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Facile Axial Ligand Substitution in Linear Mo≣Mo-Ni Complexes.
Jill A Chipman1, John F Berry1
1Department of Chemistry , University of Wisconsin, Madison , 1101 University Avenue , Madison , Wisconsin 53706 , United States.
Inorganic Chemistry
|July 20, 2018
Summary
Synthesizing robust heterotrimetallic chains with second-row transition metals like molybdenum and nickel enables clean axial ligand substitution. These new compounds exhibit stable metal-metal bonding and high-spin nickel centers.
Area of Science:
- Inorganic Chemistry
- Materials Science
- Coordination Chemistry
Background:
- Heterometallic extended metal atom chains (HEMACs) are challenging to synthesize due to side reactions affecting the metal core.
- Ligand substitution reactions on HEMACs often lead to undesirable alterations of the trimetallic core.
Purpose of the Study:
- To synthesize novel heterotrimetallic compounds incorporating second-row transition metals for enhanced stability.
- To investigate the feasibility of clean axial ligand substitution reactions on these robust HEMACs.
- To characterize the structural, electronic, and magnetic properties of the synthesized compounds.
Main Methods:
- Direct and indirect synthesis of heterotrimetallic compounds: Mo2Ni(dpa)4(OTf)2, Mo2Ni(dpa)4(NCS)2, and Mo2Ni(dpa)4(NCSe)2.
- Axial ligand substitution reactions using NaNCS and KNCSe.
- X-ray crystallography for structural determination.
- Density Functional Theory (DFT) calculations for electronic structure analysis.
- SQUID magnetometry for magnetic property assessment.
Main Results:
- Successful synthesis of three new heterotrimetallic compounds, Mo2Ni(dpa)4(OTf)2, Mo2Ni(dpa)4(NCS)2, and Mo2Ni(dpa)4(NCSe)2, in good yields.
- Clean axial ligand substitution reactions were achieved, demonstrating the robustness of the second-row transition metal core.
- X-ray structures revealed short Mo-Ni distances, indicative of strong metal-metal interactions.
- DFT calculations confirmed a 3-center 3-electron sigma bonding interaction between the Mo2 core and Ni.
- SQUID magnetometry supported the presence of a high-spin Ni2+ center (S=1).
Conclusions:
- Heterometallic cores containing second-row transition metals offer enhanced stability for ligand substitution reactions.
- The synthesized Mo2Ni(dpa)4X2 complexes are robust and allow for clean axial ligand exchange.
- The structural and electronic properties, including metal-metal bonding and magnetic behavior, are well-defined.
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