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Osmium Thioether Chemistry: Synthesis and Single-crystal X-Ray Structures of aneS3)2>*2MeNO2, i)(aneS3)>2*MeNO2 and aneS39>PF6*0.5CH2Cl2 (aneS3 = 1,4,7-trithiacyclononane)

DOI: 10.1039/DT9920002977

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2977 - 2986 (1992)

Update date:2022-08-04

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Authors:

Bell, Michael N.Bell, Michael N.

Blake, Alexander J.Blake, Alexander J.

Christie, Robert M.Christie, Robert M.

Gould, Robert O.Gould, Robert O.

Holder, Alan J.Holder, Alan J.

et al.et al.

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Article abstract of DOI:10.1039/DT9920002977

Treatment of <i)>2> with 4 molar equivalents of <9>aneS3 in EtOH for 48 h followed by addition of NH4PF6 affords the bis(sandwich) complex aneS3)22 in 55percent yield.An alternative and more direct route is by reaction of 2 with 2 molar equivalents of <9>aneS3 in refluxing water-dimethylformamide-MeOH (3:1:1 v/v/v) for 48 h followed by addition of NH4PF6.The complex aneS3)2>2*2MeNO2 crystallises in the monoclinic space group P21/a (alt.P21/c, no. 14) with a = 9.6621(5), b = 15.1573(8), c = 10.6367(7) Angstroem, β= 100.524(5) deg and Z = 2.A single-crystal X-ray structure determination shows a centrosymmetric cation with homoleptic thioether co-ordination at OsII, Os-S(1) 2.3313(18), Os-S(4) 2.3380(19) and Os-S(7) 2.3408(20) Angstroem, consistent with a d6 metal centre.The ion aneS3)2>2+ shows a reversible oxidation at E1/2 = +1.16 V vs. ferrocene-ferrocenium.Coulometry confirms this oxidation to be a one-electron process.Electrochemical or chemical oxidation of aneS3)2>2+ gives aneS3)2>3+ which has been characterised by electronic and ESR spectroscopy.Reaction of <i)>2> with 2 molar equivalents of <9>aneS3 in MeOH followed by addition of NaBPh4 affords the mixed-sandwich complex i)(<9>aneS3)>2 in 65percent yield.The complex i)(<9>aneS3)>2*MeNO2 crystallises in the triclinic space group P<*>, a = 11.5027(8), b = 13.8509(13), c = 18.3983(12) Angstroem, α = 94.72(1), β = 105.01(3), γ = 91.28(1) deg and Z = 2.The crystal structure shows facial co-ordination of both <9>aneS3 and 4-MeC6H4Pri at octahedral OsII.Interestingly, there is an unusualdisorder of the trithia macrocycle with two enantiomers of <9>aneS3 being present in the crystal: the two forms of the macrocycle were successfully modelled.Reaction of with 1 molar equivalent of <9>aneS3 in the presence of NH4PF6 in refluxing acetone (M = Ru) or refluxing 2-methoxyethanol (M = Os) for 2 h under N2 gives aneS3)>PF6.The complex aneS3)>PF6*0.5CH2Cl2 crystallises in the monoclinic space group P21/n (alt.P21/c, no. 14) with a = 15.955(6), b = 21.929(9), c = 8.895(7) Angstroem, β = 96.69(8) and Z = 4.The structure shows octahedral OsII with <9>aneS3 bound facially, Os-S(1) 2.377(3) (trans to CO), Os-S(4) 2.369(3) (trans to PPh3), Os-S(7) 2.402(3) (trans to H), Os-H 1.60(9), Os-P 2.3344(24) and Os-C 1.868(11) Angstroem.The reactivity of aneS3)>+ with O2 and chlorinated solvents is discussed.

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Product name:OsCl2(P(C6H5)3)(C6H12S3)

Cas No:145312-33-0

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