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/)

Journal Article · Wed Apr 20 04:00:00 EDT 1988 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00281a007· OSTI ID:5614917

Whitmire, K H; Cassidy, J M; Rheingold, A L; Ryan, R R

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), Journal Name: Inorg. Chem.; (United States) Vol. 27:8; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKANES
CARBONYLS
CHEMICAL PREPARATION
CRYSTAL STRUCTURE
DATA
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
IRON COMPOUNDS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
SYNTHESIS
THALLIUM COMPOUNDS
TRANSITION ELEMENT COMPOUNDS