• 분석과학
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• 제7권3호
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• pp.321-327
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• 1994

7, 7-dimethyl-1, 2, 3, 4, 5-pentaphenyl-7-silanorbornadiene을 과량의 methyl alcohol과 함께 저온 열분해반응을 시켰을 때 무색 침상 모양의 결정인 1-methoxydimethylsilyl-1, 2, 3, 4, 6-pentaphenylcyclohexa-2, 5-diene이 생성되었다. 그러나 7-silanorbornadiene을 ethyl alcohol과 함께 동시 광분해반응을 시켰을 때는 silylene이 생성되어 ethyl alcohol의 O-H 결합에 삽입 반응된 ethoxydimethylsilane이 생성되었다. 이와 같은 결과로 판단해 볼 때 7-silanorbornadiene의 저온 열분해반응과 광분해반응의 반응 메카니즘이 다르다는 사실을 알았다.

• Journal of Photoscience
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• 제1권2호
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• pp.119-122
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• 1994

$PdCI_2(PPh_3)_2$-catalyzed photolysis of 1-phenyl-4-(pentamethyldisilanyl)buta-1,3-diyne (1) in dry benzene gives 1,4-disilacyclohexa-2,5-diene type dimerization products(3-6) via silacyclopropene. The silacyclopropene is formed from the singlet excited state of 1 and this silacyclopropene reacts with $(PPh_3)_2Pd^0$to form palladasilacyclobutene. In this reaction, the silylene-palladium complex is generated and reacts with 1 to give another silacyclopropene. $PdCI_2(PPh_3)_2$catalyzed photolysis of 1 with other alkynes supports the involvement of this silylene complex.

• Bulletin of the Korean Chemical Society
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• 제15권12호
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• pp.1103-1107
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• 1994

Interaction of triethylsilane and diphenylsilane ($Ph_2$$SiH_2$, $Ph_2$$SiD_2$) with the surfaces of rhodium has been examined by trapping the reaction intermediates with 2,3-dimethyl-l,3-butadiene. 1,4-Hydrosilylation of the diene is predominantly observed to occur under mild condition over the rhodium catalyst. It is inferred from the product analyses that silylene and silyl radicals bonded to rhodium surfaces are the intermediates for addition of silylene to the diene, and for 1,4-hydrosilylation, respectively.

• 대한화학회지
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• 제60권2호
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• pp.149-153
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• 2016

• 한국섬유공학회:학술대회논문집
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• 한국섬유공학회 1987년도 제2차학술발표초록집
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• pp.65-65
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• 1987

• Bulletin of the Korean Chemical Society
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• 제15권6호
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• pp.460-465
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• 1994

New silicon-monosubstituted (${\eta}^4$-2,3,4,5-tetraphenyl-l-silacyclopentadiene)transi tion metal complexes are described. (7-Alkyl-7-silanorbornadienyl)MLn(Alkyl=Methyl: MLn=CpRu$(CO)_2$: Alkyl=Methyl: MLn=CpNi(CO): Alkyl=Ethyl: MLn=CpNi(CO)) complexes were prepared from the corresponding silole-transition metal complexes with dimethylacetylenedicarboxylate. Cycloaddition products were obtained with 2,3-dimethyl-1,3-butadiene, 2,3-butanedione, and 1,4-benzoquinone through the ruthenium-substituted silylene. We have determined the crystal structure of (1-methyl-2,3,4,5-tetraphenyl-l-silacyclopentadien yl)cyclopentadienyldicarbonylruthenium by using graphite monochromated Mo-Ka radiation. The compound was crystallized in the monoclinic space group $P2_{1/c}$ with a = 9.838(l), b = 15.972(3), c = 18.327(3) ${\AA}$, and ${\beta}= 94.28(l)^{circ}$. The ruthenium moiety CpRu$(CO)_2$ on silicon is in an axial position.

• 한국고분자학회:학술대회논문집
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• 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
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• pp.223-223
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• 2006

A Suzuki-coupling route is developed for preparation of ortho-phenylene-bridged Cp/amido complexes, one of which shows higher activity, higher 1-hexene incorporation, and higher molecular weight than the silylene-bridged standard CGC $[Me_{2}Si({\eta}^{5}-Me_{4}Cp)(N^{t}Bu)]TiCl_{2}$.

• 대한화학회지
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• 제64권4호
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• pp.231-235
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• 2020

• Bulletin of the Korean Chemical Society
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• 제31권5호
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• pp.1349-1354
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• 2010

The geometries and isomerization of the alkylidene silylenoid $H_2C$ = SiLiF as well as its insertion reactions with R-H (R = F, OH, $NH_2$) have been systematically investigated at the B3LYP/6-311+$G^*$ level of theory. The potential barriers of the three insertion reactions are 97.5, 103.3, and 126.1 kJ/mol, respectively. Here, all the mechanisms of the three reactions are identical to each other, i.e., an intermediate has been formed first during the insertion reaction. Then, the intermediate could dissociate into the substituted silylene ($H_2C$ = SiHR) and LiF with a barrier corresponding to their respective dissociation energies. Correspondingly, the reaction energies for the three reactions are -36.4, -24.3, and 3.7 kJ/mol, respectively. Compared with the insertion reaction of $H_2C$ = Si: and R-H (R = F, OH and $NH_2$), the introduction of LiF makes the insertion reaction occur more easily. Furthermore, the effects of halogen (F, Cl, Br) substitution and inorganic salts employed on the reaction activity have also been discussed. As a result, the relative reactivity among the three insertion reactions should be as follows: H-F > H-OH > H-$NH_2$.

• 대한화학회지
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• 제37권8호
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• pp.757-764
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• 1993

Phenylsilylene(PhHSi:)의 광분해 전구체인, 1,1,1,3,3,3-hexamethyl-2-phenyltrisilane(2)과 2,3-dicarbomethoxy-1,4,5,6,7-pentaphenyl-7-silanorbornadiene(5)을 10%와 73%의 수율로 각각 합성하였다. 전구체 2를 254 nm의 빛을 조사시켜 광분해 실험시킨 결과 triethylsilane 존재하에서는 phenylsilylene이 Si-H 결합에 삽입된 생성물인 1,1,1-triethyl-2-phenyldisilane (6)이 44%의 수율로 얻어졌고, diphenylacetylene 존재하에서는 phenylsilylene이 삼중결합에 첨가된 후 diphenylacetylene과 [2＋2] 첨가반응이 일어나 얻어진 생성물, 1-phenyl-1-silacyclopenta-2,4-diene(4)과 phenyl-silylene이 삼중결합에 첨가된 다음 곧 이합체화되어진 화합물인 1,2-diphenyl-1,2-disilacyclohexa-2,5-diene(10)이 각각 68% 와 26%의 수율로 얻어졌다. Neat 광반응에서는 생성된 phenylsilylene이 분자간 C-H 삽입반응을 하여 생성된 화합물, 1,5-dihydrosilanthren(11)과 전구체 2가 Si-H 결합에 삽입된 화합물, 1,2-diphenyltrisilane(12)이 5%와 7%의 수율로 각각 얻어졌다. 같은 조건에서 화합물 5를 triethylsilane과 methanol 존재하에서 광분해시킨 결과 phenylsilylene은 생성되지 않고 분자내 1,5-sigmatropic 자리옮김에 의한 silylenolether가 생성됨을 확인하였다.