2(CH2SCH 2CH2)2S}(CO)6{Cu(MeCN)}]PF 6 containing a labile acetonitrile ligand which undergoes substitution by phosphines. The dimeric compound [(CO)6Co 2{μ-(CCH2SCH2-CH2SCH 2CH2SCH2C)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.

UR - http://www.scopus.com/inward/record.url?scp=37049084940&partnerID=8YFLogxK

U2 - 10.1039/DT9930002765

DO - 10.1039/DT9930002765

M3 - Article

AN - SCOPUS:37049084940

SN - 1472-7773

SP - 2765

EP - 2773

JO - Journal of the Chemical Society. Dalton Transactions

JF - Journal of the Chemical Society. Dalton Transactions

IS - 18

ER -

Synthesis and co-ordination chemistry of dicobalt-complexed thiacycloalkynes

Abstract

Access to Document

Other files and links

Fingerprint

Cite this