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A Series of Cyanide-Bridged Binuclear Complexes
Michael T Mock1, Matthew T Kieber-Emmons, Codrina V Popescu
1Department of Chemistry and Biochemistry University of Delaware, Newark, Delaware 19716.
Inorganica Chimica Acta
|February 18, 2010
Summary
This study details the synthesis and characterization of novel cyanide-bridged binuclear complexes containing nickel and various metals. The research confirms the greater stability of the cyanide-bridged isomer over its linkage isomer through experimental and computational methods.
Area of Science:
- Coordination Chemistry
- Inorganic Synthesis
- Supramolecular Chemistry
Background:
- Cyanide ligands are versatile bridges in constructing polynuclear metal complexes.
- Understanding the structural and energetic preferences of linkage isomers is crucial for designing advanced materials.
Purpose of the Study:
- To synthesize and characterize a series of cyanide-bridged binuclear nickel-metal complexes.
- To investigate the isomerization and relative stability of cyanide-bridged complexes and their linkage isomers.
Main Methods:
- Coupling reactions involving potassium cyanide complexes and metal precursors.
- Structural characterization using X-ray diffraction.
- Spectroscopic analysis including C-13 NMR and IR spectroscopy.
- Density Functional Theory (DFT) calculations.
Main Results:
- A series of isostructural cyanide-bridged binuclear complexes ('S(3)')Ni-CN-M[Tp(tBu)] (M = Fe, Co, Ni, Zn) were successfully synthesized.
- An anionic copper(I) analogue was also prepared.
- Experimental and DFT studies confirmed the isomerization to the more stable Ni-CN-Zn isomer, which is approximately 5 kcal/mol more stable.
Conclusions:
- The synthetic strategy provides access to diverse cyanide-bridged binuclear complexes.
- The Ni-CN-Zn linkage isomer is thermodynamically favored over other linkage isomers.
- This work contributes to the understanding of isomerism and stability in cyanide-bridged coordination compounds.
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