Thermolysis of methoxy-substituted polysilanes

Atwell, William H.; Weyenberg, Donald R.

doi:10.1016/s0022-328x(00)85171-2

Cited by 66 publications

(25 citation statements)

References 7 publications

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“…The pathway to the trisilane 4 is believed to proceed by extrusion of 1 from 2 (a-elimination [23,24]) and concomitant insertion of 1 into the Si-Cl bond of the intermediate (NN)Si(Cl)-SiCl 3 (Scheme 4). Similar silylene extrusions were observed when the disilanes (NN)Si(X)-(R)Si(NN) (X = Cl or Br, R = alkyl) where heated [9].…”

Section: Resultsmentioning

confidence: 99%

The stable silylene Si[(NCH2But)2C6H4-1,2]: Reactions with Group 14 element halides

Gehrhus

Hitchcock

Jansen

2006

Journal of Organometallic Chemistry

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Section: Resultsmentioning

confidence: 99%

The stable silylene Si[(NCH2But)2C6H4-1,2]: Reactions with Group 14 element halides

Gehrhus

Hitchcock

Jansen

2006

Journal of Organometallic Chemistry

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“…It is not an overstatement that the 1966 discovery by Atwell and Weyenberg that the 1,2-shift of methoxy groups in disilanes takes place under relatively mild conditions ushered in the use of silylenes as synthetic reagents 9 . The ease of elimination, alkoxy > hydrogen > chlorine, has been measured quantitatively 10 .…”

Section: A Thermolysis Of Polysilanesmentioning

confidence: 99%

Silylenes

Gaspar¹,

West²

2009

Patai's Chemistry of Functional Groups

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Introduction Generation of Silylenes Reactions of Silylenes Theoretical Calculations Spectroscopic Characterization of Silylenes Kinetics of Silylene Reactions Silylene–Transition Metal Complexes Special Topics Speculations on the Future of Silylene Chemistry

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“…The thermolysis of niethoxypolysilanes has been reported to produce divalent organosilico~i (silylene) species (1,2). It seemed possible that a-alkoxyalkylmonosilanes might similarly ~lnder-go this sort of reaction to produce carbenes, and indeed, since this work was completed, Atwell et al have reported such behavior on therrnolysis of (di1netlioxyniethy1)trimethoxysilaiie (3).…”

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confidence: 88%

Alkoxycarbenes from the thermolysis of silyl ketals

Brook¹,

Dillon²

1969

Can. J. Chem.

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It is shown that a,a-dimethoxybenzylsilancs thermally rearrange to give methoxysilanes and phenylmcthoxycarbene; the latter species has been trappcd by a variety of reagents. The rcarrangcment involves rctcntion of config~~ration at an asymmetric silicon center. Whilc a,a-dimctlioxycthylsilancs eliminate methanol when heated, metlioxybenzhydrylsilancs rcarrangc to methoxysilane and diphcnylcarbene b~~i ~~~onorncthoxybenzylsilanes or 2-silyldioxolancs do not thermally rearrange up to 250".Czinadian Journal of Chemistry, 47, 4347 (1969) The thermolysis of niethoxypolysilanes has been reported to produce divalent organosilico~i (silylene) species (1,2). It seemed possible that a-alkoxyalkylmonosilanes might similarly ~lnder-go this sort of reaction to produce carbenes, and indeed, since this work was completed, Atwell et al. have reported such behavior on therrnolysis of (di1netlioxyniethy1)trimethoxysilaiie (3). a-Alkoxyalkylsilanes are generally difficult to synthesize, but a convenient source was found to be the ketals 1 of acylsilancs, which could be prepared either rrom tlie dithiane precursors (4,5) of the acylsilancs by reaction in methanol over several days with a ~n i x t~~r e of mercuric prepared from the acylsilanes and ethylene glycol i n hot clilor~form containing boron trifluoride ethcratc. Attempts to prepare simple ketals using boron trifluoride etlierate and alcohols were not successful. Details of tlie c o n i p o~~n d s prepared will be found in the Experimental section.While tlie dioxolanes of acetyl and benzoyltriphenylsilane were thermally stable to at least 250°, it was found that the dimethoxy ketals, when pyrolyzed at 150-20O0, readily decoliiposed in one of two ways. Where there was hydrogen a to the carbon bearing the alkoxy groups, e.g. l b , methanol was thermally eliminated and an en01 ether was formed. This type of reaction has been For personal use only.

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Thermolysis of methoxy-substituted polysilanes

Cited by 66 publications

References 7 publications

The stable silylene Si[(NCH2But)2C6H4-1,2]: Reactions with Group 14 element halides

The stable silylene Si[(NCH2But)2C6H4-1,2]: Reactions with Group 14 element halides

Silylenes

Alkoxycarbenes from the thermolysis of silyl ketals

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