Assembly of NHC-stabilized 2-hydrophosphasilenes from Si(<scp>iv</scp>) precursors: a Lewis acid–base complex

Dhara, Debabrata; Mandal, Debdeep; Maiti, Avijit; Yildiz, Cem B.; Kalita, Pankaj; Chrysochos, Nicolas; Schulzke, Carola; Chandrasekhar, Vadapalli; Jana, Anukul

doi:10.1039/c6dt04321f

Cited by 19 publications

(17 citation statements)

References 52 publications

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“…Addition of a Lewis base to the donor‐stabilized phosphasilenes with four‐coordinate silicon might lead to a ligand exchange at the silicon atom. Quantitative ligand exchange in 42 to give the less sterically hindered complexes 42 c , d has been observed at room temperature (Scheme ) …”

Section: Reactivitymentioning

confidence: 99%

“…Hyperconjugation of the P ‐trimethysilyl group with phosphorus in 41 is responsible for an increased shielding of the P and Si atoms of the Si=P bond and some shortening of the Si=P bond length. The 1 J Si,P coupling constants increase in the following order: 40 < 41 < 43 < 42 , ranging from 120.7 Hz in 40 to 157.8 Hz in 42 (R= i Pr, Ar=Tip) …”

Section: Structure and Synthesismentioning

confidence: 99%

“…As discussed above, NHC‐stabilized Si ‐H phosphasilenes 40 – 43 (Figure ) display similar characteristic structural and electronic features. Compared to the phosphasilenes with three‐coordinate silicon, the Si−P bond lengths in 40 – 43 are elongated, ranging from 2.1459(17) Å in 41 to 2.1652(8) Å in 43 …”

Section: Structure and Synthesismentioning

confidence: 99%

“…A convenient and mild approach to NHC–phosphasilene complexes involves reaction of halogenosilyl‐substituted secondary phosphanes with two equivalents of NHCs . One equivalent of NHC acts as an organic base eliminating HCl and another equivalent is involved in complex formation.…”

Section: Structure and Synthesismentioning

confidence: 99%

“…One equivalent of NHC acts as an organic base eliminating HCl and another equivalent is involved in complex formation. This method has been successfully employed for the preparation of a number of 2‐hydroarylphosphasilene–NHC complexes 42 a – d and 2‐chlorophosphasilene 44 (Scheme ).…”

Section: Structure and Synthesismentioning

confidence: 99%

See 4 more Smart Citations

Advances in Phosphasilene Chemistry

Nesterov

Breit

Inoue

2017

Chemistry A European J

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Heavier alkene analogues possess unique electronic properties and reactivity,e ncouraging multidisciplinary research groups to utilize them in the rational designo fn ovel classes of compounds and materials.P hosphasilenes are heavier imine analogues,c ontaining highly reactiveS i =P double bonds. Recent achievements in this field are closely related to the progress in the chemistry of stable low-coordinate silicon compounds. In this Review,w eh avea ttempted to summarize in ac omprehensive way the availabled ata on the structures, syntheses, electronic andc hemical properties of these compounds, with an emphasis on recent achievements.

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Section: Reactivitymentioning

confidence: 99%

Section: Structure and Synthesismentioning

confidence: 99%

Section: Structure and Synthesismentioning

confidence: 99%

Section: Structure and Synthesismentioning

confidence: 99%

Section: Structure and Synthesismentioning

confidence: 99%

See 3 more Smart Citations

Advances in Phosphasilene Chemistry

Nesterov

Breit

Inoue

2017

Chemistry A European J

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Cleavage of a P=P Double Bond Mediated by N‐Heterocyclic Carbenes

et al. 2017

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The reaction of the bulky diphosphenes (Rind)P=P(Rind) (1; Rind=1,1,3,3,5,5,7,7‐octa‐R‐substituted s‐hydrindacen‐4‐yl) with two molecules of N‐heterocyclic carbene (NHC; 1,3,4,5‐tetramethylimidazol‐2‐ylidene) resulted in the quantitative formation of the NHC‐bound phosphinidenes NHC→P(Rind) (2), along with the cleavage of the P=P double bond. The reaction times are dependent on the steric size of the Rind groups (11 days for 2 a (R=Et) and 2 h for 2 b (R=Et, Me) at room temperature). The mechanism for the double bond‐breaking is proposed to proceed via the formation of the NHC‐coordinated, highly polarized diphospehenes 3 as an intermediate. Approach of a second NHC to 3 induces P−P bond cleavage and P−C bond formation, which proceeds through a transition state with a large negative Gibbs energy change to afford the two molecules of 2, thus being the rate‐determining step of the overall reaction with the activation barriers of 80.4 for 2 a and 29.1 kJ mol−1 for 2 b.

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Ein dreigliedriges cyclisches Phosphasilen

Heider¹,

Willmes²,

Mühlhausen³

et al. 2019

Angewandte Chemie

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Kleine ungesättigte Phosphorcyclen sind aufgrund ihrer Ringspannung und der zusätzlichen Funktionalitäten der Doppelbindung und des freien Phosphor‐Elektronenpaars vielseitige Reagenzien. Wir berichten hier über die Synthese und Isolierung des kleinstmöglichen, cyclischen Phosphasilens als stabiles Addukt mit einem N‐heterocyclischen Carben (NHC). Erste Reaktivitätsstudien zeigen, (a) dass der PSi2‐Ring mittels des freien Elektronenpaares am Phosphor ein kompetenter Ligand für das Fe(CO)4 Fragment ist und (b) dass die Abstraktion des NHCs mit BPh3 zu einer raschen Kopf‐Kopf‐ oder Kopf‐Schwanz‐Dimerisierung der PSi2‐Einheit führt. Die relativ leichte NHC‐Abspaltung deutet die Verfügbarkeit der P=Si‐Doppelbindung für weitere Manipulationen an.

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Assembly of NHC-stabilized 2-hydrophosphasilenes from Si(iv) precursors: a Lewis acid–base complex

Cited by 19 publications

References 52 publications

Advances in Phosphasilene Chemistry

Advances in Phosphasilene Chemistry

Cleavage of a P=P Double Bond Mediated by N‐Heterocyclic Carbenes

Ein dreigliedriges cyclisches Phosphasilen

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