Organosubstituierte 2,5‐Dihydro‐1,2,5‐selenasilaborole – Herstellung, Charakterisierung und π‐Komplexierung

Köster, Roland; Seidel, Günter; Boese, Roland; Wrackmeyer, Bernd

doi:10.1002/cber.19881211111

Cited by 50 publications

(3 citation statements)

References 33 publications

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“…Although 77 Se NMR spectroscopy is a convenient and versatile method for characterizing selenium compounds, 77 Se NMR data for polyhedral boranes are extremely rare. To the best of our knowledge, the only example to have been reported, apart from some selenaborole derivatives, , is [H 3 B-μ 2 -Se(B 2 H 5 )] - , for which δ( 77 Se) = −473.8 . A 77 Se chemical shift in a similar region is predicted for 4 [δ = −122 for the GIAO-MP2/962+(d)//MP2/962(d) level; for HF, δ = −282], and we note this value for future reference.…”

Section: Resultsmentioning

confidence: 59%

Molecular Structures of arachno-Decaborane Derivatives 6,9-X₂B₈H₁₀ (X = CH₂, NH, Se) Including a Gas-Phase Electron-Diffraction Study of 6,9-C₂B₈H₁₄

Hnyk¹,

Bühl

Holub³

et al. 2006

Inorg. Chem.

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The molecular structures of the three heterodecaboranes arachno-6,9-C2B8H14, arachno-6,9-N2B8H12, and arachno-6,9-Se2B8H10 have been determined by ab initio MO theory. In addition, the structure of arachno-6,9-C2B8H14 was experimentally determined using gas-phase electron diffraction (GED). The accuracy of all four of these structures has been confirmed by the good agreement of the (11)B chemical shifts calculated at the GIAO-MP2 level with the experimental values. A comparison of the GIAO-HF and GIAO-MP2 methods shows that for these heteroborane clusters, electron correlation effects on the computed delta((11)B) values are quite substantial and that it is necessary to go beyond the HF level in the NMR computation.

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Section: Resultsmentioning

confidence: 59%

Molecular Structures of arachno-Decaborane Derivatives 6,9-X₂B₈H₁₀ (X = CH₂, NH, Se) Including a Gas-Phase Electron-Diffraction Study of 6,9-C₂B₈H₁₄

Hnyk¹,

Bühl

Holub³

et al. 2006

Inorg. Chem.

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“…Some of the reaction products that could be identified by NMR spectroscopy are the corresponding imidazole‐2‐thione (IPr)S or imidazole‐2‐selenones (IMes)Se and (IPr)Se,, which indicates lability of the NHC–phosphorus bond. Furthermore, the formation of poly(phenylphosphinidenes) (PPh) n was observed by 31 P NMR spectroscopy during the reaction of 1b with selenium. The reaction of 1c with selenium in C 6 D 6 afforded a greenish solution, with several 31 P NMR spectroscopic signals between 83 and 120 ppm, indicating the formation of (PhP) 3 Se 2 and (PhP) 3 Se 3 (see the Supporting Information) , .…”

Section: Resultsmentioning

confidence: 99%

N‐Heterocyclic Carbene Adducts of Phenyldioxophosphorane and Its Heavier Sulfur and Selenium Analogues

et al. 2017

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The reactions of the N-heterocyclic carbene-phenylphosphinidene adducts (NHC)PPh with dioxygen, elemental sulfur or selenium are reported. For NHC = 1,3,4,5-tetramethylimidazolin-2-ylidene (IMe), the corresponding complexes (IMe)PE 2 Ph of phenyldioxophosphorane (PhPO 2 ), phenyldithioxophosphorane (PhPS 2 ) and phenyldiselenoxophosphorane (PhPSe 2 ) were isolated and fully characterised, including determination of their molecular structures by single-crystal X-ray diffraction analyses. For the adducts of the sterically more demanding carbenes 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-yl- [a]

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“…3200 cm-' (NaNH2-1 b). Die Verbindungen vom Typ 6 und 7 haben NH-Absorptionsbanden bei 3200-3350 (6) bzw. um 3450 cm-' (7).…”

Section: +unclassified

Organosubstituierte 2,5‐Dihydro‐1,2,5‐azasilaborole — Herstellungsmethoden und spektroskopische Charakterisierung

