<i>Z</i>-selective dimerization of terminal alkynes by a (PNNP)Fe<sup>II</sup> complex

Stevens, Jeremiah E.; Miller, Justin D.; Fitzsimmons, Matthew C.; Moore, Curtis E.; Thomas, Christine M.

doi:10.1039/d4cc00469h

Chem. Commun.

2024

DOI: 10.1039/d4cc00469h

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Z-selective dimerization of terminal alkynes by a (PNNP)Fe^II complex

Jeremiah E. Stevens,

Justin D. Miller,

Matthew C. Fitzsimmons

et al.

Abstract: A (PNNP)FeII complex is shown to catalyze the dimerization of terminal alkynes via a metal–ligand cooperative mechanism.

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2024

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Influence of η¹‐Acetylide Ligands on the Spin State and Catalytic Activity of Iron(II) PNP Pincer Complexes

Eder,

Stöger,

Kirchner

et al. 2024

Eur J Inorg Chem

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Here, we report the preparation, structures and reactivity of iron(II) PNP pincer complexes bearing one, two or three η1‐acetylide ligands bound to the metal center. The described complexes are accessible through the reaction of either one, two or ≥ 3 equivalent of LiCCR (R = SiMe3, Ph) with the dibromide complex [Fe(PNP)Br2] (1). Through increasing the number of η1‐acetylides the overall ligand field strength can be modulated resulting in S = 2, S = 1 and S = 0 spin states for mono‐, bis‐ and tris‐acetylated complexes, respectively. These findings are supported by DFT calculations on the spin state spitting in these complexes and appear to affect their binding affinity towards additional co‐ligands. The Fe(II) mono‐, bis‐ and tris‐acetylides were tested as catalyst in the catalytic dimerization of terminal alkynes. These test reactions revealed that only the bis‐acetylated complexes are catalytically competent while mono‐acetylated species are inactive. The tris‐acetylated complexes were found to be off‐cycle intermediates in the presence of lithium acetylides.

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Influence of η¹‐Acetylide Ligands on the Spin State and Catalytic Activity of Iron(II) PNP Pincer Complexes

Eder,

Stöger,

Kirchner

et al. 2024

Eur J Inorg Chem

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Tuning the Pyridone Scaffold within a Rhodium-NHC Platform for gem-Specific Alkyne Dimerization via a Ligand-Assisted Proton Shuttle Mechanism

Español-Sánchez,

Galiana-Cameo,

Urriolabeitia

et al. 2024

Organometallics

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A series of mononuclear square-planar Rh{κ 2 N,O-BHetA}(η 2coe)(NHC) (BHetA = Bis-Heteroatomic Acidato) complexes have been prepared. Modifications of the pyridonato BHetA-type ligand architecture include 4-Me, 5-Me, 6-Me, 3-Br, 4-Br, 4-OMe, and 5-NO 2 substitutions as well as pyrimidonato, succinimidato, and 2-piperidonato catalysts. Two structural isomers have been observed for the complexes, depending on the stereoelectronic properties of the ligand. The structure−activity relationship has been studied for gem-specific alkyne dimerization via a cooperative ligandassisted proton shuttle mechanism. Density functional theory calculations have revealed a mechanistic pathway involving the hemilabile coordination of the BHetA ligand, CMD deprotonation, π-alkyne protonation, and reductive elimination. The increase in oxygen basicity imparted by the substituent in the pyridonato ligand is key, the 4-methyl derivative being the most active catalyst. However, a favored iminol−amide tautomerization precludes an increase in catalytic activity for the more basic saturated piperidonato catalyst.

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Z-selective dimerization of terminal alkynes by a (PNNP)Fe^II complex

Abstract: A (PNNP)FeII complex is shown to catalyze the dimerization of terminal alkynes via a metal–ligand cooperative mechanism.

Cited by 2 publications

References 27 publications

Influence of η¹‐Acetylide Ligands on the Spin State and Catalytic Activity of Iron(II) PNP Pincer Complexes

Influence of η¹‐Acetylide Ligands on the Spin State and Catalytic Activity of Iron(II) PNP Pincer Complexes

Tuning the Pyridone Scaffold within a Rhodium-NHC Platform for gem-Specific Alkyne Dimerization via a Ligand-Assisted Proton Shuttle Mechanism

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Z-selective dimerization of terminal alkynes by a (PNNP)FeII complex

Abstract: A (PNNP)FeII complex is shown to catalyze the dimerization of terminal alkynes via a metal–ligand cooperative mechanism.

Cited by 2 publications

References 27 publications

Influence of η1‐Acetylide Ligands on the Spin State and Catalytic Activity of Iron(II) PNP Pincer Complexes

Influence of η1‐Acetylide Ligands on the Spin State and Catalytic Activity of Iron(II) PNP Pincer Complexes

Tuning the Pyridone Scaffold within a Rhodium-NHC Platform for gem-Specific Alkyne Dimerization via a Ligand-Assisted Proton Shuttle Mechanism

Contact Info

Product

Resources

About

Z-selective dimerization of terminal alkynes by a (PNNP)Fe^II complex

Influence of η¹‐Acetylide Ligands on the Spin State and Catalytic Activity of Iron(II) PNP Pincer Complexes

Influence of η¹‐Acetylide Ligands on the Spin State and Catalytic Activity of Iron(II) PNP Pincer Complexes