A series of electronically and coordinatively unsaturated four-coordinate organocobalt(II) complexes, [PhTt tBu ]Co(R) ([PhTt tBu ] ) phenyltris((tert-butylthio)methyl)borate; R ) Me, Et, Ph, Bn) have been prepared by reaction of [PhTt tBu ]CoCl with the corresponding R 2 Mg reagent. These high-spin, S ) 3/2, complexes have been characterized spectroscopically and several of their structures determined by X-ray diffraction. The R ) allyl derivative, [PhTt tBu ]Co(η 3 -allyl), is low spin. Reaction of [PhTt tBu ]Co(R) with CO yielded the acyl adducts [PhTt tBu ]Co(CO)C(O)R when R ) Me, Et, Ph. These five-coordinate, lowspin complexes possess square pyramidal stereochemistry with a thioether occupying the apical position. In contrast, [PhTt tBu ]Co(R), R ) Bn or allyl, reacted with CO generating the brown cobalt(I) dicarbonyl [PhTt tBu ]Co(CO) 2 . The latter reaction is proposed to proceed via CO-promoted Co-C bond homolysis. The Ni complex [κ 2 -PhTt tBu ]Ni(η 3 -allyl) shows no reactivity with CO under similar conditions. Each of the [PhTt tBu ]Co(R) species reacts with NO, generating brown [κ 2 -PhTt tBu ]Co(NO) 2 in good yield.
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