Contributions to group IV organometallic chemistry

Cragg, R. H.; Lane, Rob D.

doi:10.1016/0022-328x(84)80700-7

Cited by 19 publications

(3 citation statements)

References 6 publications

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“…The 29 Si and 13 C NMR resonances for the silyl portions of selected reactants and products are recorded in Tables and , respectively; all values are in accord with published data as referenced. − Additionally, mass spectral data for Me 3 SiC 6 H 4 - p- X (X = MeO, CF 3 , F, Me 2 N) are in total accord with literature values …”

Section: Methodssupporting

confidence: 74%

Formation of Silicon−Carbon Bonds by Photochemical Irradiation of (η⁵-C₅H₅)Fe(CO)₂SiR₃ and (η⁵-C₅H₅)Fe(CO)₂Me to Obtain R₃SiMe

et al. 2010

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Photochemical irradiation of an equimolar mixture of (η 5 -C 5 H 5 )Fe(CO) 2 SiR 3 , FpSiR 3 , and FpMe leads to the efficient formation of the silicon-carbon coupled product R 3 SiMe, R 3 = Me 3 , Me 2 Ph, MePh 2 , Ph 3 , ClMe 2 , Cl 2 Me, Cl 3 , Me 2 Ar (Ar = C 6 H 4 X, X = F, OMe, CF 3 , NMe 2 . Similar chemistry occurs with related germyl and stannyl complexes at slower rates, Si > Ge> ≫Sn. Substitution of an aryl hydrogen in FpSiMe 2 C 6 H 4 R′ has little effect upon the rate of the reaction whereas progressive substitution of methyl groups on silicon by Cl slows the process. Also changing FpMe to FpCH 2 SiMe 3 dramatically slows the reaction as does the use of (η 5 -C 5 Me 5 )Fe(CO) 2 derivatives. A mechanism involving the initial formation of the 16e -intermediate (η 5 -C 5 H 5 )Fe(CO)Me followed by oxidative addition of the Fe-Si bond, accounts for the experimental results obtained.

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Section: Methodssupporting

confidence: 74%

Formation of Silicon−Carbon Bonds by Photochemical Irradiation of (η⁵-C₅H₅)Fe(CO)₂SiR₃ and (η⁵-C₅H₅)Fe(CO)₂Me to Obtain R₃SiMe

et al. 2010

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“…The 1 H, 13 C, 19 F, and 29 Si NMR spectra of ( E )- 2a − g , ( E , E )- 3a − d , ( E )- 4d − g , and ( E )- 5 were measured to clarify their structures and coordination states of their silicon atoms. The 29 Si NMR chemical shifts (δ Si ) are summarized in Table and compared with those of the corresponding phenyl-substituted references (δ Si ‘). ,, In the 29 Si NMR spectra, each chemical shift of ( E )- 2a − g and ( E , E )- 3a,b is near those of the corresponding phenyl-substituted derivatives. The respective differences of the chemical shifts (Δδ Si = δ Si − δ Si ‘) between ( E )- 2a − g and the corresponding phenyl derivatives are less than 3 ppm.…”

Section: Nmr Spectral Propertiesmentioning

confidence: 99%

Reversible Photoswitching of the Coordination Numbers of Silicon in Organosilicon Compounds Bearing a 2-(Phenylazo)phenyl Group

et al. 2006

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Several organosilicon compounds bearing a 2-(phenylazo)phenyl group were synthesized from the corresponding chlorosilanes and 2-lithioazobenzene prepared by halogen-lithium transmetalation of 2-iodoazobenzene. Their structures were determined by (1)H, (13)C, (19)F, and (29)Si NMR spectra, UV-vis spectra, and X-ray crystallographic analyses. In the UV-vis spectra, silyl groups caused red shifts of both the n-pi and pi-pi transitions of the azo group compared with the transitions of the unsubstituted azobenzene. The E-isomers of the fluorosilanes showed an intramolecular interaction between a nitrogen atom of the azo group and the silicon atom, leading their intermediate structures between a distorted trigonal bipyramidal structure and a tetrahedral structure around the silicon atoms, which were revealed by the X-ray crystallographic analyses and the NMR spectra. On the other hand, silanes without fluorine atoms showed tetrahedral structures in the absence of such an interaction. The photoirradiation of the E-isomers of the fluorosilanes afforded reversibly the corresponding Z-isomers in good yields. The silicon atoms of the Z-isomers were found to be tetracoordinate in the absence of Si-N interactions by the (29)Si NMR spectra. The coordination numbers of the silicon atom of the fluorosilanes were reversibly switched between four and five by photoirradiation. These properties were compared to those of a tetrafluoro[2-(phenylazo)phenyl]silicate.

