Structurally distinctive dinuclear Ni(II) complexes with furan or thiophene tethered amine-pyrazolyl tripodal hybrid ligands have been synthesized and crystallographically characterized. All complexes are catalytically active towards cross-coupling of aryl/alkyl Grignard reagents with β-H containing alkyl halides at room temperature in the presence of N,N,N′,N′-tetramethylethylenediamine (TMEDA). The catalytic efficacy of the complexes is dependent on the tether substituent at the central amine. Two species, Ni(II) TMEDA and Mg(II) TMEDA complexes, have been isolated from the catalytic reaction mixtures under different conditions. Some ligand-stabilized Ni(II) and Mg(II) bimetallic species have also been identified in the ESI-MS spectra.