Differences in the nature and stability of cadmium complexes with group 15/group 16 donor ligands as determined by multinuclear ( sup 31 P, sup 77 Se, sup 113 Cd) magnetic resonance and electrochemical techniques

Journal Article · Wed Dec 13 04:00:00 EST 1989 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00324a017· OSTI ID:7121436

Bond, A M; Ellis, S R ^[1]; Colton, R; Ebner, J ^[2]

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1. Deakin Univ., Geelong, Victoria (Australia)
2. Univ. of Melbourne, Parkville, Victoria (Australia)

Multinuclear ({sup 31}P, {sup 77}Se, {sup 113}Cd) magnetic resonance and electrochemical studies have been carried out to investigate the nature and stability of cadmium complexes with Ph{sub 2}PCH{sub 2}P(E)Ph{sub 2} (E = S (dpmS), Se (dpmSe)) and Ph{sub 2}P(E)CH{sub 2}P(E)Ph{sub 2} (E = S (dpmS{sub 2}), Se (dpmSe{sub 2})) in dichloromethane solution. The NMR studies indicate a cadmium preference for selenium or sulfur rather than phosphorus coordination in the dpmE complexes but are limited in scope with the NMR technique to examination rather than phosphorus coordination in the dpmE complexes but are limited in scope with the NMR technique to examination of the 1:2 cadmium to ligand stoichiometry due to the labile nature of the systems in the presence of excess ligand. Cadmium-selenium coupling is observed in some cases. The electrochemical reductions of both (Cd(dpmE){sub 2}){sup 2+} and (Cd(dpmE{sub 2}){sub 2}){sup 2+} at a mercury electrode are reversible two-electron processes. Ligand coordination numbers of 4 and 6 are attained with the dpmE complexes, but the dpmE{sub 2} complexes have a maximum ligand coordination number of 4 even at very high ligand to metal concentration ratios. The magnitudes of the calculated stability constants suggest that all of the dpmE and dpmE{sub 2} complexes of cadmium(II) are essentially nondissociated in solution. The use of a Cd(Hg) amalgam electrode allows examination of the voltammetry of these cadmium systems in the presence of substoichiometric ligand concentrations and reemphasizes the high stability of the dpmE and dpmE{sub 2} complexes. The preference of cadmium for the group 16 donor atoms rather than phosphorus in the dpmE complexes is confirmed by an investigation of the interactions of cadmium perchlorate with PPh{sub 3} and PPh{sub 3}Se and by suitable mixing experiments. 25 refs., 4 figs., 5 tabs.

• OSTI ID: 7121436
• Journal Information: Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 28:25; ISSN 0020-1669; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
AROMATICS
BETA DECAY RADIOISOTOPES
BETA-MINUS DECAY RADIOISOTOPES
CADMIUM 113
CADMIUM COMPLEXES
CADMIUM ISOTOPES
CHEMICAL REACTIONS
COMPLEXES
DATA
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
INFORMATION
INTERMEDIATE MASS NUCLEI
ISOMERIC TRANSITION ISOTOPES
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
NMR SPECTRA
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PHOSPHORUS 31
PHOSPHORUS ISOTOPES
RADIOISOTOPES
RESONANCE
SECONDS LIVING RADIOISOTOPES
SELENIUM 77
SELENIUM COMPLEXES
SELENIUM ISOTOPES
SPECTRA
STABLE ISOTOPES
YEARS LIVING RADIOISOTOPES