Stable Two-Legged Parent Piano-Stool and Mixed Diborabenzene-E4 (E=P, As) Sandwich Complexes of Group 8

Maximilian Dietz; Merle Arrowsmith; Stephan Reichl; Leonardo I Lugo-Fuentes; J Oscar C Jiménez-Halla; Manfred Scheer; Holger Braunschweig

doi:10.1002/anie.202206840

Stable Two-Legged Parent Piano-Stool and Mixed Diborabenzene-E₄ (E=P, As) Sandwich Complexes of Group 8

Angew Chem Int Ed Engl. 2022 Sep 5;61(36):e202206840. doi: 10.1002/anie.202206840. Epub 2022 Jul 27.

Authors

Maximilian Dietz^{1

2}, Merle Arrowsmith^{1

2}, Stephan Reichl³, Leonardo I Lugo-Fuentes⁴, J Oscar C Jiménez-Halla⁴, Manfred Scheer³, Holger Braunschweig^{1

2}

Affiliations

¹ Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
² Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
³ Institute of Inorganic Chemistry, University of Regensburg, Universitätsstraße 31, 93040, Regensburg, Germany.
⁴ Departamento de Química, División de Ciencias Naturales y Exactas, Unversidad de Guanajuato, Noria Alta S/N, Col. Noria Alta, Guanajuato, C.P. 36050, Gto., Mexico.

Abstract

A cyclic alkyl(amino)carbene-stabilized 1,4-diborabenzene (DBB) ligand enables the isolation of 18-electron two-legged parent piano-stool Fe⁰ and Ru⁰ complexes, [(η⁶ -DBB)M(CO)₂ ], the ruthenium complex being the first of its kind to be structurally characterized. [(η⁶ -DBB)Fe(CO)₂ ] reacts with E₄ (E=P, As) to yield mixed DBB-cyclo-E₄ sandwich complexes with planar E₄ ^2- ligands. Computational analyses confirm the strong electron-donating capacity of the DBB ligand and show that the E₄ ligand is bound by four equivalent Fe-P σ bonds.

Keywords: 1,4-Diborabenzene; Bonding; Group 8 Metals; Parent Piano-Stool Complex; Pnictogen Reduction.

Abstract

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