<p>The addition of CO to (Triphos)FeBr<sub>2</sub> (Triphos = PhP(CH<sub>2</sub>CH<sub>2</sub>PPh<sub>2</sub>)<sub>2</sub>) resulted in formation of six-coordinate (Triphos)FeBr<sub>2</sub>(CO). This coordination compound was found to have <i>cis</i>-bromide ligands and a <i>mer</i>-Triphos ligand by single crystal X-ray diffraction. Once characterized, the reactivity of this compound toward NaEt<sub>3</sub>BH and NaBH<sub>4</sub> was investigated. Adding 1 eq. of NaEt<sub>3</sub>BH to (Triphos)FeBr<sub>2</sub>(CO) resulted in formation of (Triphos)FeH(Br)(CO), while the addition of 2.2 eq. afforded previously described (Triphos)Fe(CO)<sub>2</sub>. In contrast, adding 2.2 eq. of NaBH<sub>4</sub> to (Triphos)FeBr<sub>2</sub>(CO) resulted in carbonyl dissociation and formation of diamagnetic (Triphos)FeH(<i>η</i><sup>2</sup>-BH<sub>4</sub>), which has been structurally characterized. Notably, efforts to prepare (Triphos)FeH(<i>η</i><sup>2</sup>-BH<sub>4</sub>) following 2.2 eq. NaBH<sub>4</sub> addition to (Triphos)FeBr<sub>2</sub> were unsuccessful. The importance of these observations as they relate to previously reported (Triphos)Fe reactivity and recent developments in Fe catalysis are discussed.</p
