σ-Complexes of transition metals-key intermediates in metal-mediated bond activation and homogeneous catalysis-have traditionally been isolable only when chelating or when one of the participating atoms is hydrogen. Here, by treating the Lewis-basic transition metal complex [Pt(PEt(3))(4)] with an electron-poor borirene, we isolate a complex with an unsupported borirene ligand bound, not through the unsaturated C=C bond, but exclusively via a B-C single bond. Using NMR spectroscopy, X-ray crystallography and density functional theory calculations, we show, herein, that coordination of the borirene ligand is based on electron donation from the B-C σ bond to the metal, aided by a strong Pt-to-B dative interaction. The complex is the first isolable non-agostic σ-complex featuring two p-block elements and has broad implications as a model for the metal-mediated activation of strong p-block-p-block σ-bonds.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1038/ncomms1884 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Borirenes and Boriranes: Development and Perspectives.
Chemistry
February 2024
Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Strained compounds constitute a highly topical area of research in chemistry. Borirene and borirane both feature a BC three-membered ring. They can be viewed as the structural analogues of cyclopropane and cyclopropene, where a CH unit of the carbonaceous counterparts is replaced with BH, respectively.
View Article and Find Full Text PDFTheoretical Investigation of Promising Molecules for Obtaining Complexes with Planar Tetracoordinate Carbon.
ACS Omega
October 2016
Guizhou Provincial Key Laboratory of Computational Nano-Material Science, Guizhou Education University, 115 Gaoxin Road, Wudang District, Guiyang 550018, P. R. China.
We have theoretically investigated the stability, chemical bonding, and coordination ability of the 2-Me-2-borabicyclo[1.1.0]but-1(3)-ene (2-Me-2BB) molecule using density functional theory and ab initio molecular dynamics (AIMD) simulations.
View Article and Find Full Text PDFBoron-Metallated Borirenes and Bis(Borirenes).
Chemistry
June 2016
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Heating the metalloborylene complex [{(η(5) -C5 Me5 )Fe(CO)2 }(μ-B){Cr(CO)5 }] with alkynes and diynes leads to the formation of B-metallated borirenes and a bis(B-metallated borirene) through formal transfer of the metalloborylene moiety [(η(5) -C5 Me5 )(OC)2 Fe(B:)]. By using this protocol, a range of B-metallated borirenes with electron-donating and electron-withdrawing substituents are prepared, and these are studied spectroscopically, structurally, and computationally. The yellow-orange color of the complexes is additionally explained through time-dependent density functional theory calculations.
View Article and Find Full Text PDFTrihapto ligation of a borirene to a single metal atom: a heterocyclic analogue of the η³-cyclopropenyl ligand.
Angew Chem Int Ed Engl
June 2014
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany) http://www-anorganik.chemie.uni-wuerzburg.de/Braunschweig/.
The first example of a complex containing an η(3)-coordinated borirene ligand bound to a single metal atom was prepared by photolytic transfer of an arylborylene ligand to diphenylacetylene and loss of three CO ligands from the precursor. The η(3)-borirene complex possesses a chromium(0) atom which is also bound to one phenyl group in an η(6) fashion. The complex was isolated in 15% yield along with the corresponding metal-free borirene, which was isolated in 62% yield.
View Article and Find Full Text PDFUnsupported boron-carbon σ-coordination to platinum as an isolable snapshot of σ-bond activation.
Nat Commun
May 2012
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, Würzburg, Germany.
σ-Complexes of transition metals-key intermediates in metal-mediated bond activation and homogeneous catalysis-have traditionally been isolable only when chelating or when one of the participating atoms is hydrogen. Here, by treating the Lewis-basic transition metal complex [Pt(PEt(3))(4)] with an electron-poor borirene, we isolate a complex with an unsupported borirene ligand bound, not through the unsaturated C=C bond, but exclusively via a B-C single bond. Using NMR spectroscopy, X-ray crystallography and density functional theory calculations, we show, herein, that coordination of the borirene ligand is based on electron donation from the B-C σ bond to the metal, aided by a strong Pt-to-B dative interaction.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!