skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Investigations of the technetium-hydrazido Core. Synthesis and structural characterization of ((n-C sub 4 H sub 9 ) sub 4 N)(Tc sub 2 (NNPh sub 2 ) sub 2 (C sub 6 Cl sub 4 O sub 2 ) sub 4 ) times CH sub 2 Cl sub 2 times 2CH sub 3 OH, a Tc(V)/Tc(VI) Catecholate complex with the hydrazido ligands adopting the unusual. eta. sup 1 bridging mode

Journal Article · · Inorganic Chemistry; (United States)
DOI:https://doi.org/10.1021/ic00009a016· OSTI ID:5942182
;  [1];  [2]
  1. Johnson Matthey, West Chester, PA (United States)
  2. Syracuse Univ., NY (United States)

Reaction of oxo-bis(tetrachlorocatecholate) Tc(V) complex ((n-C{sub 4}H{sub 9}){sub 4}N)(TcO(C{sub 6}Cl{sub 4}O{sub 2}){sub 2}) (1) with n, N-diphenylhydrazine in Ch{sub 2}Cl{sub 2} yields the binuclear paramagnetic Tc(V)/Tc(VI) mixed-valence complex ((n-C{sub 4}H{sub 9}){sub 4}N)(Tc{sub 2}(NNPh{sub 2}){sub 2}(C{sub 6}Cl{sub 4}O{sub 2}){sub 4}){times}CH{sub 2}Cl{sub 2}{times}2CH{sub 3}OH (2). The structure of the molecular anion of 2 consists of two distorted octahedral Tc centers bridged by two hydrazido (2{minus}) groups bonding s in the {eta}{sup 1} mode, an unusual bonding motif for this ligand, having previously described only for cyclopentadienyl-metal species. Complex 2 is also a unique example of a Tc(V)/Tc(VI) mixed-valence species; the Tc-Tc distance of 2.612 (2) {angstrom} is consistent with direct metal-metal interaction. Crystal data for 1 and 2. 46 refs., 2 figs., 5 tabs.

OSTI ID:
5942182
Journal Information:
Inorganic Chemistry; (United States), Vol. 30:9; ISSN 0020-1669
Country of Publication:
United States
Language:
English

Similar Records

f-Element/crown ether complexes. 10. Oxidation of UCl/sub 4/ to (UO/sub 2/Cl/sub 4/)/sup 2/minus// in the presence of crown ethers: Structural characterization of crown ether complexed ammonium ions ((NH/sub 4/)(15-crown-5)/sub 2/)/sub 2/(UO/sub 2/Cl/sub 4/) /times/2CH/sub 3/CN, ((NH/sub 4/)(benzo-15-crown-5)/sub 2/)/sub 2/(UCl/sub 6/) /times/ 4CH/sub 3/CN, and ((NH/sub 4/)(dibenzo-18-crown-6))/sub 2/(UO/sub 2/Cl/sub 4/) /times/ 2CH/sub 3/CN and synthesis of (Na(12-crown-4)/sub 2/)/sub 2/(UO/sub 2/Cl/sub 4/) /times/ 2OHMe and (UO/sub 2/Cl/sub 2/(OH/sub 2/)/sub 3/) /times/ 18-crown-6 /times/ H/sub 2/O /times/ OHMe
Journal Article · Wed Dec 30 00:00:00 EST 1987 · Inorg. Chem.; (United States) · OSTI ID:5942182

Ionization of TiCl{sub 4} and MgCl{sub 2} during the formation of a high-activity {alpha}-Olefin polymerization catalyst. Crystal structures of [cis-(C{sub 2}H{sub 4}(CO{sub 2}Et){sub 2}){sub 2}Cl{sub 2}Ti][SbCl{sub 6}]{sub 2}{center_dot}CH{sub 2}Cl{sub 2} and [Mg(C{sub 2}H{sub 4}(CO{sub 2}Et){sub 2}){sub 3}][MgCl{sub 4}]{center_dot}2CH{sub 2}Cl{sub 2}
Journal Article · Wed Mar 27 00:00:00 EST 1996 · Inorganic Chemistry · OSTI ID:5942182

Synthesis, spectroscopy, and structural characterization of five-coordinate, bis(aryldiazenido)technetium complexes and their protonation reactions. X-ray structure of (TcCl(PPh sub 3 ) sub 2 (NNC sub 6 H sub 4 Br) sub 2 )
Journal Article · Wed Oct 04 00:00:00 EDT 1989 · Inorganic Chemistry; (USA) · OSTI ID:5942182