• Title/Summary/Keyword: Metallacycles

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Synthesis of a Platinum-Pincer Complex and Application to Catalytic Silylcyanation (백금 핀서 화합물의 합성 및 Silylcyanation 촉매반응에 대한 응용)

  • Kim, Yun Tae;Yoon, Myeong Sik
    • Applied Chemistry for Engineering
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    • v.27 no.4
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    • pp.366-370
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    • 2016
  • A platinum(II) pincer complex composed of two six-membered fused metallacycles was directly synthesized using 1,3-bis(2-pyridyloxy)benzene and $K_2PtCl_4$. The structure of the complex was elucidated via NMR and X-ray crystallography analysis. The stable complex was formed due to the six-membered fused cycle structure around the Pt(II) center which reduced the bond angle strain. The complex was applied to the silylcyanation reaction of aldehydes and imines and showed an efficient catalytic activity with 99% yield.

Synthesis, Structures, and Catalytic Properties of Ionic Metallacyclodimeric Palladium(II) Complexes

  • Kim, Sung Min;Park, Kyung Hwan;Lee, Haeri;Moon, So Yun;Jung, Ok-Sang
    • Bulletin of the Korean Chemical Society
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    • v.33 no.12
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    • pp.4069-4073
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    • 2012
  • Metallacyclodimeric complexes of $[(Me_4en)Pd(L)]_2(ClO_4)_4$ ($Me_4en$ = N,N,N',N'-tetramethylethylenediamine; L = dimethylbis(4-pyridyl)silane (dmps), methylvinylbis(4-pyridyl)silane (mvps)) have been synthesized, and their structures have been characterized by X-ray single crystallography. The skeletal structures consist of one 20-membered metallamacrocycle, two 5-membered metallacycles, and four pyridyl groups. The local geometry around the palladium(II) ion approximates to a typical square planar arrangement with four nitrogen donors. Delicate difference in catalytic effects on hydrogenation was investigated based on the structure of catalyst and substrates.

First Hydrogelation of Discrete Metal Complexes. Structures and Fluxional Behavior of Cyclopalladium(II) Complexes

  • Na, Young-Mee;Noh, Tae-Hwan;Ha, Byung-Jo;Hong, Jong-Ki;Jung, Ok-Sang
    • Bulletin of the Korean Chemical Society
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    • v.30 no.3
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    • pp.573-576
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    • 2009
  • The reaction of $(en)Pd(NO_3)_2$ (en = ethylenediamine) with 1,4-bis(dimethyl-4-pyridylsilyl)benzene (L) affords cyclodimer, $[(en)Pd(L)]_2(NO_3)_4$, whereas the reaction of $(tmeda)Pd(NO_3)_2$ (tmeda = N,N,N’,N’-tetramethylethylenediamine) with L gives cyclotrimer, $[(tmeda)Pd(L)]_3(NO_3)_6$. Both complexes exist as catenane in water. The catenated cyclodimer is rigid whereas the catenated cyclotrimer is dynamic in water. The catenated cyclotrimers afford hydrogel containing 98.5% water below 2 ${^{\circ}C}$. The hydrogel changes to its sol around 38 ${^{\circ}C}$, and to its clear solution at 78 ${^{\circ}C}$. Such a notable difference between $[(en)Pd(L)]_2(NO_3)_4$ and $[(tmeda)Pd(L)]_3(NO_3)_6$ might be explained by their different dynamic behavior via ring size effects.