Insertion reactions of thermally generated stannylenes R2Sn into Sn-X (X = Cl, Br, SPh) and Sn-Sn bonds

Gross, Lutz-Werner; Moser, R.; Neumann, Wilhelm P.; Scherping, Karl-Heinz

doi:10.1016/s0040-4039(00)86909-9

Cited by 31 publications

(10 citation statements)

References 11 publications

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“…In each we observe reaction resulting in the production of two fluorosilanes obtained by the migration of an R or methyl group to the chloromethyl moiety with loss of chloride. In all of these com- Me2RSiCH2Cl R = Me3SiCH2 (7) a large number of products; these were not characterized R = Me3SiO (8) no reaction with KF; many products with CsF R = CH2C1 (9) yields Me2SiF, and CH2=CH, Me3SiX X = CH2CH2CH2C1 (10) no reaction with KF or CsF X = CHC12 (11) yields Me3SiF and CH2C12 X = CHC1CH3 (12) no reaction with KF or CsF "All results were determined by GC and GC-MS. pounds except Me3SiCH2Cl there is a competition between two potential migrating groups (eq 1). Our earlier report1 Me2RSiCH,Cl---Me2(RCH2)SiF + MeREtSiF " 18-crown-6 (i) suggested that the major factor controlling migration was the ability of the migrating group to support the negative charge generated in the transition state.…”

Section: Resultsmentioning

confidence: 99%

“…We have explored other substitution patterns in the silane reaction with KF (Table II). We see examples of rearrangement (compound 9) and cleavage (compound 11) as well as very complex reaction where we have not attempted to sort out the products (compound 7) and no reaction (compounds 8,10, and 12). We have observed no product which would result from F" substitution of any (chloroalkyl)silane.…”

Section: Discussionmentioning

confidence: 99%

“…These two products, derived from Me and R migration, respectively, had almost identical retention times, and some care was required for analysis. Generally, we were able to use packed gc columns although these mixtures were also analyzed by capillary (9) Seyferth, D.; Kógler, . P. J. Inorg.…”

Section: Methodsmentioning

confidence: 99%

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Fluoride-ion-induced rearrangements of chloromethyl-substituted silanes

Damrauer¹,

Yost²,

Danahey³

et al. 1985

Organometallics

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Fluoride ion solubilized by 18-crown-6 has been reacted in aromatic solvents like toluene, o-xylene, and mesitylene with a variety of chloromethyl-and chloroalkyl-substituted silanes. Although both rearrangement and cleavage reactions have been demonstrated, this paper mainly deals with the effect of substituents on the rearrangement. In the case of some substituents like vinyl and aryl ones, secondary reactions occur. These are shown to result from the reaction of RCH2", where R = vinyl and aryl, and primary products like Me2(RCH2)SiF. Hammett relative reactivity studies are used to probe the details of both the primary and secondary reactions and demonstrate that for the primary reaction pentacoordination followed by rearrangement is controlled by substituents capable of supporting negative charge. To a greater extent this is also true of the secondary reaction substituent effects.

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Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

See 1 more Smart Citation

Fluoride-ion-induced rearrangements of chloromethyl-substituted silanes

Damrauer¹,

Yost²,

Danahey³

et al. 1985

Organometallics

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“…Thus, formation of the ansa tristanna tungsten complex 13 by insertion of Me 2 Sn into the Sn−Sn bond with concomitant relief of molecular strain appears plausible, as depicted in the left section of Scheme . This notion is further supported by the known reactivity of stannylenes with respect to insertion reactions into Sn−X and Sn−Sn bonds …”

Section: Resultsmentioning

confidence: 82%

Half-Sandwich Tungsten Complexes with Metal- and η⁵-Cyclopentadienyl-Bound Functional Stannyl Groups and Their Transformation into Ansa Complexes