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“…This triplet might be assigned to an alkylation product of phenylsilane with trimethylaluminum as a component of MAO or with TIBA, both known as strong alkylating agents and available in excess amounts after the alkylation of the titanium compound as well. For an alkylation product of phenylsilane with trimethylaluminum, PhSiH 2 CH 3 , the 29 Si NMR shift at −36.80 ppm is known 17. The dehydrogenative coupling product of phenylsilane, PhH 2 SiSiH 2 Ph, for example, observable in the reaction of phenylsilane catalyzed by Cp 2 Ti(μ‐H)(μ‐HSiHPh)TiCp 2 , a reaction product of Cp 2 Ti(CH 3 ) 2 and phenylsilane in the absence of MAO and TIBA,18 can be excluded because of its 29 Si NMR triplet at −61.3 ppm 19…”

Section: Resultsmentioning

confidence: 99%

The influence of phenylsilane on the syndiotactic polymerization of styrene with ?5-pentamethylcyclopentadienyl titanium trifluoride

Schellenberg

Newman

2000

J. Polym. Sci. A Polym. Chem.

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The syndiotactic polystyrene polymerization activity of a fluorinated half‐sandwich complex, η5‐pentamethylcyclopentadienyl titanium trifluoride (Cp*TiF3), in the presence of relatively low amounts of methylalumoxane (MAO; MAO/Cp*TiF3 molar ratio = 200/1) and triisobutylaluminum, is significantly increased by the addition of phenylsilane in molar ratios to Cp*TiF3 ranging from about 300/1 to 600/1, if the phenylsilane is added to the monomer. Lower amounts of phenylsilane, such as a 100/1 molar ratio to Cp*TiF3, lead to a reduced polymerization activity in comparison with styrene without phenylsilane. A prereaction of phenylsilane with the catalyst mixture shows a behavior that is strongly dependent on the storage time of the composition and the temperature. A storage time of about 16 h is sufficient to reduce the polymerization conversion to about half of the original value. The results are discussed on the basis of a chain‐transfer reaction with phenylsilane and several catalyst complexes of different stabilities and activities, including an alkylation product of phenylsilane. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3476–3485, 2000

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Contributions to group IV organometallic chemistry

Cited by 19 publications

References 6 publications

Formation of Silicon−Carbon Bonds by Photochemical Irradiation of (η⁵-C₅H₅)Fe(CO)₂SiR₃ and (η⁵-C₅H₅)Fe(CO)₂Me to Obtain R₃SiMe

Formation of Silicon−Carbon Bonds by Photochemical Irradiation of (η⁵-C₅H₅)Fe(CO)₂SiR₃ and (η⁵-C₅H₅)Fe(CO)₂Me to Obtain R₃SiMe

Reversible Photoswitching of the Coordination Numbers of Silicon in Organosilicon Compounds Bearing a 2-(Phenylazo)phenyl Group

The influence of phenylsilane on the syndiotactic polymerization of styrene with ?5-pentamethylcyclopentadienyl titanium trifluoride

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Contributions to group IV organometallic chemistry

Cited by 19 publications

References 6 publications

Formation of Silicon−Carbon Bonds by Photochemical Irradiation of (η5-C5H5)Fe(CO)2SiR3 and (η5-C5H5)Fe(CO)2Me to Obtain R3SiMe

Formation of Silicon−Carbon Bonds by Photochemical Irradiation of (η5-C5H5)Fe(CO)2SiR3 and (η5-C5H5)Fe(CO)2Me to Obtain R3SiMe

Reversible Photoswitching of the Coordination Numbers of Silicon in Organosilicon Compounds Bearing a 2-(Phenylazo)phenyl Group

The influence of phenylsilane on the syndiotactic polymerization of styrene with ?5-pentamethylcyclopentadienyl titanium trifluoride

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Formation of Silicon−Carbon Bonds by Photochemical Irradiation of (η⁵-C₅H₅)Fe(CO)₂SiR₃ and (η⁵-C₅H₅)Fe(CO)₂Me to Obtain R₃SiMe

Formation of Silicon−Carbon Bonds by Photochemical Irradiation of (η⁵-C₅H₅)Fe(CO)₂SiR₃ and (η⁵-C₅H₅)Fe(CO)₂Me to Obtain R₃SiMe