Reactions of a carbosilylated methylenephosphonium ion with π-conjugated hydrocarbons

Thomaier, Jörg; Alcaraz, Gilles; Hillebrecht, Harald; Marchand, Christina; Heim, Udo

doi:10.1016/s0022-328x(96)06960-4

Cited by 15 publications

(8 citation statements)

References 16 publications

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“…A The distances of the C2(7)xC3(6) bonds [1.401(5) belong-A ] ing to the annulated benzo groups, as well as to the tropylidene ring, are typical for conjugated arene CxC bonds. The remaining two [C1wC2 (7)] bonds connecting the arene ring with the bow-carbon center of the seven-membered ring [1.514(4), 1.521 (4) correspond to CwC single bonds. These A ] structural features are found in the structures of all compounds discussed in this work.…”

Section: Resultsmentioning

confidence: 99%

Dibenzotropylidene phosphanes (TROPPs): synthesis and coinage metal complexes

Thomaier¹,

Boulmaâz²,

Schönberg³

et al. 1998

New J. Chem.

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Section: Resultsmentioning

confidence: 99%

Dibenzotropylidene phosphanes (TROPPs): synthesis and coinage metal complexes

Thomaier¹,

Boulmaâz²,

Schönberg³

et al. 1998

New J. Chem.

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“…Iminium salts are of utmost importance in organic synthesis,1 owing in particular to their key role as intermediates in many enantioselective organocatalytic transformations of carbonyl compounds 2. However, the synthetic utility of their phosphorus analogues, methylenephosphonium ions,3, 4 remains limited to a few examples of [2+2]4h,j and [2+4]4b,e,g cycloaddition, the ene reaction,4b,e electrocyclic cyclization with an arene ring,4e,f stereoselective rearrangement to give phosphaalkenes,4d and the phospha‐Stork reaction 4l. Whereas the reactivity of iminium salts is governed by the strong electrophilicity of the carbon atom (Scheme ), the methylenephosphonium salts undergo regioselective addition of nucleophiles (Nu=F − , Cl − , and MeO − )3a,b, 4a at the electropositive phosphorus center (Scheme ).…”

Section: Methodsmentioning

confidence: 99%

Designed Single‐Step Synthesis, Structure, and Derivative Textural Properties of Well‐Ordered Layered Penta‐coordinate Silicon Alcoholate Complexes

Michaelis

Ong

et al. 2014

Chemistry A European J

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The controllable synthesis of well-ordered layered materials with specific nanoarchitecture poses a grand challenge in materials chemistry. We report the solvothermal synthesis of two structurally analogous 5-coordinate organosilicate complexes via a novel transesterification mechanism. Since the polycrystalline nature of the intrinsic hypervalent Si complex thwarts the endeavor in determining its structure, a novel strategy concerning the elegant addition of a small fraction of B species as an effective crystal growth mediator and a sacrificial agent is proposed to directly prepare diffraction-quality single crystals without disrupting the intrinsic elemental type. In the determined crystal structure, two monomeric primary building units (PBUs) self-assemble into a dimeric asymmetric secondary BU via strong Na+-O2− ionic bonds. The designed one-pot synthesis is straightforward, robust, and efficient, leading to a well-ordered (10ī)-parallel layered Si complex with its principal interlayers intercalated with extensive van der Waals gaps in spite of the presence of substantial Na+ counterions as a result of unique atomic arrangement in its structure. On the other hand, upon fast pyrolysis, followed by acid leaching, both complexes are converted into two SiO2 composites bearing BET surface areas of 163.3 and 254.7 m2 g−1 for the pyrolyzed intrinsic and B-assisted Si complexes, respectively. The transesterification methodology merely involving alcoholysis but without any hydrolysis side reaction is designed to have generalized applicability for use in synthesizing new layered metal-organic compounds with tailored PBUs and corresponding metal oxide particles with hierarchical porosity.

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“…With transient 2n , which is located electronically between 2e,f , both types of adducts 14n and 15n were isolated . Note that 2f also reacts with dimethylfulvene and anthracene, affording the Diels−Alder adducts 16f and 16 ‘ f , respectively (Figure ) 6 Ene and Diels−Alder reactions involving methylenephosphonium salts. …”

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confidence: 97%

“…According to calculations,22b 10 is 120 and 260 kJ mol -1 higher in energy than the ylide and the phosphine, respectively, which makes the characterization of the carbodiphosphorane 10 rather surprising (eq 11). Also noteworthy is the reaction of 2f with an excess of AlCl 3 , which afforded the adduct 11 , formally resulting from the addition of Cl - at phosphorus and Al 2 Cl 6 to the negatively charged carbon center (eq 12) …”

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confidence: 99%