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Synthesis and Structures of Intramolecularly Base-Coordinated Group 15 Aryl Halides
Claire J. Carmalt1, Alan H. Cowley, Robert D. Culp
1Department of Chemistry & Biochemistry, The University of Texas at Austin, Austin, Texas 78712, and School of Chemistry, Cantock's Close, University of Bristol, Bristol BS8 1TS, U.K.
Inorganic Chemistry
|June 18, 1997
Summary
New group 15 monochlorides and dihalides featuring bulky aryl ligands were synthesized. X-ray crystal structures reveal trends in intramolecular coordination, linking Lewis acidity to E-X sigma orbitals in these antimony and bismuth compounds.
Area of Science:
- Organometallic Chemistry
- Inorganic Chemistry
- Materials Science
Background:
- Group 15 elements (e.g., antimony, bismuth) form compounds with diverse structures and properties.
- Aryl ligands with coordinating groups can influence the reactivity and structure of metal complexes.
- Understanding the electronic properties and coordination behavior of these compounds is crucial for developing new materials and catalysts.
Purpose of the Study:
- To synthesize and characterize novel group 15 monochlorides and dihalides with bulky aryl ligands.
- To investigate the structural features and intramolecular coordination in these compounds using X-ray crystallography.
- To correlate the observed structural trends with the Lewis acidity of the complexes.
Main Methods:
- Synthesis of group 15 monochlorides and dihalides via salt elimination reactions using organolithium reagents and metal halides.
- Purification and characterization of the synthesized compounds.
- X-ray crystal structure determination for key compounds to elucidate their solid-state structures and coordination modes.
Main Results:
- Four group 15 monochlorides (EAr(2)Cl) and four group 15 dihalides (EArX(2)) were successfully prepared, where E = Sb, Bi and Ar represents specific bulky aryl ligands.
- X-ray crystal structures were determined for compounds 4-6, 8, 9, and 11, revealing distinct coordination environments.
- Observed trends in intramolecular nitrogen coordination correlate with the Lewis acidity, which is associated with the E-X sigma orbitals.
Conclusions:
- The study successfully synthesized and structurally characterized novel group 15 organometallic compounds.
- Intramolecular coordination plays a significant role in the electronic properties and Lewis acidity of these complexes.
- The findings provide insights into the structure-property relationships of group 15 halides with bulky ligands.