Cadmium polysulfide complexes, (Cd(S sub x )(S sub y )) sup 2 minus : Syntheses, crystal and molecular structures, and sup 113 Cd NMR studies

Journal Article · Wed May 17 04:00:00 EDT 1989 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00309a020· OSTI ID:7071706

Banda, R M.H.; Dance, I G; Bailey, T D; Craig, D C; Scudder, M L ^[1]

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1. Univ. of New South Wales, Kensington (Australia)

Controlled methods for the formation of cadmium polysulfide complexes in nonaqueous solution, mainly dimethylformamide (DMF), have been developed. The preferred method is CdS + Na{sub 2}S + S{sub 8} in DMF, which allows a wide range for the solution compositional variables Cd{sup 2+} + n(S{sub m}){sup 2{minus}} to be attained. {sup 113}Cd NMR spectroscopy reveals the existence of the series of monocadmium complexes (Cd(S{sub x}){sub 2}){sup 2{minus}}, which are in NMR slow exchange (<10{sup 2} s{sup {minus}1}) at ambient temperature. The principal Cd NMR resonances are assigned to (Cd(S{sub 5}){sub 2}){sup 2{minus}} (740 ppm), (Cd(S{sub 5})(S{sub 6})){sup 2{minus}} (695 ppm), and (Cd(S{sub 6}){sub 2}){sup 2{minus}} (648 ppm), with (Cd(S{sub 6})(S{sub 7})){sup 2{minus}} (616 ppm) also postulated. Crystal structures of (Ph{sub 4}P){sub 2}(Cd(S{sub 6}){sub 2}) (6) and (Ph{sub 4}P){sub 2}((S{sub 6}){sub 0.56}(S{sub 7}){sub 0.44}Cd(S{sub 6})) (7), isolated from these solutions, reveal the variability of cadmapolysulfane ring sizes and conformations in crystals. Modifications of the cadmapolysulfane ring sizes, which occur on redissolution of 6 and on development of sulfur addition and abstraction reagents, were clearly evident in the Cd NMR spectra. Crystal data: 6, space group P{bar 1}, a = 11.849 (6) {angstrom}, b = 11.990 (6) {angstrom}, c = 19.856 (10) {angstrom}, {alpha} = 92.05 (3){degree}, {beta} = 92.88 (3){degree}, {gamma} = 111.88 (2){degree}, V = 2610 (2) {angstrom}{sup 3}, 3561 observed reflections (Mo K{alpha}, I > 3{sigma}(I)), R = 0.055; 7, space group P{bar 1}, a = 11.913 (5) {angstrom}, b = 12.010 (5) {angstrom}, c = 19.785 (8) {angstrom}, {alpha} = 92.01 (3){degree}, {beta} = 93.05 (3){degree}, {gamma} = 111.65 (2){degree}, V = 2623 (2) {angstrom}{sup 3}, 5211 observed reflections (Mo K{alpha}, I > 3{sigma}(I)), R = 0.054. 43 refs., 7 figs., 9 tabs.

• OSTI ID: 7071706
• Journal Information: Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 28:10; ISSN 0020-1669; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical &amp; Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
&amp; Isotope Separation
BETA DECAY RADIOISOTOPES
BETA-MINUS DECAY RADIOISOTOPES
CADMIUM 113
CADMIUM COMPOUNDS
CADMIUM ISOTOPES
CADMIUM SULFIDES
CHALCOGENIDES
CRYSTAL STRUCTURE
DATA
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
INFORMATION
INORGANIC PHOSPHORS
INTERMEDIATE MASS NUCLEI
ISOMERIC TRANSITION ISOTOPES
ISOTOPES
MAGNETIC RESONANCE
MOLECULAR STRUCTURE
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
PHOSPHORS
RADIOISOTOPES
RESONANCE
STABLE ISOTOPES
SULFIDES
SULFUR COMPOUNDS
SYNTHESIS
YEARS LIVING RADIOISOTOPES