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Synthesis and Reactivity of Iron Complexes with a Biomimetic SCS Pincer Ligand.

ABSTRACT: Recent experimental evidence suggests that the FeMoco of nitrogenase undergoes structural rearrangement during N₂ reduction, which may result in the generation of coordinatively unsaturated iron sites with two sulfur donors and a carbon donor. In an effort to synthesize and study small-molecule model complexes with a one-carbon/two-sulfur coordination environment, we have designed two new SCS pincer ligands containing a central NHC donor accompanied by thioether- or thiolate-functionalized aryl groups. Metalation of the thioether ligand with Fe(OTf)₂ gives 6-coordinate complexes in which the SCS ligand binds meridionally. In contrast, metalation of the thiolate ligand with Fe(HMDS)₂ gives a four-coordinate pseudotetrahedral amide complex in which the ligand binds facially, illustrating the potential structural flexibility of these ligands. Reaction of the amide complex with a bulky monothiol gives a four-coordinate complex with a one-carbon/three-sulfur coordination environment that resembles the resting state of nitrogenase. Reaction of the amide complex with phenylhydrazine gives a product with a rare κ¹-bound phenylhydrazido group which undergoes N-N cleavage to give a phenylamido complex.

SUBMITTER: Speelman AL

PROVIDER: S-EPMC8207233 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The 15e square-planar complexes [Co(PCPMe-iPr)Cl] (2a) and [Co(PCP-tBu)Cl] (2b), respectively, react readily with NaBH4 to afford complexes [Co(PCPMe-iPr)(η2-BH4)] (4a) and [Co(PCP-tBu)(η2-BH4)] (4b) in high yields, as confirmed by IR spectroscopy, X-ray crystallography, and elemental analysis. The borohydride ligand is symmetrically bound to the cobalt center in η2-fashion. These compounds are paramagnetic with effective magnetic moments of 2.0(1) and 2.1(1) μB consistent with a d7 low-spin system corresponding to one unpaired electron. None of these complexes reacted with CO2 to give formate complexes. For structural and reactivity comparisons, we prepared the analogous Ni(II) borohydride complex [Ni(PCPMe-iPr)(η2-BH4)] (5) via two different synthetic routes. One utilizes [Ni(PCPMe-iPr)Cl] (3) and NaBH4, the second one makes use of the hydride complex [Ni(PCPMe-iPr)H] (6) and BH3·THF. In both cases, 5 is obtained in high yields. In contrast to 4a and 4b, the borohydride ligand is asymmetrically bound to the nickel center but still in an η2-mode. [Ni(PCPMe-iPr)(η2-BH4)] (5) loses readily BH3 at elevated temperatures in the presence of NEt3 to form 6. Complexes 5 and 6 are both diamagnetic and were characterized by a combination of 1H, 13C{1H}, and 31P{1H} NMR, IR spectroscopy, and elemental analysis. Additionally, the structure of these compounds was established by X-ray crystallography. Complexes 5 and 6 react with CO2 to give the formate complex [Ni(PCPMe-iPr)(OC(C=O)H] (7). The extrusion of BH3 from [Co(PCPMe-iPr)(η2-BH4)] (4a) and [Ni(PCPMe-iPr)(η2-BH4)] (5) with the aid of NH3 to yield the respective hydride complexes [Co(PCPMe-iPr)H] and [Ni(PCPMe-iPr)H] (6) and BH3NH3 was investigated by DFT calculations showing that formation of the Ni hydride is thermodynamically favorable, whereas the formation of the Co(II) hydride, in agreement with the experiment, is unfavorable. The electronic structures and the bonding of the borohydride ligand in [Co(PCPMe-iPr)(η2-BH4)] (4a) and [Ni(PCPMe-iPr)(η2-BH4)] (5) were established by DFT computations.

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Synthesis and Reactivity of Iron Complexes with a Biomimetic SCS Pincer Ligand.

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