Structures, Bonding, and Reactivity of M-S-M' (M and M' = Rh, W, and Cu) Groups in Higher-Nuclearity Heterometallic Sulfide Clusters

Seiji Ogo, Takayoshi Suzuki, Yoshiki Ozawa, Kiyoshi Isobe

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Abstract

This paper reports (i) a rational synthesis of heterometallic sulfide clusters with M-S-M' (M and M' = Rh, W, and Cu) groups, (ii) structures and bonding of the M-S-M' groups determined by X-ray crystallographic analysis and IR spectroscopy, and (iii) reactivity of the M-S-M' groups unique to higher-nuclearity heterometallic sulfide clusters toward H2O and H2S. A branched-type octanuclear sulfide cluster [{Cp*RhP(OEt)3(μ-WS4)(CuCl)Cu} 2-(μ-Cl)2] (4, Cp* = η5-C5Me5) was stepwise prepared from the following sequence: [Cp*RhP(OEt)3Cl2] (1, mononuclear) → [Cp*RhP(OEt)3WS4] (2, dinuclear) → [Cp*RhP(OEt)3(μ-WS4)CuCl] (3, linear-type trinuclear) → 4 by a systematic building-block method. A bridging sulfide ligand in the W-S-Cu group of 4 reacts with a water-saturated CH2Cl2 solution to convert the terminal O atom of [{Cp*RhP(OEt)3(μ-WOS3)(CuCl)Cu} 2(μ-Cl)2] (5, linked incomplete cubane-type octanuclear) with a drastic structural change in the cluster framework. The transformation reaction of 4 to 5 includes the first example of the conversion of the bridging S atom in the M-S-M' group into the terminal O atom without releasing the metal atoms, and this reaction is peculiar to the higher-nuclearity heterometallic sulfide cluster 4. Clusters 4, 5, and 6 ([Cp*RhP(OEt)3(μ-WOS3)CuCl], butterfly-type trinuclear) react with H2S in CH2Cl2 giving 3 as a major product. The formation of 3 in these reactions are based on the reactivity of M-S-Cu groups in the sulfide clusters toward H2S: the (μ3-S)-Cu bonds are easily broken by H2S, but not the (μ2-S)-Cu ones. The crystal data for 1, 2, 3, 4, 5, and 6 confirmed by X-ray analysis are as follows. 1: C16H30Cl2O3PRh, orthorhombic, P21cn, a = 8.988(3) Å, b = 28.591(5) Å, c = 8.276(3) Å, 2 = 4. 2: C16H30O3PRhS4W, monoclinic, P21/n, a = 14.633(2) Å, b = 15.191(2) Å, c = 11.490(1) Å, β = 104.97(1)°, Z = 4. 3: C16H30ClCuO3PRhS4W, monoclinic, P21/m, a = 10.221(2) Å, b = 11.943(2) Å, c = 10.809(1) Å, β = 94.40(1)°, Z = 2. 4: C32H60Cl4Cu4O6P 2Rh2S8W2, monoclinic, P21/n, a = 10.170(3) Å, b = 14.495(3) Å, c = 19.411(3) Å, β = 104.42(1)°, Z = 2. 5·2DMF: C38H74Cl4Cu4N2O 10P2Rh2S6W2, monoclinic, P21/c, a = 10.011(3) Å, b = 17.115(3) Å, c = 18.678(3) Å, β = 95.10(2)°, Z = 2. 6: C16H30ClCuO4PRhS3W, orthorhombic, P21nb, a = 14.515(2) Å, b = 17.225(3) Å, c = 10.261(3) Å, Z = 4.

Original languageEnglish
Pages (from-to)6093-6101
Number of pages9
JournalInorganic chemistry
Volume35
Issue number21
DOIs
Publication statusPublished - 1996
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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