Accession Number:

ADA279746

Title:

Synthesis and Characterization of Single-Source Molecular Precursors to Binary Metal Sulphides: Bis(Diethyldithiocarbamato) M(II)Trialkylphosphine (M=Zn and Cd) Adducts

Descriptive Note:

Technical rept.

Corporate Author:

NEW MEXICO UNIV ALBUQUERQUE

Report Date:

1994-05-06

Pagination or Media Count:

41.0

Abstract:

Monomeric, five-coordinate bisdiethyldithiocarbamatoMII trialkylphosphine complexes, 1 MZn, alkylMe, 2 MZn, alkylEt, 3 MCd, alkylMe, and 4 MCd, alkylEt have been synthesized by addition of trialkylphosphine ligands to toluene solutions of bisdiethyldithiocarbamato MII MZn, and Cd. The bidentate ligand, 1,2-bisdiethylphosphinoethane DEPE reacted with bisdiethyldithiocarbamatoMII MZn, Cd and a 11 mixture of Et2NCS22Zn2Et2NCS22Cd2 in toluene to form five-coordinate, dinuclear DEPE-bridged complexes, Et2NCS22M2mu-DEPE, 5 MZn, 6 MCd and 7 Et2NCS22ZnmuEt2PCH2CH2PEt2CdEt2NCS22, respectively. The composition and structure of all compounds was confirmed by elemental analyses, infra-red spectroscopy, 1H, 13C 1H and 31P1H nuclear magnetic resonance NMR and in selected cases by X-ray crystallography. The solid-state structures of Et2NCS2 2ZnPMe31 and Et2NCS22CdPEt34 have been determined by single-crystal X-ray diffraction. Thermogravimetric analysis TGA of compounds 1-3 showed that the PR3 ligands dissociated prior to thermal decomposition. However, compound 4 exhibited a single weight loss to give crystalline CdS as determined by X-ray powder diffraction, electron diffraction and transmission electron microscopy. The homobimetallic species, 5 and 6 also decomposed to give ZnS and CdS, respectively while the heterobimetallic species, 7, thermally decomposed to give crystalline Zn0.5S according to X-ray powder diffraction data.

Subject Categories:

  • Organic Chemistry
  • Physical Chemistry
  • Crystallography
  • Atomic and Molecular Physics and Spectroscopy

Distribution Statement:

APPROVED FOR PUBLIC RELEASE