Synthesis, Characterization, and Reactivity of Thioether-Ligated Organoiron(II) Complexes

IF 2.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2024-08-06 DOI:10.1021/acs.organomet.4c00197

Roark D. O’Neill, William G. Dougherty, Glenn P. A. Yap, Navamoney Arulsamy, Charles G. Riordan, Michael T. Mock

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Abstract

In this work we report a series of four-coordinate organoiron(II) complexes in a sulfur-rich ligand environment. The high-spin, S = 2, compounds [PhTt^tBu]Fe(R) (R = Et, Ph, Mes, Bn, CH₂SiMe₃) (Mes = 2,4,6-Me₃C₆H₂; Bn = CH₂C₆H₅) [PhTt^tBu]⁻ = (phenyltris((tert-butylthio)methyl)borate) bearing an anionic tripodal thioether ligand were synthesized and characterized by NMR spectroscopy and structurally characterized by single-crystal X-ray crystallography. Exposure of [PhTt^tBu]Fe(R) (R = Me, Et, Ph, CH₂SiMe₃) to 1 atm of CO afforded diamagnetic, six-coordinate complexes [PhTt^tBu]Fe(CO)₂(R). The carbonylation of [PhTt^tBu]Fe(R) (R = Bn, Mes) formed two Fe products: [PhTt^tBu]Fe(CO)₂(R), and a five-coordinate, low-spin, S = 1/2, [PhTt^tBu]Fe(CO)₂, the latter due to homolytic Fe–C bond cleavage.

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硫醚配位有机铁（II）配合物的合成、表征和反应活性

在这项工作中，我们报告了一系列富硫配体环境中的四配位有机铁（II）配合物。高自旋、S = 2 的化合物 [PhTttBu]Fe(R) （R = Et、Ph、Mes、Bn、CH2SiMe3）（Mes = 2,4,6-Me3C6H2；Bn = CH2C6H5）[PhTttBu]- = (苯基三((叔丁基硫代)甲基)硼酸酯)，带有阴离子三足硫醚配体。将[PhTttBu]Fe(R)（R = Me、Et、Ph、CH2SiMe3）暴露于 1 atm 的 CO 中，可得到二磁性六配位络合物 [PhTttBu]Fe(CO)2(R)。[PhTttBu]Fe(R)（R = Bn，Mes）的羰基化反应产生了两种铁产物：[PhTttBu]Fe(CO)2(R)和五配位、低自旋、S = 1/2的[PhTttBu]Fe(CO)2。

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来源期刊

Organometallics 化学-无机化学与核化学

CiteScore

5.60

自引率

7.10%

发文量

382

审稿时长

1.7 months

期刊介绍： Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.