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Reactivity of a Stable and Highly Electron-Rich (η-Diborabenzene)nickel(0) Synthon.
Inorg Chem
January 2025
Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, Würzburg 97074, Germany.
The reaction of the diborabenzene (DBB) nickel(0) pogo-stick complex [(η-DBB)Ni(CO)] () with a large excess of [Ni(CO)] yields the dark green, unstable dinickel(0) complex [(η-DBB)Ni(μ-CO)Ni(CO)] (), which loses one CO ligand to yield the purple, bimetallic Ni half-sandwich complex [(η-DBB)Ni(μ-CO)(η-CO)] (). The addition of the chromium aminoborylene complex [(OC)Cr{BN(TMS)}] (TMS = trimethylsilyl) to does not result in the expected borylene transfer but in the formation of the black Ni-Cr complex [(η-DBB)Ni(μ-CO)Cr(CO)] (), alongside the dimeric iminoborane [(TMS)BN(TMS)] (), which results from the rearrangement of the released BN(TMS) aminoborylene moiety. Furthermore, the oxidative addition of methyl triflate (MeOTf) to leaves the (η-DBB)Ni moiety intact and provides the ionic Ni half-sandwich complex [(η-DBB)NiMe(CO)]OTf (), while reaction with pentaphenylborole (PPB) yields the unique, dark-blue, unsymmetrical sandwich complex [(η-DBB)Ni(μ-CO)(η-PPB)] ().
View Article and Find Full Text PDFExperimental Observation of a Terminal Borylene-Dinitrogen Adduct via Cleavage of a 1,2,3,4,5-Diboratriazoline.
Angew Chem Int Ed Engl
November 2024
Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
While azides do not react with simple alkenes except under harsh conditions, a diboron alkene analogue, the doubly cyclic alkyl(amino)carbene (CAAC)-stabilized dicyanodiborene 1, reacts spontaneously with organic azides (7-10 equiv.) at room temperature to yield two equivalents of stable CAAC-imino(cyano)boranes (2-R). NMR-spectroscopic monitoring of the reaction mixtures shows the initial formation of a 1 : 1 mixture of 2-R and a relatively long-lived intermediate (Int), which in the presence of excess azide is converted into a second equivalent of 2-R.
View Article and Find Full Text PDFExperimental and Computational Study of a Confirmed Borylene-to-Diborene Dimerization.
J Am Chem Soc
October 2023
Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
While the dimerization of heavier group 13 carbene analogues to the corresponding alkene analogues is known and relatively well understood, the dimerization of dicoordinate borylenes (LRB:, L = neutral donor; R = anionic substituent) to the corresponding diborenes (LRB═BRL) has never been directly observed. In this study we present the first example of a formal borylene-to-diborene dimerization through abstraction of a labile phosphine ligand from the tricoordinate hydroborylene precursor (CAAC)(MeP)BH (CAAC = cyclic alkyl(amino)carbene) by bulky Lewis-acidic dihaloboranes (BXY, X = Cl, Br, Y = aryl, boryl), generating the corresponding dihydrodiborene (CAAC)HB═BH(CAAC) and (MeP)BXY as the byproduct. An in-depth experimental and computational mechanistic analysis shows that this seemingly simple process (2 LL'BH + 2 BXY → LHB═BHL + 2 L'BXY) is in fact based on a complex sequence of finely tuned processes, involving the one-electron oxidation of and PMe abstraction from the borylene precursor by BXY, multiple halide transfers between (di)boron intermediates and BXY/[BXY], and multiple one-electron redox processes between diboron intermediates and the borylene precursor, which make the reaction ultimately autocatalytic in [(CAAC)(MeP)BH].
View Article and Find Full Text PDFA Neutral Borylene and its Conversion to a Radical by Selective Hydrogen Transfer.
Inorg Chem
June 2023
Universität Göttingen, Institut für Anorganische Chemie, Tammannstrasse 4, 37077 Göttingen, Germany.
A successful selective reduction of XB-Tip (Tip = 1,3,5-Pr-CH, X = I, Br) with KC and Mg metal, respectively, in the presence of a hybrid ligand (CH(PPh)LSi) leads to a stable low-valent five-membered ring as a boryl radical [CH(PPh)LSiBTip][Br] () and neutral borylene [CH(PPh)LSiBTip] (). Compound reacts with 1,4-cyclohexadiene, resulting in hydrogen abstraction to afford the radical [CH(PPh)LSiB(H)Tip] (). Quantum chemical studies reveal that compound is a B-centered radical, and compound is a phosphane and silylene stabilized neutral borylene in a trigonal planar environment, whereas compound is an amidinate-centered radical.
View Article and Find Full Text PDFAuthentic Sn═B-Double Bonds in Polar Stannaborene Derivatives.
J Am Chem Soc
June 2023
Institut für Anorganische Chemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany.
We report on the synthesis of an authentic Sn═B-moiety realized in a stannaborenyl anion and stannaborenium cation. Starting with an oxidative addition of boron tribromide to a stannylene-phosphine Lewis pair [-CH(Ar*BrSn-BBr-PPh)] () [Ar* = CH(2,6-Trip), Trip = 2,4,6-CHPr] was synthesized. Reduction of with magnesium yields the Grignard-type stannaborene [-CH(Ar*Sn═B{PPh}MgBr{thf})] () featuring a Sn═B double bond and a B-Mg interaction.
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