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• W1979848497 abstract "The monomeric lithium (fluorosilyl)phosphanides Is2Si(F)P[LiLn]R (1) (Is = 2,4,6-triisopropylphenyl; L = THF, n = 2, 3; R = SiiPr3 (a), SiMe3 (b), SitBuMe2 (c), SiPh2Me (d), SiPh3 (e), Si(Naph)3 (f), SitBu2H (g), GetBu2H (h, L = DME, n = 1)) and the related lithium (fluorosilyl)arsanides Is2Si(F)As[Li(THF)2]R (3) (R = SiiPr3 (a), SiPh2Me (b), SiCy2Me (c, Cy = cyclohexyl)) eliminate LiF and THF (DME) upon heating to give the corresponding silylidenephosphanes and -arsanes 2 and 4, respectively. The reactivity of the SiE bonds (E = P (2a), As (4a)) toward P4, elemental sulfur, and tellurium is very similar and leads to the corresponding 1,2,3-triphospha-4-silabicyclo[1.1.0]butane (12) and to two isomers of arsadiphosphasilabicyclo[1.1.0]butanes, namely 1-(triisopropylsilyl)-4,4-diisityl-1-arsa-2,3-diphospha-4-silabicyclo[1.1.0]butane (13) and 3-(triisopropylsilyl)-4,4-diisityl-1-arsa-2,3-diphospha-4-silabicyclo[1.1.0]butane (14), respectively. The reaction of S8 and Te with 2a gives rise to the corresponding silaphosphathia- and telluracyclopropanes 16 and 17, respectively. The reaction of 2a with phenylacetylene yields Is2Si(C⋮CPh)PH(SiiPr3) (18), and benzonitrile reacts with 2g and 4c to give the [2 + 2]-cycloadducts Is2SiE(SiR3)C(Ph)N (E = P (19), E = As (20)). Only 4c reacts with tert-butylphosphaacetylene to give Is2SiAs(SiCy2Me)PC(tBu) (43). 2a reacts with cyclopentadiene to provide the expected hetero Diels−Alder product (22). The reaction of 2a with benzophenone leads to the corresponding 2,1,3-silaphosphaoxetane (23), and treatment of 2a with 1,2-diphenyl-1,2-diketone unexpectedly provides the [2 + 2]-cycloadduct Is2SiP(SiiPr3)C(Ph)(COPh)O (27) as the thermodynamic product. The 2,4-di-tert-butyl-o-quinone solely yields the [2 + 4]-cycloadduct Is2SiP(SiiPr3)O(aryl)O (aryl = 2,4-di-tert-butylphenylene) (31). The cycloaddition reactions of 2a and 4a with diphenyldiazomethane, mesityl azide, and mesityl isocyanide were also investigated, and the respective [2 + n]-cycloadducts (n = 1, 2, 3) were characterized by means of NMR spectroscopy. For example, 4a reacts with diphenyldiazomethane to give the [2 + 1]-cycloadduct Is2SiAs(SiiPr3)NNCPh2 (29). The structures of 1h, 20, 23, and 29 were determined by X-ray crystallography." @default.
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• W1979848497 date "1996-04-02" @default.
• W1979848497 modified "2023-10-14" @default.
• W1979848497 title "Synthesis and Unusual Reactivity of Compounds Containing Silicon−Phosphorus and Silicon−Arsenic Double Bonds: New Silylidenephosphanes and -arsanes of the Type R₂SiE(SiR₃) (E = P, As)" @default.
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• W1979848497 doi "https://doi.org/10.1021/om9508851" @default.
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