Reversible Base Coordination to a Disilene

Leszczyńska, Kinga; Abersfelder, Kai; Mix, Andreas; Neumann, Beate; Stammler, Hans‐Georg; Cowley, Michael J.; Jutzi, Peter; Scheschkewitz, David

doi:10.1002/anie.201202277

Cited by 105 publications

(53 citation statements)

References 43 publications

(50 reference statements)

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“…These results indicate that on the coordination of DMAP, the Si1 À Si2 and Si2 À Si3 bond distances of 1 were elongated (2.286 and 2.244 Å), whereas the Si1 À Si3 bond distance was shortened (2.620 Å). A similar elongation of Si ¼ Si double bonds on the coordination of Lewis bases has been reported by Scheschkewitz et al 26 The frontier orbitals of 1 opt and 1ÁDMAP opt are shown in Fig. 3b,c.…”

supporting

confidence: 84%

“…The endocyclic Si1-Si2 and ARTICLE Si2-Si3 bond distances, 2.2906(6) and 2.2556(6) Å, respectively, are between the typical Si À Si (ca. 2.36 Å) 27 and Si ¼ Si bond distances (2.118-2.289 Å) 31,32 , and close to those of N-heterocyclic carbene-coordinated cyclotrisilene (trisilacyclopropene) (2.2700(5)Å) 26 , indicating a significant double-bond character in Si1 À Si2 and Si2 À Si3 bonds. The geometry around Si2 is considerably pyramidalized with the sum of bond angles around Si2 (except the angles involving Si2 À N1 bond) of 312.63(4)°, whereas that around Si3 is almost planar with the sum of bond angles around Si3 (except the bond angles involving Si1 À Si3 bond), 359.30(4)°.…”

mentioning

confidence: 58%

“…DMAP. To obtain monomeric Si 4 BBE 1, we investigated the thermolysis reaction in the presence of a Lewis base, because coordinating to a Lewis base may stabilize Si 4 BBE 1, similar to other unsaturated silicon compounds [14][15][16]26 . The reaction of 2 in the presence of 7.6 equiv.…”

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confidence: 99%

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A heavy analogue of the smallest bridgehead alkene stabilized by a base

2014

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Bicyclo[1.1.0]but-1(2)-ene (BBE), one of the smallest bridgehead alkenes and C 4 H 4 isomers, exists theoretically as a reactive intermediate, but has not been observed experimentally. Here we successfully synthesize the silicon analogue of BBE, tetrasilabicyclo[1.1.0]but-1(2)-ene (Si 4 BBE), in a base-stabilized form. The results of X-ray diffraction analysis and theoretical study indicate that Si 4 BBE predominantly exists as a zwitterionic structure involving a tetrasilahomocyclopropenylium cation and a silyl anion rather than a bicyclic structure with a localized highly strained double bond. The reaction of base-stabilized Si 4 BBE with triphenylborane affords the [2 þ 2] cycloadduct of Si 4 BBE and the dimer of an isomer of Si 4 BBE, tetrasilabicyclo[1.1.0]butan-2-ylidene (Si 4 BBY). The facile isomerization between Si 4 BBE and Si 4 BBY is supported by theoretical calculations and trapping reactions. Structure and properties of a heavy analogue of the smallest bridgehead alkene are disclosed.

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confidence: 84%

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confidence: 58%

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A heavy analogue of the smallest bridgehead alkene stabilized by a base

2014

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“…16). B. Blom and M. Driess cyclotrisilene with exclusively carbon-based substituents by Scheschkewitz, Jutzi and co-workers [105]. In this instance, salt metathesis of 107 with the lithium disilenide (Trip) 2 Si ¼ Si(Trip)(Li{dme} 2 ) (111) afforded a mixture containing 85% of the cyclotrisilene (112).…”

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confidence: 96%

Recent Advances in Silylene Chemistry: Small Molecule Activation En-Route Towards Metal-Free Catalysis

Blom

Drieß

2013

Structure and Bonding

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*2 Si: (Cp* ¼ η 5 -C 5 Me 5 ), the first isolable Si(II) compound, and later in 1994 with the discovery of the first N-heterocyclic silylene by West and Denk, heralding the beginning of a bourgeoning era in low-valent silicon chemistry. Since these and other key discoveries, massive advances have been made in understanding and elucidating the nature of these reactive compounds, and their ability, for example, to activate small molecules, or behave as ligands in transition metal complexes which can perform a variety of catalytic or stoichiometric transformations. In this chapter, recent advances in silylene chemistry will be presented, with a particular focus on developments in the last 10 years approximately. A key emphasis will rest on the reactivity of isolable silylenes, including their coordination towards metals, with respect to small molecule bond activation, and potential catalytic transformations. Although metalcoordinated silylene complexes have been shown to be catalytically useful in a variety of transformations, metal-free catalysis with silylenes is still a target.

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“…More recently, Scheschkewitz and co-workers reported the synthesis of the first aryl substituted cyclotrisilenes and their reactivity towards N-heterocyclic carbenes. [4]…”

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Phosphide Delivery to a Cyclotrisilene

et al. 2014

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The reactivity of the 2-phosphaethynolate anion (PCO−) towards a cyclic trisilene (cSi3(Tip)4) is reported. The result is the net activation of the P=C and Si=Si multiple bonds of the precursors affording a heteroatomic bicyclo[1.1.1]pentan-2-one analogue ([P(CO)Si3(Tip)4]−; 1). This reaction can be interpreted as the formal addition of a phosphide and a carbonyl across the Si=Si double bond. Photolytic decarbonylation of 1 results in the incorporation of the phosphide vertex into the cyclotrisilene scaffold, yielding a congener of the cyclobutene anion with considerable allylic character.

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Reversible Base Coordination to a Disilene

Cited by 105 publications

References 43 publications

A heavy analogue of the smallest bridgehead alkene stabilized by a base

A heavy analogue of the smallest bridgehead alkene stabilized by a base

Recent Advances in Silylene Chemistry: Small Molecule Activation En-Route Towards Metal-Free Catalysis

Phosphide Delivery to a Cyclotrisilene

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