[2+2] Cycloadduct of Titanium Silylidene and Benzonitrile

Lee, Vladimir Ya.; Horiguchi, Satoru; Gapurenko, Olga A.; Minyaev, R. M.; Sekiguchi, Akira

doi:10.1002/ejic.201900601

Cited by 10 publications

(5 citation statements)

References 21 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Given that relative atomic charges derived from an NPA (natural population analysis) of 1 indicates a positive relative charge at silicon (NPA Si =+1.14; NPA Ni =−0.59), it's not surprising that in the aforementioned cases the heteroatom binds silicon, forming planar and cyclic [SiNiCX] cores (X=O or N). This is in contrast to the reactivity of Sekiguchi's titanium–silylene complex (Figure ), which forms both regio‐isomers in the reaction with benzonitrile . Observing the frontier orbitals of 1 , one can see that the LUMO represents the π*‐orbital of the Si−Ni bond, considerably weighted towards Si II , whereas the HOMO is a filled 3 d orbital at Ni 0 .…”

Section: Figurementioning

confidence: 77%

Cycloaddition Chemistry of a Silylene‐Nickel Complex toward Organic π‐Systems: From Reversibility to C−H Activation

Hadlington

Kostenko

Drieß

2020

Chemistry A European J

View full text Add to dashboard Cite

Thev ersatile cycloaddition chemistry of the SiÀ Ni multiple bond in the acyclic( amido)(chloro)silylene! Ni 0 complex 1,[ ( TMS L)ClSi!Ni(NHC) 2 ]( TMS L = N(SiMe 3 )Dipp; Dipp = 2,6-iPr 2 C 6 H 4 ;N HC = C[(iPr)NC(Me)] 2 ), towardu nsaturated organic substrates is reported, which is both reminiscento fa nd expanding on the reactivity patternso f classical Fischer and Schrock carbene-metal complexes. Thus, 1:1r eactiono f1 with aldehydes,i mines, alkynes, and even alkenes proceed to yield [2+ +2] cycloaddition products, leading to ar ange of four-membered metallasilacycles. This cycloaddition is in factr eversible for ethylene, whereas addition of an excesso ft his olefin leads to quantitative sp 2 -CH bond activation, via a1 -nickela-4-silacyclohexanei ntermediate.T hese results have been supported by DFT calculations giving insights into key mechanistic aspects.

show abstract

Section: Figurementioning

confidence: 77%

Cycloaddition Chemistry of a Silylene‐Nickel Complex toward Organic π‐Systems: From Reversibility to C−H Activation

Hadlington

Kostenko

Drieß

2020

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…Unfortunately, no cycloreversion products were detected, and further studies are required to understand the limits to Si‐based metathesis at Schrock‐type tetrylenes. Following up on this work, Sekiguchi and coworkers also reacted 32 with benzonitrile to form metalacyclic complex 34 [79] …”

Section: Reactivity With Unsaturated Substratesmentioning

confidence: 98%

“…Following up on this work, Sekiguchi and coworkers also reacted 32 with benzonitrile to form metalacyclic complex 34 . [79] …”

Section: Reactivity With Unsaturated Substratesmentioning

confidence: 99%

Cooperativity in Transition Metal Tetrylene Complexes

Somerville

Campos

2021

Eur J Inorg Chem

View full text Add to dashboard Cite

Cooperative reactivity between transition metals and ligands, or between two metals, has created significant opportunities for the development of new transformations that would be difficult to carry out with a single metal. Here we explore cooperativity between transition metals and divalent heavier group 14 elements (tetrylenes), a less‐explored facet of the field of cooperativity. Tetrylenes combine their strong σ‐donor properties with an empty p‐orbital that can accept electron density. This ambiphilicity has allowed them to form metal tetrylene and metallotetrylene complexes that place a reactive site adjacent to the metal. We have selected examples to demonstrate what has been achieved so far regarding cooperative reactivity, as this already spans metal‐, tetrylene‐ or multi‐site‐centred bond cleavage, cycloaddition, migration, metathesis, and insertion. We also highlight some challenges that need to be overcome for this cooperativity to make it to catalysis.

show abstract

“…[4][5][6][7][8][9][10][11][12] Moreover, they represent the prospects of new avenues for transition metal/P-element cooperation. [13][14][15][16][17][18][19][20][21][22][23][24][25] However, the coordination chemistry of tetrylenes remains considerably less explored than their lighter carbene congeners, in no little part due to reduced stability. To overcome this limitation base-stabilized tetrylenes have been explored and their complexes have found relevance in catalysis.…”

mentioning

confidence: 99%

Dehydrogenative Double C—H Bond Activation in a Germylene-Rhodium Complex

Bajo¹,

Alcaide²,

López-Serrano³

et al. 2021

Preprint

View full text Add to dashboard Cite

Transition metal tetrylene complexes offer great opportunities for molecular cooperation due to the ambiphilic character of the group 14 element. Here we focus on the coordination of germylene [(ArMes2)2Ge:] (ArMes = C6H3-2,6-(C6H2-2,4,6-Me3)2) to [RhCl(COD)]2 (COD = 1,5-cyclooctadinene), which yields a neutral germyl complex in which the rhodium center exhibits both η6- and η2-coordination to two mesityl rings in an unusual pincer-type structure. Chloride abstraction from this species triggers a singular dehydrogenative double C—H bond activation across the Ge/Rh motif. We have isolated and fully characterized three rhodium-germyl species associated to three C—H cleavage events along this process. The reaction mechanism has been further investigated by computational means, supporting the key cooperative action of rhodium and germanium centers.Transition metal tetrylene complexes offer great opportunities for molecular cooperation due to the ambiphilic character of the group 14 element. Here we focus on the coordination of germylene [(ArMes2)2Ge:] (ArMes = C6H3-2,6-(C6H2-2,4,6-Me3)2) to [RhCl(COD)]2 (COD = 1,5-cyclooctadinene), which yields a neutral germyl complex in which the rhodium center exhibits both η6- and η2-coordination to two mesityl rings in an unusual pincer-type structure. Chloride abstraction from this species triggers a singular dehydrogenative double C—H bond activation across the Ge/Rh motif. We have isolated and fully characterized three rhodium-germyl species associated to three C—H cleavage events along this process. The reaction mechanism has been further investigated by computational means, supporting the key cooperative action of rhodium and germanium centers.

show abstract

[2+2] Cycloadduct of Titanium Silylidene and Benzonitrile

Cited by 10 publications

References 21 publications

Cycloaddition Chemistry of a Silylene‐Nickel Complex toward Organic π‐Systems: From Reversibility to C−H Activation

Cycloaddition Chemistry of a Silylene‐Nickel Complex toward Organic π‐Systems: From Reversibility to C−H Activation

Cooperativity in Transition Metal Tetrylene Complexes

Dehydrogenative Double C—H Bond Activation in a Germylene-Rhodium Complex

Contact Info

Product

Resources

About