To explore metal–metal multiple bonds between first row transition metals, Ti/Co complexes supported by two phosphinoamide ligands have been synthesized and characterized. The Ti metalloligand Cl₂Ti(XylNPⁱPr₂)₂ (1) was treated with CoI₂ under reducing conditions, permitting isolation of the Ti/Co complex [(μ-Cl)Ti(XylNPⁱPr₂)₂CoI]₂ (2). One electron reduction of complex 2 affords ClTi(XylNPⁱPr₂)₂CoPMe₃ (3), which features a metal–metal triple bond and an unprecedentedly short Ti–Co distance of 2.0236(9) Å. This complex is shown to promote the McMurry coupling reaction of aryl ketones into alkenes, with concomitant formation of the tetranuclear complex [Ti(μ₃-O)(NXylPⁱPr₂)₂CoI]₂ (4). A cooperative mechanism involving bimetallic CO bond activation and a cobalt carbene intermediate is proposed.