Dinickela-bicyclo[4,4,0]-decadiene Complex with a Linear Heterometallic Mg-Ni-Ni-Mg Chain

Area of Science:

• Organometallic Chemistry
• Coordination Chemistry
• Inorganic Chemistry

Background:

• Transition metal-diene complexes are fundamental organometallic compounds.
• Conjugated dienes typically act as neutral π-donor ligands.
• Doubly reduced enediyl derivatives are known, but dinuclear complexes were unexplored.

Purpose of the Study:

• To synthesize and characterize novel dinuclear transition metal complexes with doubly reduced diene ligands.
• To investigate the bonding modes and structural features of these complexes.
• To explore the reactivity of these complexes with additional dienes and carbon monoxide.

Main Methods:

• Synthesis of a heterometallic complex [(LMg)2Ni2(C4H6)2] via reaction of LMgBu·Et2O with Ni(cod)2.
• Experimental characterization including X-ray crystallography.
• Computational studies (DFT) to elucidate bonding.
• Reactivity studies with butadiene and carbon monoxide.

Main Results:

• A heterometallic complex with a linear Mg-Ni-Ni-Mg chain was synthesized.
• Two s-trans-butadiene ligands were found bridging the Ni-Ni bond in a doubly reduced enediyl configuration.
• The complex exhibits a dinickela-bicyclo[4,4,0]-decadiene framework.
• Reactions with butadiene and CO led to complexes with altered ligand arrangements.

Conclusions:

• This work reports the first dinuclear transition metal complexes featuring doubly reduced enediyl ligands.
• The unique bonding arrangement offers new insights into metal-diene interactions.
• The reactivity studies highlight the versatility of these novel organometallic frameworks.