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Dicoordinate copper(I) silanechalcogenolates.

Iliana Medina¹, Heiko Jacobsen, Joel T Mague

¹Department of Chemistry, Tulane University, New Orleans, Louisiana 70118, USA.

Inorganic Chemistry

|October 24, 2006

Summary

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New copper silanechalcogenolates featuring oxygen, sulfur, and selenium were synthesized. The copper-oxygen compound exhibits a unique linear geometry, explained by electrostatic interactions and Pauli repulsion, not pi delocalization.

Area of Science:

Organometallic Chemistry
Inorganic Chemistry
Materials Science

Background:

Copper complexes with chalcogenolates are of interest due to their diverse reactivity and structural motifs.
Silanechalcogenolates offer unique steric and electronic properties for stabilizing metal centers.

Purpose of the Study:

To synthesize and characterize novel copper silanechalcogenolates with oxygen, sulfur, and selenium.
To investigate the structural and electronic properties of these complexes, particularly the coordination geometry around the copper atom.

Main Methods:

Synthesis of copper silanechalcogenolates via reaction of a copper precursor with lithiated silanechalcogenolates in acetonitrile.
Characterization using X-ray crystallography to determine solid-state structures.

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Computational analysis using Density Functional Theory (DFT) to understand bonding and geometry.

Main Results:

Three copper silanechalcogenolates, tBu3PCuESiPh3 (E = O, S, Se), were successfully prepared as crystalline, thermally labile solids.
X-ray crystallography revealed monomeric structures with no copper-copper interactions and linear or near-linear copper coordination.
Complex 1 (E=O) displayed a unique linear oxygen atom and an exceptionally short Cu-O bond, contrasting with bent S and Se analogues.

Conclusions:

The linear geometry and short Cu-O bond in complex 1 are attributed to a balance of electrostatic interactions and Pauli repulsion, rather than pi delocalization.
The study highlights the tunable nature of copper silanechalcogenolates and provides insights into bonding principles in low-coordinate metal complexes.