Synthesis of Boryl-Substituted Disilane, Disilene, and Silyl Cation

Liu, Zhaocai; Zhang, Jianying; Yang, Hao; Cui, Chunming

doi:10.1021/acs.organomet.0c00148

Cited by 19 publications

(20 citation statements)

References 54 publications

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“…Protection from NHCs is a developed approach to synthesize stable multiple bonded compounds. Recently, Frenking, jones and co-workers (in 2009) [34] and Yim, So and co-workers (in 2013) [35] for the first time isolated NHC stabilized dimeric germanium(0) complex (28) and NHSi ligands stabilized germanium(0) dimer {: Ge=Ge :} complex (29), respectively ( Figure 1).…”

Section: Digermenes (> Ge=gementioning

confidence: 98%

“…The charge separation was further supported by natural population analysis, having a negative charge on Si atom (À 0.268) and a positive charge on B atom (+ 0.357). Also, the large up-field shift of the 29 Si resonance of the sp 2 Si atom pointed towards the contribution from > Si À B=N + < , another charge-separated resonance structure. The crystal structure showed a bond length of 1.8379 (17) Å between silicon and boron atom, which is about 10% shorter than the typical SiÀ B single bond length of silylboranes (2.038-2.1249 Å), showing the double bond character.…”

Section: Silaborenes (> Si=bà )mentioning

confidence: 99%

“…To study the substituent effect, Cui et al [29] performed the chemical reduction of (boryl)SiBr 2 R (R=H, Ph). Reduction of (boryl)SiPhBr 2 (26) with 2 equiv.…”

Section: Disilenes (> Si=simentioning

confidence: 99%

“…Recent developments showed that the boryl ligands (predominantly (HCDippN) 2 B; Dipp = 2,6-i Pr 2 C 6 H 3 ) [28a,b] can also be used for the stabilization of disilenes (Si=Si). [26,29] By using these boryl ligands, Aldridge et al [36] synthesized the first group 14 vinylidene compound, (boryl) 2 Ge=Ge. When [(HC(MeCMesN) 2 )Mg] 2 (Mes = 2,4,6-Me 3 C 6 H 2 ) was reacted with (NHC)-stabilized (boryl)germanium(II) chloride (30) gave unsymmetrical mono NHC-stabilized digermyne complex (31), whereas excess potassium metal (or KC 8 ) generated highly reduced formally Ge(0) compound, (32;Scheme 14).…”

Section: Digermenes (> Ge=gementioning

confidence: 99%

“…The 11 B NMR showed a broad signal at δ = + 87.7 ppm. The 29 Si NMR showed two resonances at δ = + 23.3 and at δ = À 128.1 ppm which were due to t Bu 2 MeSi and unsaturated silicon skeletal atom, respectively. The large variation in chemical shift might be due to the reversed bond polarization (> Si δÀ =B δ + À ), presence of two electropositive t Bu 2 MeSi groups on sp 2 silicon atom and electronegative tmp group (tmp = 2,2,6,6-tetramethylpiperidino) on sp boron atom.…”

Section: Silaborenes (> Si=bà )mentioning

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: 98%

Section: Silaborenes (> Si=bà )mentioning

confidence: 99%

“…To study the substituent effect, Cui et al [29] performed the chemical reduction of (boryl)SiBr 2 R (R=H, Ph). Reduction of (boryl)SiPhBr 2 (26) with 2 equiv.…”

Section: Disilenes (> Si=simentioning

confidence: 99%

Section: Digermenes (> Ge=gementioning

confidence: 99%

Section: Silaborenes (> Si=bà )mentioning

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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Synthesis of an N‐Heterocylic Boryl‐Stabilized Disilyne and Its Application to the Activation of Dihydrogen and C−H Bonds

Ding

Zhang

et al. 2022

Angewandte Chemie

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The synthesis of low-valent silicon compounds that enable the activation of small molecules has been of great current interest. Reduction of N-heterocyclic boryltribromosilane (NHB)SiBr 3 (2, NHB = [ArN(CMe) 2 NAr]B, Ar = 2,6-iPr 2 C 6 H 3 ) with three equiv. of lithium in diethyl ether yielded the NHBstabilized disilyne (NHB)Si�Si(NHB) (3). Disilyne 3 slowly reacted with toluene, leading to the activation of one benzylic CÀ H bond and one C=C double bond with the formation of 4. Treatment of 3 with dihydrogen under 1 atm at room temperature resulted in the exclusive formation of the first boryl-stabilized 1,2dihydrodisilene. Compounds 3-5 have been characterized by single-crystal X-ray diffraction studies, which indicated the co-planarity of the BÀ SiÀ SiÀ B plane with the NHB rings in compounds 3 and 5. DFT calculations indicated the significant π electron delocalization of the SiÀ Si multiple bonds to the BÀ N bonds in NHB rings.

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Geometrically Compelled Silicon(II)/Silicon(IV) Donor–Acceptor Interaction Enables the Enamination of Nitriles

Kong,

Li,

Dai

et al. 2023

Angewandte Chemie

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Discovering new bonding scenarios and subsequently exploring the reactivity contribute substantially to advance the main group element chemistry. Herein, we report on the isolation and characterization of an intriguing class of the hydrido‐benzosiloles 2–4. These compounds exhibit a side arm of the amidinatosilylenyl group, featuring unidirectional silicon(II)/silicon(IV) donor‐acceptor interaction on account of the geometric constraint. Furthermore, the reactions involving 2–4 with nitriles yield the tricyclic compounds that edge‐fused of the Si‐heteroimidazolidine‐CN2Si2, silole‐C4Si, and phenyl‐C6‐rings (5–13). These compounds are manifesting a unique reaction that the silicon(II)/silicon(IV) interaction enables the enamination of the α‐H‐bearing nitriles. The reaction mechanism involved in H‐shift under oxidative addition at silylene followed by hydrosilylation of a ketenimine intermediate was revealed by density function theory (DFT) calculations.

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Synthesis of Boryl-Substituted Disilane, Disilene, and Silyl Cation

Cited by 19 publications

References 54 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

Synthesis of an N‐Heterocylic Boryl‐Stabilized Disilyne and Its Application to the Activation of Dihydrogen and C−H Bonds

Geometrically Compelled Silicon(II)/Silicon(IV) Donor–Acceptor Interaction Enables the Enamination of Nitriles

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