Zirconium-Sulfur Chemistry. Synthesis and Structural Characterization of the Zr3S3(tBuS)2(BH4)4(THF)2, Zr6S6(tBuS)4(BH4)8(THF)2, Zr3(S)(tBuS)10, and (Mg(THF)6)[Zr2(SPh)7.2(CH2Ph)1.8]2·3THF Clusters. Activation and Cleavage of the C-S Bond in Zirconium-Coordinated Alkanethiolate Ligands

D. Coucouvanis*, A. Hadjikyriacou, R. Lester, M. G. Kanatzidis

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

34 Scopus citations


New zirconium thiolate complexes have been obtained by the acidification of either the Zr(BH4)4 or the Zr(CH2Ph)4 complexes by RSH molecules in reactions that produce either B2H6 or toluene as byproducts. The polynuclear clusters Zr3S3(tBuS)2(BH4)4(THF)2, I, and Zr6S6(tBuS)4(BH4)8(THF)2, II, are obtained from tBuSH and Zr- (BH4)4. The Zr3(S)(tBuS)10 cluster, III, is obtained from tBuSH and Zr(CH2Ph)4. The sulfido ligands in these clusters are obtained from the zirconium-coordinated tBuS- ligands as a result of C-S bond activation followed by what appears to be mainly a heterolytic bond cleavage reaction. The (Mg(THF)6)[Zr2(SPh)7.2(CH2Ph)1.8]2·3THF cluster, IV, was obtained from Zr(CH2Ph)4 and PhSH in the presence of H2CPhMgCl. The absence of S2- ligands in IV is attributed to a stronger C-S bond in the Z-coordinated PhS- ligands. The compounds I-IV crystallize all in the space group P21/c. The cell dimensions are a = 11.545(3) Å, b = 16.481(4) Å, c = 18.118(4) Å, and β = 91.23(2)° for I, a = 12.443(1) Å, β = 15.197(2) Å, c = 18.365(2) Å, and β = 70.214(7)° for II, a = 22.009(8) Å, b = 11.372(4) Å, c = 26.980(7) Å, and β = 101.93(3)° for III, and a = 14.352(6) Å, b = 22.307(14) Å, c = 23.554(8) Å, and β = 95.46(3)° for IV. The data for all structures were obtained on an automatic diffractometer employing Mo Kα radiation. Full matrix refinement of 235 parameters on 2169 data for I, 278 parameters on 3102 data for II, 315 parameters on 3966 data for III, and 387 parameters on 2582 data for IV gave final Rw values of 0.050, 0.043, 0.069, and 0.070, respectively. The structures of I-III are closely related and contain the [Zr33- S)22S)3]n+ core, with a distorted hexagonal bipyramidal structure, as a structural feature. In I and II the Zr3 subunits (n = 4) show two µ2-tBu thiolates and a µ2-sulfide ligands bridging the Zr atoms in the equatorial plane and two µ3-sulfido ligands serving as “capping” ligands on the axial positions. In III (n = 6) three µ2-tBu thiolates bridge the Zr atoms in the equatorial plane and µ3-sulfido and µ3-thiolato ligands serve as “capping” ligands on the axial positions. The coordination geometries of the Zr atoms are distorted octahedral, and in I and II BH4- and THF ligands are involved in coordination. Only sulfur ligands are coordinated to the zirconium atoms in III.

Original languageEnglish (US)
Pages (from-to)3645-3655
Number of pages11
JournalInorganic chemistry
Issue number17
StatePublished - Aug 1 1994

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Fingerprint Dive into the research topics of 'Zirconium-Sulfur Chemistry. Synthesis and Structural Characterization of the Zr<sub>3</sub>S<sub>3</sub>(<sup>t</sup>BuS)<sub>2</sub>(BH<sub>4</sub>)<sub>4</sub>(THF)<sub>2</sub>, Zr<sub>6</sub>S<sub>6</sub>(<sup>t</sup>BuS)<sub>4</sub>(BH<sub>4</sub>)<sub>8</sub>(THF)<sub>2</sub>, Zr<sub>3</sub>(S)(<sup>t</sup>BuS)<sub>10</sub>, and (Mg(THF)<sub>6</sub>)[Zr<sub>2</sub>(SPh)<sub>7.2</sub>(CH<sub>2</sub>Ph)<sub>1.8</sub>]<sub>2</sub>·3THF Clusters. Activation and Cleavage of the C-S Bond in Zirconium-Coordinated Alkanethiolate Ligands'. Together they form a unique fingerprint.

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