A series of thallium-iron carbonyl cluster molecules: Structural comparisons of (Et/sub 4/N)/sub 2/(Tl/sub 2/Fe/sub 4/(CO)/sub 16/), (Et/sub 4/N)/sub 4/(Tl/sub 4/Fe/sub 8/(CO)/sub 30/), and (Et/sub 4/N)/sub 6/(Tl/sub 6/Fe/sub 10/(CO)/sub 36/)
Thallium salts and in situ generated K/sup +/(HFe(CO)/sub 4/)/sup /minus// react to form K/sup +/(Tl(Fe(CO)/sub 4/)/sub 2/). The (Et/sub 4/N)/sup +/ salt exists as a dimer in the solid state. Results of single crystal x-ray analysis of (Et/sub 4/N)/sub 2/(TlFe/sub 4/(CO)/sub 16)(Et4/N)/sub 2/(I) are reported. The dimerization occurs through the formation of an asymmetric Tl/sub 2/Fe/sub 2/Parallelogram with Tl-Fe distances of 2.632 (5) and 3.038 (4) /angstrom/. The Fe atoms in the parallelogram are pseudooctahedrally coordinated by the two thallium atoms and four carbonyls. The remaining Fe(CO)/sub 4/ groups are trigonal bipyramids with thalliums located in axial sites (d/sub Tl-Fe/ = 2.553 (5) /angstrom/). (Et/sub 4/N)/sub 2/(I) is monomeric in solution and loses CO upon standing or irradiation to produce (Et/sub 4/N)/sub 4/(Tl/sub 4/Fe/sub 8/(CO)/sub 30/) ((Et/sub 4/N)/sub 4/(II)), which has also been characterized by single-crystal x-ray diffraction: monoclinic space group P2/sub 1//n, with a = 12.723 (6) /angstrom/, b = 16.077 (6) /angstrom/, c = 21.430 (9) /angstrom/, /beta/ = 95.97 (4)/degree/, Z = 2, and V = 4360.2 /angstrom//sup 3/. It too contains a Tl/sub 2/Fe/sub 2/ parallelogram with d/sub Tl-Fe/ = 2.781 (5) and 2.786 (6) /angstrom/. In addition those two thalliums bridge Fe/sub 2/(CO)/sub 6/(/mu/-CO)(/mu/-TlFe(CO)/sub 4/) groups. The CO loss reaction is reversible under pressures of CO. Structural comparisons are made of (Et/sub 4/N)/sub 2/(I) and (Et/sub 4/N)/sub 4/(II) to the previously reported (Et/sub 4/N)/sub 4/(Tl/sub 6/Fe/sub 10/(CO)/sub 36/) ((Et/sub 4/N)/sub 4/(III)): monoclinic space group P2/sub 1//n with a = 12.266 (5) /angstrom/, b = 20.547 (3) /angstrom/, c = 22.892 (6) /angstrom/, /beta/ = 93.24 (3)/degree/, Z = 2, and V = 5759.7 /angstrom/. 33 refs., 4 figs., 10 tabs.
- Research Organization:
- Rice Univ., Houston, TX (USA)
- OSTI ID:
- 5614917
- Journal Information:
- Inorg. Chem.; (United States), Vol. 27:8
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALKANES
CHEMICAL PREPARATION
CRYSTAL STRUCTURE
CARBONYLS
IRON COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
THALLIUM COMPOUNDS
EXPERIMENTAL DATA
DATA
HYDROCARBONS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties