SiSi Double Bonds: Synthesis of an NHC‐Stabilized Disilavinylidene

Ghana, Priyabrata; Arz, Marius I.; Das, Ujjal; Schnakenburg, Gregor; Filippou, Alexander C.

doi:10.1002/ange.201504494

Cited by 35 publications

(14 citation statements)

References 78 publications

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“…[8c] In digermavinylidene (33), the four atoms that defined the B 2 GeGe unit, lied within a single plane. The structural analysis of 33 revealed the presence of weak interaction between flanking arene π systems (aryl rings of each of the boryl ligands) and vacant in-plan p orbital at Ge2, confirmed by variable-temper- 2.167(2) C SIdipp À Si2À Si1: 97.6(1)° [16] 2.4716(11) Si2À Si1À Si2*: 115.09(3)° [24] 2.223 17B1À Si1À Si2: 127.34 14°, B2À Si2À Si1: 128.20 14° [ 27] Scheme 13. General synthetic methods for digermene: a) photolysis or ring opening of cyclotrigermanes, [31,32a] b) reductive dehalogenation [31,32b-d] and c) dimerization.…”

Section: Digermenes (> Ge=gementioning

confidence: 95%

“…DFT studies revealed cyclic delocalization of six mobile electrons of the π-, σand non-bonding type across the central four-membered ring. The reduction and isomerization studies of the dismutational isomer of the hexasilabenzene (16) was carried out by Scheschkewitz and co-workers. [23h-j] Recently, Iwamoto and Ishida et al synthesized a tetrasilicon compound (18), analogue of bicyclo [1.1.0]but-1(3)-ene, having a formal double bond between bridgehead silicon atoms.…”

Section: Disilenes (> Si=simentioning

confidence: 99%

“…Recently, Filippou et al . reported another NHC stabilized disilene complex ( 6 , disilavinylidene) [16] . The synthesis of 6 involved three‐steps; first, the reaction of SiBr 2 (SIDipp) with 1,2‐dibromodisilene ( E )‐Tbb(Br)Si=Si(Br)Tbb (Tbb = C 6 H 2 ‐2,6‐[CH(SiMe 3 ) 2 ] 2 ‐4‐ t Bu) at 100 °C resulted in the formation of intermediate 5′ ( (SIDipp)Br 2 SiSi(Br)Tbb), which rearranged via a 1,2 migration to give the NHC‐stabilized bromo(silyl)silylene, ( 5 ).…”

Section: Homonuclear Multiple Bondmentioning

confidence: 99%

“…In recent years, the chemistry of multiple bonded compounds of silicon and germanium has shown remarkable progress. Given the growing interest in heavier main group multiple bonded compounds, this report presents a brief overview on the early reports, followed by detailed information on the latest developments of multiple bonded silicon and germanium with group 13 and heavier elements of groups [14][15][16]. There are reports on the development of multiple bonded compounds compiled rather specifically on group 14 homonuclear double or triple bonded compounds E=E/E � E (E=Si, Ge, Sn or Pb), [9] or heteronuclear combinations E=E'/E � E' (E=Si, Ge, Sn or Pb; E' = group 13-16 element) [10] or both [11] and their reactivity studies.…”

Section: Introductionmentioning

confidence: 99%

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Bonding Relationship between Silicon and Germanium with Group 13 and Heavier Elements of Groups 14–16

Agarwal

Bose

2020

Chemistry An Asian Journal

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The topic of heavier main group compounds possessing multiple bonds is the subject of momentous interest in modern organometallic chemistry. Importantly, there is an excitement involving the discovery of unprecedented compounds with unique bonding modes. The research in this area is still expanding, particularly the reactivity aspects of these compounds. This article aims to describe the overall developments reported on the stable derivatives of silicon and germanium involved in multiple bond formation with other group 13, and heavier groups 14, 15, and 16 elements. The synthetic strategies, structural features, and their reactivity towards different nucleophiles, unsaturated organic substrates, and in small molecule activation are discussed. Further, their physical and chemical properties are described based on their spectroscopic and theoretical studies.

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Section: Digermenes (> Ge=gementioning

confidence: 95%

Section: Disilenes (> Si=simentioning

confidence: 99%

Section: Homonuclear Multiple Bondmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Bonding Relationship between Silicon and Germanium with Group 13 and Heavier Elements of Groups 14–16

Agarwal

Bose

2020

Chemistry An Asian Journal

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“…Tw oa lternative mechanisms can be considered:1)the direct silylene insertion into aS i À Xb ond (X = H, Cl) of as econd monomer;o r2 )atwostep process involving the first formation of disilenes 4 followed by a1 ,2-migration of substituent X. [16,17] However, all attempts to find ar eaction pathway leading to disilenes 4 failed, even though dimers 4 are aminimum on the potential energy surface,a nd the dimerization process is only slightly endergonic in the case of 2a-H (DG 1 = 12.6 kJ mol À1 ). The formation of 4b-Cl is more endergonic (DG 1 = 66.9 kJ mol À1 ), which is probably due to steric reasons.Itisimportant to note that the optimized geometries of 4a,b reveal that they can be regarded as silylenes stabilized by as econd silylene ligand, rather than symmetric disilene structures (Figure 4).…”

Section: Methodsmentioning

confidence: 99%

Reversible Dimerization of Phosphine‐Stabilized Silylenes by Silylene Insertion into Si^II–H and Si^II–Cl σ‐Bonds at Room Temperature

et al. 2015

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Reversible Dimerization of Phosphine‐Stabilized Silylenes by Silylene Insertion into Si^II–H and Si^II–Cl σ‐Bonds at Room Temperature

et al. 2015

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Contrary to the classical silylene dimerization leading to ad isilene structure,p hosphine stabilized hydroand chloro-silylenes (2a,b)u ndergo an unique dimerization via silylene insertion into SiÀX s-bonds (X = H, Cl), whichi s reversible at room temperature.DFT calculations indicate that the insertion reaction proceeds in one step in ac oncerted manner.The dimerization of silylenes to the corresponding disilene is one of the most common reactions of these low-coordinate silicon species (type A). Since the synthesis of the first stable silylene by West et al., [1] as ignificant number of disilenes were synthesized by this method. [2] It has been experimentally and theoretically shown that the bonding situation in disilenes and their stability strongly depend on the nature of the substituents. [3] Indeed, ar eversible disilene-silylene equilibrium has been observed for some sterically overcrowded silylenes I [4] and II, [5] and p-donor (Br,a mino) substituted species III, [6] IV, [7] and V. [8] Particularly,i nt he case of V,i ts dimer is stable only in the solid state.Theoretical calculations predicted that silylenes with al arge singlet-triplet energy gap (DE ST )a nd featuring an electronegative group with al one pair dimerize by the interaction between the substituent lone pair and the silylene empty orbital, leading to af our-membered ring structures (type B). [9, 7b] It is interesting to note that in the case of bisdiisopropylamino silylene IV,b oth types of dimerization processes (Si=Si bonded A,and N-bridged B)were observed, spectroscopically in solution, depending on the temperature. [7,10] In contrast, the stable cyclic diaminosilylene VI does not dimerize to the corresponding tetraaminodisilene,o rNbridged dimer,but instead undergoes the insertion reaction of another silylene into aS i ÀNb ond to generate the transient amino-silyl silylene VII (inserted dimer,t ype C), which readily dimerizes to the diaminodisilyl disilene VIII. [11] Interestingly,b oth steps are reversible at room temperature, and such ad imerization process (type C), involving ar eversible silylene insertion into a s-bond, in mild conditions,i s extremely rare,a lthough non-reversible insertion reactions are typical for transient silylenes.H erein we report the reversible dimerization of phosphine-stabilized silylenes 2, leading to inserted dimers 3 (type C), which can be isolated and fully characterized in the solid state.Recently,wehave reported the synthesis of the first stable phosphine-supported Si II hydride 2c-H and chloride 2c-Cl (Scheme 1) [12,15] by reduction of the corresponding chlorosilane derivatives 1c-X (X = H, Cl), and the unique reactivity of 2c-H with olefins as well as with diphenylacetylene. [13] In the present study,wehave investigated the relationship between Scheme 1. Synthesis of hydro-and chlorosilylenes (2a,b,c-X)and their reversible dimerization by silylene insertion into a s-SiÀXb ond (X = H, Cl).

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SiSi Double Bonds: Synthesis of an NHC‐Stabilized Disilavinylidene

Cited by 35 publications

References 78 publications

Bonding Relationship between Silicon and Germanium with Group 13 and Heavier Elements of Groups 14–16

Bonding Relationship between Silicon and Germanium with Group 13 and Heavier Elements of Groups 14–16

Reversible Dimerization of Phosphine‐Stabilized Silylenes by Silylene Insertion into Si^II–H and Si^II–Cl σ‐Bonds at Room Temperature

Reversible Dimerization of Phosphine‐Stabilized Silylenes by Silylene Insertion into Si^II–H and Si^II–Cl σ‐Bonds at Room Temperature

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SiSi Double Bonds: Synthesis of an NHC‐Stabilized Disilavinylidene

Cited by 35 publications

References 78 publications

Bonding Relationship between Silicon and Germanium with Group 13 and Heavier Elements of Groups 14–16

Bonding Relationship between Silicon and Germanium with Group 13 and Heavier Elements of Groups 14–16

Reversible Dimerization of Phosphine‐Stabilized Silylenes by Silylene Insertion into SiII–H and SiII–Cl σ‐Bonds at Room Temperature

Reversible Dimerization of Phosphine‐Stabilized Silylenes by Silylene Insertion into SiII–H and SiII–Cl σ‐Bonds at Room Temperature

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Reversible Dimerization of Phosphine‐Stabilized Silylenes by Silylene Insertion into Si^II–H and Si^II–Cl σ‐Bonds at Room Temperature

Reversible Dimerization of Phosphine‐Stabilized Silylenes by Silylene Insertion into Si^II–H and Si^II–Cl σ‐Bonds at Room Temperature