1989

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1825 Die Verbindungen (E)-RiR'EIwC(R3)=C(R4)BR$ [(E)-l a bis -g] stellt man aus Na[R$sBCrCR3] mit CIEI'''R~RZ' [El' ' = Si, Ge, Sn] oder aus R:R2'SiC=CR3 rnit BR?' (R4*5 = CHI, C6H5) her. Aus (CH3)2Si(C = CCH3)2 und B(C2H5), sind das substituierte Silo1 lz, aus (CH,),SiC=CH und B(C2HS), im Autoklaven u. a. (Z/E)-1 t zugsnglich. -CISi(CH3)2C(CH3)= C(C2HS)B(C2H5)CI (C) und LiN(CH& bilden (E)-ln. -(E)-la bis (E)-lg bzw. (E)-laGe und (E)-laSn reagieren mit MNH2 (M = Na, K) zu den Additionsverbindungen MNH2-1, aus denen unter R2H-Abspaltung die festen Alkalimetall-Heterocyclen M-2 gebildet werden. (E)-1 a und (E)-1 b liefern mit LiNH2 (E)-C2H5CH =CR?Si(CH3)3 (A, B). -' Aus M-2a bis M-2g erhalt man beim Erhitzen unter RSH (C2H&Abspaltung glatt M-3, die mit CH31 zu den Heterocyclen CH3NSi(CH3,R')C(R3) = C(R4)BRS (4a -0 reagieren. Die I-Phenyl-Derivate 59, b gewinnt man aus 4a, b mit Anilin. Aus M-tc,d sind mit HCI die Verbindungen 6c,d zuginglich, die unter C2H6-Abspaltung 7c, d liefern. Aus der 5-Chlor-Verbindung 4i stellt man die Heterocyclen 4 mit R5 = H, C(CH3), und N(CH3)* her. -Samtliche Verbindungen werden mit Multikern-NMR-Spektroskopie, die fliichtigen Verbindungen 1 und 4 -7 auch massenspektrometrisch charakterisiert.Die aus den substituierten Alkenen (E)-1 iiber die cyclischen Alkalimetall-Verbindungen M-2 und M-3 praparativ leicht zuganglichen, einfach ungesattigten Heterocyclen rnit E1SiC2B-Atomgruppierung [El = N2.3), P4), S5), Se6)] sind cycloenantiotope und mit ungleichen Si-Substituenten ( R2 # R2) cyclodiastereotope Verbindungen. Die q4-Verkniipfung der Ringverbindungen 4, 5 und 7 an einem ubergangsmetall-Fragment LM fiihrt zu Racematen cycloenantiomerer bzw. cyclodiastereomerer rr-K~rnplexe'~~'. 4,5-Diethyl-2,2,3-trimethyl-Derivate der Verbindungen LM-q4-ElSiC2B und M ( T~~-E~S~C~B )~ rnit El = S5), Se6), und P 12) wurden bereits beschrieben. Unter Abwandlung der Substituenten R2 bis R5 haben wir jetzt verschiedene neue organosubstituierte 2,5-Dihydro-l,2,5-azasilaborole vom Typ 4 und 5 hergestellt und berichten nachfolgend iiber die Ergebnisse, die auch die Herstellung der NH2-und NH-Verbindungen des Typs 6 und 7 einschlieoen. In der nachfolgenden Arbeit werden die (Ligand)ubergangsmetall-q4-~9 -1 1 ) Organosubstituted 2,5Dihydnr-l,Z~~S-rrzssilaboroles - Methods of Preparation and Speetroawpk Characterisation *f The compounds (E)"$R2'EI''C(R3)-C(R4)BR~ [(E)-la to -g] are prepared from Na[Rf5BC = CR3] with CIEI''R$R' [El'' = Si, Ge, Sn] or from R$R2'SiC=CR3 with BRl5 (R4sS = CHk C6H5). The substituted silo1 l z is obtained from (CHJ)~S~(C=CCH& and B(C2H5)3, the mixture of (Z/E)-1 t from (CH3hSiC E CH and B(C2HS)3. -CISi(CH3)2C(CH3) = C(C2Hs)B(C2H5)CI (C) reacts with LiN(CHJ2 to form (CH3)2NSi(CH3)2C(CH3) = C(C2Hs)-B(C2Hs)N(CHJ2 (E)-ln. -@)-la to (E)-lg or (E)-laGe and (E)-laSn add MNHz (M = Na, K) to yield the compounds MNH2-1, which react to the solid alkaline metal heterocycles M-2 after liberating R2H. From. (E)-1 a or (E)-1 b with LiNHl the compounds (E)-C2H5CH = CR4SSi(CH3), (A, B) are obtained. ...

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Organosubstituierte 2,5‐Dihydro‐1,2,5‐selenasilaborole – Herstellung, Charakterisierung und π‐Komplexierung

Cited by 50 publications

References 33 publications

Molecular Structures of arachno-Decaborane Derivatives 6,9-X₂B₈H₁₀ (X = CH₂, NH, Se) Including a Gas-Phase Electron-Diffraction Study of 6,9-C₂B₈H₁₄

Molecular Structures of arachno-Decaborane Derivatives 6,9-X₂B₈H₁₀ (X = CH₂, NH, Se) Including a Gas-Phase Electron-Diffraction Study of 6,9-C₂B₈H₁₄

N‐Heterocyclic Carbene Adducts of Phenyldioxophosphorane and Its Heavier Sulfur and Selenium Analogues

Organosubstituierte 2,5‐Dihydro‐1,2,5‐azasilaborole — Herstellungsmethoden und spektroskopische Charakterisierung

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Organosubstituierte 2,5‐Dihydro‐1,2,5‐selenasilaborole – Herstellung, Charakterisierung und π‐Komplexierung

Cited by 50 publications

References 33 publications

Molecular Structures of arachno-Decaborane Derivatives 6,9-X2B8H10 (X = CH2, NH, Se) Including a Gas-Phase Electron-Diffraction Study of 6,9-C2B8H14

Molecular Structures of arachno-Decaborane Derivatives 6,9-X2B8H10 (X = CH2, NH, Se) Including a Gas-Phase Electron-Diffraction Study of 6,9-C2B8H14

N‐Heterocyclic Carbene Adducts of Phenyldioxophosphorane and Its Heavier Sulfur and Selenium Analogues

Organosubstituierte 2,5‐Dihydro‐1,2,5‐azasilaborole — Herstellungsmethoden und spektroskopische Charakterisierung

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Molecular Structures of arachno-Decaborane Derivatives 6,9-X₂B₈H₁₀ (X = CH₂, NH, Se) Including a Gas-Phase Electron-Diffraction Study of 6,9-C₂B₈H₁₄

Molecular Structures of arachno-Decaborane Derivatives 6,9-X₂B₈H₁₀ (X = CH₂, NH, Se) Including a Gas-Phase Electron-Diffraction Study of 6,9-C₂B₈H₁₄