Donor–acceptor chemistry in the main group

Rivard, Eric

doi:10.1039/c4dt00481g

Cited by 114 publications

(62 citation statements)

References 110 publications

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“…Notably, the transition metal iminoboryl systems were found to be stable against oligomerization, yet reactive towards a variety of substrates. [6,7] In recent years, it has been shown that stable singlet carbenes [8] can be used, in place of transition metals, to not only stabilize a variety of highly reactive species, [9] but also to activate small molecules and enthalpically strong bonds. [10,11] Herein, we report that a singlet cyclic (alkyl)(amino)carbene (CAAC) [12] reacts with bis(trimethylsilyl)dihaloboranes, and allows for the preparation of room-temperature-stable iminoboryl-carbene adducts.…”

Section: Introductionmentioning

confidence: 99%

Oxidative Addition at a Carbene Center: Synthesis of an Iminoboryl–CAAC Adduct

Dahcheh

Stephan

Bertrand

2014

Chemistry A European J

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The reaction of a cyclic (alkyl)(amino)carbene (CAAC) with dichloro- and dibromobis(trimethylsilyl)aminoborane results in the formation of haloiminoborane-CAAC adducts. When the iodo analogue is used, an oxidative addition at the carbene center affords a cationic iminoboryl-CAAC adduct, featuring a boron-nitrogen triple bond. Similar salts are also obtained by halide abstraction from the chloro- and bromoiminoborane-CAAC adducts. The reactivity of all of these compounds towards CO2 is discussed.

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Section: Introductionmentioning

confidence: 99%

Oxidative Addition at a Carbene Center: Synthesis of an Iminoboryl–CAAC Adduct

Dahcheh

Stephan

Bertrand

2014

Chemistry A European J

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“…Some remarkable examples of the application of this strategy have been the subject of a recent Perspective article, and most feature the use of N-heterocyclic carbene stabilized acceptors behaving as donors. 47 Analogous Lewis-basic behaviour for phosphine stabilized complexes has only been reported for a few acceptor elements. In group 14, the most diverse examples are from the coordination chemistry of phosphonium ylides and double ylides (carbodiphosphoranes).…”

Section: Coordination and Oxidation Of Lone Pair Bearing Acceptor-cenmentioning

confidence: 98%

Phosphine complexes of lone pair bearing Lewis acceptors

Chitnis

Burford

2015

Dalton Trans.

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An overview of the synthesis, structures and reaction chemistry of coordination complexes featuring an acceptor with at least one lone pair and at least one phosphine donor is presented. One or more examples of complexes have been structurally-characterized for the majority of p-block elements but few are known for most elements. The unusual condition of a p-block element centre accommodating a lone pair of electrons and offering a low energy LUMO gives the element centre the potential to behave as both a Lewis acid and a Lewis Base. The structural diversity and reactivity of the phosphine complexes highlights new directions in main group chemistry and by comparison with transition metal coordination chemistry, the featured complexes demonstrate significant configurational and stereochemical flexibility. Ligand exchange, oxidation and reduction chemistry at the lone pair bearing acceptor centre reveals unusual reactivity and an interesting class of ligands and inorganic reagents, with new possibilities for catalysis or small molecule activation.

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“…Key to these developments have been the usage of suitable synthetic methodologies in combination with thermodynamic and kinetic stabilization by appropriately chosen ligands. In particular, for the heavier carbon analogue silicon, a plethora of studies reported new low-valent compounds in recent years [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25] and the chemistry of silylene base adducts has already been carefully developed [14,[26][27][28][29][30][31][32][33][34][35][36]. Before these findings, silyliumylidene ions, cationic Si(II) species were found to be promising as similar versatile Lewis amphiphiles [37,38].…”

Section: Introductionmentioning

confidence: 99%

S–H Bond Activation in Hydrogen Sulfide by NHC-Stabilized Silyliumylidene Ions

et al. 2018

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Reactivity studies of silyliumylidenes remain scarce with only a handful of publications to date. Herein we report the activation of S-H bonds in hydrogen sulfide by mTer-silyliumylidene ion A (mTer = 2,6-Mes 2 -C 6 H 3 , Mes = 2,4,6-Me 3 -C 6 H 2 ) to yield an NHC-stabilized thiosilaaldehyde B. The results of NBO and QTAIM analyses suggest a zwitterionic formulation of the product B as the most appropriate. Detailed mechanistic investigations are performed at the M06-L/6-311+G(d,p)(SMD: acetonitrile/benzene)//M06-L/6-311+G(d,p) level of density functional theory. Several pathways for the formation of thiosilaaldehyde B are examined. The energetically preferred route commences with a stepwise addition of H 2 S to the nucleophilic silicon center. Subsequent NHC dissociation and proton abstraction yields the thiosilaaldehyde in a strongly exergonic reaction. Intermediacy of a chlorosilylene or a thiosilylene is kinetically precluded. With an overall activation barrier of 15 kcal/mol, the resulting mechanistic picture is fully in line with the experimental observation of an instantaneous reaction at sub-zero temperatures.

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Donor–acceptor chemistry in the main group

Cited by 114 publications

References 110 publications

Oxidative Addition at a Carbene Center: Synthesis of an Iminoboryl–CAAC Adduct

Oxidative Addition at a Carbene Center: Synthesis of an Iminoboryl–CAAC Adduct

Phosphine complexes of lone pair bearing Lewis acceptors

S–H Bond Activation in Hydrogen Sulfide by NHC-Stabilized Silyliumylidene Ions

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