Journal ArticleDOI
Electronically Induced Steric Clash: Synthesis of NMe2-Modified β-Diketiminate-Supported Boron Difluoride Compounds
Balasubramanian Murugesapandian,Rakesh Ganguly,Peter T. K. Lee,Milena Petković,Jason A. C. Clyburne,Dragoslav Vidovic +5 more
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In this article, the synthesis and structural features of NMe2-modified β-diketiminate-supported boron difluoride compounds (LArBF2: LAr = [HC(NAr)2(CNMe2)2]Abstract:
We report on the synthesis and structural features of NMe2-modified β-diketiminate-supported boron difluoride compounds (LArBF2: LAr = [HC(NAr)2(CNMe2)2]–; LPh: Ar = Ph; LTol: Ar = p-tolyl; LXyl: Ar = m-xylyl). The title compounds were prepared in moderate yields (~65 %) by in situ deprotonation of the corresponding ligands LArH using KH, followed by the addition of BF3OEt2. According to solid-state and theoretical analyses of the BF2 compounds, the lone pair at each NMe2 group is involved in electron delocalization within the central BC3N2 ring. As a result, the N-aryl substituents sterically clash with the NMe2 groups, causing this central ring to pucker. Several attempts were made to prepare heavy analogues (e.g. LArBX2, X = Cl, Br, I) but only unidentifiable product mixtures were observed. It appears that the observed steric clash between the N-aryl substituents and the NMe2 groups prevented the formation of these heavy analogues.read more
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N-nacnac stabilized tetrylenes: access to silicon hydride systems via migration processes
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Reactivity of 1,3-dichloro-1,3-bis(dimethylamino)-propenium salts with primary amines
TL;DR: In this paper, the mechanisms of the intramolecular rearrangements have been investigated at the ωB97X-D/6-311G(d,p) level of theory, suggesting that the reactions proceed through putative keteniminium species.
References
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Journal ArticleDOI
The Chemistry of β-Diketiminatometal Complexes
Journal ArticleDOI
Stable Magnesium(I) Compounds with Mg-Mg Bonds
TL;DR: The reductions of two magnesium(II) iodide complexes with potassium metal in toluene, leading to thermally stable magnesium(I) compounds, (L)MgMg(L) in moderate yields, consistent with central Mg 2+2 units that have single, covalent magnesium-magnesium bonding interactions.
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Single-site beta-diiminate zinc catalysts for the alternating copolymerization of CO2 and epoxides: catalyst synthesis and unprecedented polymerization activity.
Ming Cheng,David Roger Moore,Joseph J. Reczek,Bradley M. Chamberlain,Emil B. Lobkovsky,Geoffrey W. Coates +5 more
TL;DR: Copolymerizations of cyclohexene oxide (CHO) and CO2 with (BDI-1)ZnX with ligand effects were shown to dramatically influence the polymerized activity as minor steric changes accelerated or terminated the polymerization activity.
Journal ArticleDOI
N2 Reduction and Hydrogenation to Ammonia by a Molecular Iron-Potassium Complex
TL;DR: A molecular iron complex that reacts with N2 and a potassium reductant to give a complex with two nitrides, which are bound to iron and potassium cations, which give structural and spectroscopic insight into N2 cleavage and N-H bond-forming reactions of iron.