sup 77 Se NMR spectroscopic and x-ray crystallographic characterization of bis(cyclopentadienyl)titanium selenide sulfide mixtures, (Ti(C sub 5 H sub 5 ) sub 2 Se sub x S sub 5 minus x )

Journal Article · Wed Apr 17 00:00:00 EDT 1991 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00008a036· OSTI ID:5564053

Pekonen, P; Hiltunen, Y; Laitinen, R S ^[1]; Valkonen, J ^[2]

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1. Univ. of Oulu, Linnanmaa (Finland)
2. Univ. of Jyvaeskylae (Finland)

Mixed crystals of bis(cyclopentadienyl)titanium selenide sulfides, (Ti(C{sub 5}H{sub 5}){sub 2}Se{sub x}S{sub 5-x}), have been prepared by reacting (Ti(c{sub 5}H{sub 5}){sub 2}Cl{sub 2}) with a series of lithium polyselenide and polysulfide mixtures at different molar ratios. The reaction products were studied with {sup 77}Se NMR spectroscopy and x-ray crystallography. When the initial lithium polyselenide/polysulfide mixture was either sulfur-rich or selenium-rich, mainly (Ti(C{sub 5}H{sub 5}){sub 2}S{sub 5}) or (Ti(c{sub 5}H{sub 5}){sub 2}se{sub 5}) were formed, respectively. However, when the initial molar ratio of selenium and sulfur was near unity, several different (Ti(c{sub 5}H{sub 5}){sub 2}Se{sub x}Se{sub 5-x})species were formed. The product from the reaction with initial molar ratio of selenium and sulfur of 3:2 was subjected to a more detailed study. Both the crystal and molecule structures of the complex were determined and are reported. According to the {sup 77}Se NMR spectra the main selenium-containing components in the product are (Ti(C{sub 5}H{sub 5}){sub 2}Se{sub 5}), (Ti(C{sub 5}H{sub 5}){sub 2}Se{sub 4}S), (Ti(C{sub 5}H{sub 5}){sub 2}Se{sub 3}S{sub 2}), (Ti(C{sub 5}H{sub 5}){sub 2}Se{sub 3}S), and (Ti(C{sub 5}H{sub 5}){sub 2}Se{sub 2}S{sub 3}). The product also contains (Ti(C{sub 5}H{sub 5}){sub 2}S{sub 5}). The refined occupation factors sulfur and selenium from the crystal structure determination agree well with the relative abundance of the different molecular species as calculated from the NMR spectrum. 26 refs., 4 figs., 5 tabs.

• OSTI ID: 5564053
• Journal Information: Inorganic Chemistry; (United States), Vol. 30:8; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CYCLOPENTADIENE
CRYSTAL STRUCTURE
SELENIUM COMPOUNDS
SULFUR COMPOUNDS
TITANIUM COMPLEXES
EXPERIMENTAL DATA
MOLECULAR STRUCTURE
NMR SPECTRA
SELENIUM 77
ALKENES
COMPLEXES
CYCLOALKENES
DATA
DIENES
EVEN-ODD NUCLEI
HYDROCARBONS
INFORMATION
INTERMEDIATE MASS NUCLEI
ISOMERIC TRANSITION ISOTOPES
ISOTOPES
NUCLEI
NUMERICAL DATA
ORGANIC COMPOUNDS
POLYENES
RADIOISOTOPES
SECONDS LIVING RADIOISOTOPES
SELENIUM ISOTOPES
SPECTRA
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400202 - Isotope Effects
Isotope Exchange
& Isotope Separation