Coordination chemistry of the rhenium-organodiazenido core with facultative tetradentate ligands possessing thiolate-amine and thiolate-thioether donor sets. Crystal and molecular structures of [Re(SCH2CH2NMeCH2CH2NMeCH 2CH2S) (N2COC6H4-p-Cl) (PPh3 ...

Terrence Nicholson, Jon Zubieta

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Abstract

Full title: Coordination chemistry of the rhenium-organodiazenido core with facultative tetradentate ligands possessing thiolate-amine and thiolate-thioether donor sets. Crystal and molecular structures of [Re(SCH2CH2NMeCH2CH2NMeCH 2CH2S) (N2COC6H4-p-Cl) (PPh3)]·CH3OH, [Re(SCH2CH2S(CH2)3SCH 2CH2S)(N2COPh)(PPh3)], and [Re(SCH2CH2S(CH2)3SCH 2CH2S)(N2CO2Me)(PPh 3)]·CH2Cl2 and a comparison with the structure of the oxidation product [N,N′-dimethyl-N,N′-bis(sulfinatoethyl)ethylenediamine-S,N,N′, O′][(2-chlorophenyl)diazenido](triphenylphosphine)rhenium(I), [Re{O2SCH2CH2NMeCH2CH 2NMeCH2CH2SO2}(N2C 6H4-o-Cl)(PPh3)]. The syntheses, crystal structures, electronic spectra, and electrochemical characteristics of a series of rhenium-organodiazenido complexes with facultative tetradentate ligands are reported. Complexes of the type [Re{SCH2CH2X-(CH2)nXCH 2CH2S}(N2R)(PPh3)] (X = NCH3, n = 2, R = -COC6H4Cl (1); X = S, n = 3, R = -COC6H5 (2); X = S, n = 3, R = -CO2Me (3)) are synthesized from the reaction of [ReCl2(PPh3)2(N2R)] complexes with the appropriate tetradentate ligand. Crystal data: for 1, monoclinic space group P21/n, a = 8.683 (2) Å, b = 18.278 (4) Å, c = 24.691 (4) Å, β = 97.95 (1)°, V = 3881.2 (8) Å3, Z = 4, R = 0.055 for 2469 reflections; for 2, monoclinic space group P21/n, a = 11.804 (3) Å, b = 12.529 (3) Å, c = 21.448 (4) Å, β = 89.39 (1) Å, V = 3171.8 (9) Å3, Z = 4, R = 0.068 for 2981 reflections; for 3, monoclinic space group P21/n, a = 8.570(2) Å, b = 10.720 (2) Å, c = 35.618 (6) Å, β = 90.14(11)°, V = 3272.3 (11) Å3, Z = 4, R = 0.061 for 3172 reflections. The structures display rhenium centers in distorted octahedral environments, with coordination sites occupied by two thiolate donors and two amine or sulfido donors from the tetradentate ligands, the phosphorus donor of the PPh3 group, and the α-nitrogen of the linearly end-on coordinated organodiazenido group. The complexes are electrochemically active, exhibiting reversible 1-electron oxidations in the +0.3 to +0.5 V range. The more electron withdrawing the diazenido substituent R, the more positive the oxidation potential, suggesting that the oxidation potential is a measure of the energy of the HOMO. Although complexes of type 1-3 exhibit no tendency toward oxidation under ambient conditions, reaction of [ReCl2(PPh3)2(NH3)-(NNC 6H4Cl)] with N,N′-dimethyl-N,N′-bis(mercaptoethyl)ethylenediamine yields a product, 4, which oxidizes during subsequent chromatographic purification to yield the sulfinato derivative [Re(O2SCH2CH2N(CH3)CH 2CH2N(CH3)-CH2CH2SO 2}(N2C6H4Cl)(PPh3)] (5). Crystal data: for 5, triclinic space group P1, a = 9.060 (3) Å, b = 10.499 (3) Å, c = 19.050 (4) Å, α = 78.18 (1)°, β = 84.85 (1)°, γ = 76.34 (1)°, V = 1722.5 (10) Å3, Z = 2, R = 0.077 for 3395 reflections. The pseudooctahedral geometry about the rhenium center is generated by two amine donors, a sulfur from one sulfinato group and an oxygen from the second sulfinato group of the oxidized tetradentate ligand, the PPh3 phosphorus donor, and the α-nitrogen of the organodiazenido ligand. The structure provides the first example of a complex exhibiting coordination through the oxygen of one sulfinate group and the sulfur of the second sulfinato moiety.

Original languageEnglish (US)
Pages (from-to)2094-2101
Number of pages8
JournalInorganic Chemistry
Volume26
Issue number13
StatePublished - Dec 1 1987
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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