Reactivity of Tetrahalo- and Difluorodiboranes(4) toward Lewis Basic Platinum(0): Bis(boryl), Borylborato, and Doubly Boryl-Bridged Platinum Complexes

Jonas H Muessig; Dominic Prieschl; Andrea Deißenberger; Rian D Dewhurst; Maximilian Dietz; J Oscar C Jiménez-Halla; Alexandra Trumpp; Sunewang R Wang; Carina Brunecker; Alena Haefner; Annalena Gärtner; Torsten Thiess; Julian Böhnke; Krzysztof Radacki; Rüdiger Bertermann; Todd B Marder; Holger Braunschweig

doi:10.1021/jacs.8b08428

Reactivity of Tetrahalo- and Difluorodiboranes(4) toward Lewis Basic Platinum(0): Bis(boryl), Borylborato, and Doubly Boryl-Bridged Platinum Complexes

J Am Chem Soc. 2018 Oct 10;140(40):13056-13063. doi: 10.1021/jacs.8b08428. Epub 2018 Oct 2.

Authors

Jonas H Muessig^{1

2}, Dominic Prieschl^{1

2}, Andrea Deißenberger^{1

2}, Rian D Dewhurst^{1

2}, Maximilian Dietz^{1

2}, J Oscar C Jiménez-Halla³, Alexandra Trumpp^{1

2}, Sunewang R Wang^{1

2}, Carina Brunecker^{1

2}, Alena Haefner^{1

2}, Annalena Gärtner^{1

2}, Torsten Thiess^{1

2}, Julian Böhnke^{1

2}, Krzysztof Radacki^{1

2}, Rüdiger Bertermann^{1

2}, Todd B Marder^{1

2}, 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 , Am Hubland , 97074 Würzburg , Germany.
³ Departamento de Química, División de Ciencias Naturales y Exactas , Universidad de Guanajuato , Noria Alta S/N, Col. Noria Alta , 36050 Guanajuato , GTO , Mexico.

PMID: 30222320
DOI: 10.1021/jacs.8b08428

Abstract

The reaction of the tetrahalodiboranes(4) B₂F₄, B₂Cl₄, and B₂Br₄ with a Lewis basic platinum(0) complex led to the isolation of the cis-bis(difluoroboryl) complex cis-[(Cy₃P)₂Pt(BF₂)₂] (1) and the novel borylborato complexes trans-[(Cy₃P)₂Pt{B(X)-BX₃}] (2, X = Cl; 3, X = Br), respectively. The trans influence of the borylborato group was found to be one of the strongest ever observed experimentally. Furthermore, the reactivity of little-explored diaryldifluorodiboranes(4) F₂B-BMes₂ and the new derivative F₂B-BAn₂ (An = 9-anthryl) toward a range of platinum(0) complexes was investigated. Reactions with relatively nonbulky platinum(0) complexes led to the formation of unsymmetrical cis-bis(boryl) complexes cis-[(R₃P)₂Pt(BF₂)(BMes₂)] (6, R = Me; 7, R = Et) as well as the first example of a fourfold-unsymmetrical bis(boryl) complex, [(Me₃P)(Cy₃P)Pt(BF₂)(BMes₂)] (12). The use of a more bulky Pt complex provided access to the unprecedented dinuclear bis(boryl) complexes [{( iPr₃P)Pt}₂(μ-BF₂)(μ-BAr₂)] (8, Ar = Mes; 9, Ar = An), which feature two different μ₂-bridging boryl ligands.