Reactions of α,ω-dithiolate ligands with bis(cyclopentadienyl) molybdenum dichloride; Crystal structures of Mo(η-C5H 5)2{S(CH2)nS)} (n = 2, 3) and a layered hydrate, Mo(η-C5H5)2(SCH 2CH2O)·4.5H2O

W. Edward Lindsell, Georgina M. Rosair, Michael M. Rothmann

Research output: Contribution to journalArticle

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Abstract

Reaction of bis(cyclopentadienyl)molybdenum dichloride 1 in ethanol with 1,3-propanedithiol 2 either in the presence of base or as its thallium derivative produces [Mo(?-C5H5)2(SCH 2CH2 CH2S)] (5) containing a 6-membered ring with a chair conformation, structurally characterized by X-ray diffraction. However, reactions of compound 1 with 2,2'-thiodiethanethiol (3) or 2,2'-oxydiethanethiol (4) under the same conditions do not form complexes with 8-membered chelate rings but lead to thioether or ether bond cleavage, respectively, to yield as major products [Mo(?-C5H 5)2(SCH2CH2X)] (6, X = S, or 7, X = O), containing ligands which form 5-membered rings; crystal structures of 6 and 7 are reported and both contain chelating ligands with envelope conformations. Compound 7 readily incorporates water and the unusual crystal structure of the hydrate Mo(?-C5H5)2(SCH2 CH 2O)·4.5H2O comprises stacks of double layers of hydrated organometallic molecules of overall composition [{Mo(?-C 5H5)2(SCH2CH2O)} 2 • H2O]n separated by layers of hydrogen-bonded water molecules, interconnected by H-bonds between H 2O molecules and O-atoms of the 2-thioethoxy ligand. © 2004 Elsevier B.V. All rights reserved.

Original languageEnglish
Pages (from-to)126-133
Number of pages8
JournalJournal of Organometallic Chemistry
Volume690
Issue number1
DOIs
Publication statusPublished - 3 Jan 2005

Keywords

  • Cyclopentadienyl
  • Hydration
  • Layer structure
  • Molybdenum
  • Thiolate

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