Metal free mild and selective aldehyde cyanosilylation by a neutral penta-coordinate silicon compound

Swamy, V. S. V. S. N.; Bisai, Milan Kumar; Das, Tamal; Sen, Sakya S.

doi:10.1039/c7cc03948d

Cited by 37 publications

(26 citation statements)

References 47 publications

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“…The solid state infra‐red spectra of 17 and 18 exhibit Si‐H stretching bands at wavenumbers ( ν = 2105 cm –1 and 2118 cm –1 respectively) comparable to those recorded for related amidinato silicon(IV) hydride/chlorides (e.g. ν = 2160 cm –1 for [(Amid)SiHClMe]; [ 23 ] 2190 cm –1 for 13 ).…”

Section: Resultssupporting

confidence: 57%

s‐ and p‐Block Dinuclear Metal(loid) Complexes Bearing 1,4‐Phenylene and 1,4‐Cyclohexylene Bridged Bis(amidinate) Ligands

2020

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Treating two 2,6‐diisopropylphenyl (Dip) substituted, 1,4‐phenylene or 1,4‐cyclohexylene bridged, bis(amidine)s, viz. C6Hn{[Dip(H)N](DipN=)C}2‐1,4 (n = 4 (PhAmid2H2) or 10 (CyAmid2H2)), with groups 1 and 2 alkyl complexes, proceeded via alkane elimination and the formation of the lithium and magnesium bis(amidinate) complexes, [{(THF)2Li}2(µ‐PhAmid2)], [{(THF)3K(µ‐PhAmid2)K}∞], [(Et2O)IMg(µ‐PhAmid2)MgI(OEt2)2], and [{(Et2O)2IMg}2(µ‐CyAmid2)]. The crystal structures of the complexes reveal variable modes of coordination at the metal centre. Two lithium bis(amidinate) compounds have been utilized in salt elimination reactions with group 13 and 14 halides, yielding a series of bis(amidinato) aluminum(III), silicon(IV), germanium(II) and tin(II) halide complexes, viz. [(I2Al)2(µ‐PhAmid2)], [(X3Si)2(µ‐PhAmid2)] (X = Cl, Br or Cl/H), [(ClM)2(µ‐PhAmid2)] (M = Ge or Sn), and [(ClGe)2(µ‐CyAmid2)]. Attempts to reduce the bis(amidinato) metal(loid) halide complexes with a series of s‐block metal reducing agents have been carried out, with the aim of obtaining dinuclear or polymeric bis(amidinato) metal(I) systems. However, these reductions typically led to intractable mixtures of products. In other attempted reductions, treating [(Cl2HSi)2(µ‐PhAmid2)] with two N‐heterocyclic carbenes (NHCs), :C{(RNCMe)2} (R = Me (TMC) or Pri (IPrIMe)) led to single dehydrochlorination reactions, affording the cyclohexa‐2,5‐diene‐1,4‐diylidene bridged bis(diamide) silicon(IV) complexes, [{(NHC)Cl2Si}{µ‐(DipN)2C=(C6H4)=C(NDip)2}{SiHCl(NHC)}] (NHC = TMC or IPrIMe), in which the bis(amidinate) ligand has been transformed into a tetra(amide).

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Section: Resultssupporting

confidence: 57%

s‐ and p‐Block Dinuclear Metal(loid) Complexes Bearing 1,4‐Phenylene and 1,4‐Cyclohexylene Bridged Bis(amidinate) Ligands

2020

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“…In addition to the transition metals, the compounds of the some main-group elements may have the transition-metal-like reactivity and catalyze the oxidative addition of the C–F bond (Jana et al, 2010; Stahl et al, 2013; Swamy et al, 2017; Chu and Nikonov, 2018). In particular, recent experimental studies demonstrated that a monomeric Al(I) center supported by the NacNac − ligand (NacNac − = [ArNC(Me)CHC(Me)NAr] − and Ar = 2,6–Pr2iC 6 H 3 ) could catalyze the oxidative addition of the C–F bond (Chu et al, 2015; Crimmin et al, 2015).…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Features in Al(I)-Mediated Oxidative Addition of Aryl C–F Bonds: Insights From Density Functional Theory Calculations

Zhang

Wang

et al. 2019

Front. Chem.

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The oxidative addition of a range of robust aryl C–F bonds to a single Al(I) center supported by a (NacNac)− bidentate ligand ((NacNac)− = [ArNC(Me)CHC(Me)NAr]− and Ar = 2,6–Pr2iC6H3) have been explored by density functional theory calculations. Our calculations demonstrate that the Al(I) center-mediated C–F insertion generally proceeds via the concerted mechanism that involve both the donation (nAl→σC-F*) and back-donation (σF(p)→πAl(p)*) interactions. In addition, the predicted free energy barriers for the C–F bond activation show good agreement with the experimental information available. Finally, the comparative studies show that B(I) is the most active among group III metals (B, Al, Ga), thus supplying a testable prediction for experiments.

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“…To expand the catalytic regime of hydrocarbon soluble welldefined calciumc ompounds, we have turned our attention towardst he cyanosilylation of carbonyl compounds with Me 3 SiCN, [21] in which none of the substrates possessed an EÀH bond.U nlike carbonyl hydroborationb yh eavierm ain group compounds, whichi si ncreasingly being reported in the literature, [22] the catalytic carbonyl cyanosilylationb yc ompounds with heavier main group elements has seen only limited success with p-block elements from the groupsofRoesky, [23][24][25] Nagendran, [26,27] and others. [28,29] Furthermore, cyanosilylation of carbonylc ompounds has not been achieved thus far with any alkaline earth metal complex. Notable advances to this end have been made with lanthanide-based polyoxometallates.…”

mentioning

confidence: 99%

Beyond Hydrofunctionalisation: A Well‐Defined Calcium Compound Catalysed Mild and Efficient Carbonyl Cyanosilylation

Yadav

Dixit

Vanka

et al. 2018

Chemistry A European J

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Organocalcium compounds have been reported as efficient catalysts for various transformations, for cases in which one of the substrates contained an E-H (E=B, N, Si, P) bond. Here, we look at the possibility of employing an organocalcium compound for a transformation in which none of the precursors has a polar E-H bond. This study demonstrates the utilization of a well-defined amidinatocalcium iodide, [PhC(NiPr) CaI] (1) for cyanosilylation of a variety of aldehydes and ketones with Me SiCN under ambient conditions without the need of any co-catalyst. The reaction mechanism involves a weak adduct formation between 1 and Me SiCN leading to the activation of the Si-C bond, which subsequently undergoes σ-bond metathesis with a C=O moiety. Such a mechanistic pathway is unprecedented in alkaline earth metal chemistry. Experimental and computational studies support the mechanism.

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Metal free mild and selective aldehyde cyanosilylation by a neutral penta-coordinate silicon compound

Cited by 37 publications

References 47 publications

s‐ and p‐Block Dinuclear Metal(loid) Complexes Bearing 1,4‐Phenylene and 1,4‐Cyclohexylene Bridged Bis(amidinate) Ligands

s‐ and p‐Block Dinuclear Metal(loid) Complexes Bearing 1,4‐Phenylene and 1,4‐Cyclohexylene Bridged Bis(amidinate) Ligands

Mechanistic Features in Al(I)-Mediated Oxidative Addition of Aryl C–F Bonds: Insights From Density Functional Theory Calculations

Beyond Hydrofunctionalisation: A Well‐Defined Calcium Compound Catalysed Mild and Efficient Carbonyl Cyanosilylation

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