et al. 2010

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We report the introduction of two stannyl groups into a half-sandwich tungsten complex and their subsequent functionalization in order to generate useful precursors for the formation of diverse ansatype tungsten complexes. Bis-stannylation is achieved by treatment of the dilithiated species Li-[W(η 5 -C 5 H 4 Li)(CO) 3 ] (7) with 2 equiv of Me 3 SnCl, yielding [{Me 3 Sn(η 5 -C 5 H 4 )}(OC) 3 W(SnMe 3 )] (8). Successive chlorination is achieved by use of Me 2 SnCl 2 and SnCl 4 3 2OEt 2 and enables the selective formation of [{Me 3 Sn(η 5 -C 5 H 4 )}(OC) 3 W(SnMe 2 Cl)] ( 10), [{ClMe 2 Sn(η 5 -C 5 H 4 )}(OC) 3 -W(SnMe 2 Cl)] ( 11), and [{ClMe 2 Sn(η 5 -C 5 H 4 )}(OC) 3 W(SnMeCl 2 )] ( 12). The reaction of 11 with sodium amalgam gives a product mixture, consisting of the tristanna-bridged ansa complex [{η 1 -SnMe 2 -SnMe 2 -SnMe 2 -(η 5 -C 5 H 4 )}(CO) 3 W] (13) and the cyclic dinuclear tungsten compound [{Me 2 Sn-(η 5 -C 5 H 4 )}-(OC) 3 W] 2 ( 14). Ring closure of 12 was achieved upon reaction with Na 2 S to yield [{η 1 -Sn(Cl)Me-S-SnMe 2 -(η 5 -C 5 H 4 )}(CO) 3 W] (15), which displays a chiral, tungsten-bound tin center. All new compounds have been fully characterized by elemental analyses and, in solution, by IR and multinuclear NMR spectroscopy. The crystal structures of complexes 8, 11, 12, 14, and 15 were presented and discussed, showing Sn-W bond lengths of 2.8481(5) (8), 2.7586(3) (11), 2.7256(3) (12), 2.8180(3) ( 14), and 2.7662(2) A ˚(15).

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“…100 The reactivity of the X-H bond towards germylene insertion decreases in the following order: 100 The insertion of Me 2 Ge • • into the C-Br bond of PhCH 2 Br was studied in detail to reveal a two-step, radical abstraction-recombination process, supported by the observation of CIDNP effects. 1c Stannylenes R 2 Sn • •, albeit inert towards C-H and C-C bonds, can readily insert into weaker X-Y single bonds (X-Y = Sn-C, 103 Sn-Sn, 104 Sn-S, 104 Sn-Halogen, 1c,104 O-O 105 and S-S 105 ), thus forming the expected insertion products X-R 2 Sn-Y. 94b Similar radical pathways were suggested for the reactions of Me 2 Ge • • with CCl 4 , CCl 3 Br, PhCH 2 Cl and PhCH 2 I.…”

Section: Insertion Into Single Bondsmentioning

confidence: 99%

Heavy Analogs of Carbenes: Silylenes, Germylenes, Stannylenes and Plumbylenes

Lee

Sekiguchi

2010

Organometallic Compounds of Low‐Coordinate Si, Ge, Sn and Pb

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The Si-Si bonds of the oligo-or polysilanes chains can be cleaved upon photolysis in two ways, forming either silylenes or silyl radicals. 2 Thus, photolysis of both poly(di-nbutylsilane) and poly(di-n-hexylsilane) with shorter wavelength light [248 nm (pulsed) or 254 nm (CW)] resulted in both extrusion of silylenes R 2 Si • • (R = n-butyl or n-hexyl) trapped with Et 3 SiH and homolytic Si-Si bond cleavage, whereas only polysilyl radicals were observed upon irradiation with longer wavelength light (λ > 300 nm). 3 Among the most frequently used precursors for the photochemical generation of silylenes are trisilanes RR Si(SiMe 3 ) 2 , which readily eliminate hexamethyldisilane Me 3 Si-SiMe 3 to form the corresponding silylenes RR Si • •. Thus, diphenylsilylene Ph 2 Si • • was produced by irradiation of Ph 2 Si(SiMe 3 ) 2 along with the by-products formed from the isomeric silatriene (Scheme 4.1). 4

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Insertion reactions of thermally generated stannylenes R2Sn into Sn-X (X = Cl, Br, SPh) and Sn-Sn bonds

Cited by 31 publications

References 11 publications

Fluoride-ion-induced rearrangements of chloromethyl-substituted silanes

Fluoride-ion-induced rearrangements of chloromethyl-substituted silanes

Half-Sandwich Tungsten Complexes with Metal- and η⁵-Cyclopentadienyl-Bound Functional Stannyl Groups and Their Transformation into Ansa Complexes

Heavy Analogs of Carbenes: Silylenes, Germylenes, Stannylenes and Plumbylenes

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Insertion reactions of thermally generated stannylenes R2Sn into Sn-X (X = Cl, Br, SPh) and Sn-Sn bonds

Cited by 31 publications

References 11 publications

Fluoride-ion-induced rearrangements of chloromethyl-substituted silanes

Fluoride-ion-induced rearrangements of chloromethyl-substituted silanes

Half-Sandwich Tungsten Complexes with Metal- and η5-Cyclopentadienyl-Bound Functional Stannyl Groups and Their Transformation into Ansa Complexes

Heavy Analogs of Carbenes: Silylenes, Germylenes, Stannylenes and Plumbylenes

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Half-Sandwich Tungsten Complexes with Metal- and η⁵-Cyclopentadienyl-Bound Functional Stannyl Groups and Their Transformation into Ansa Complexes