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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 41, Number 12
JKCSEZ 41(12)
December 20, 1997 

Synthesis of Cp*Ru(CO)(PR3)H Type Complexes and Photo-Induced H/D Exchange Reaction

Cp*Ru(CO)(PR3)H형 착물의 합성과 광반응에 의한 H/D 교환반응
Dong Hwan Lee*, Sng Il Kim, Jang Il Kim, Yung Hee Oh, Sang Kyu Kam

이동환, 김승일,김장일,오영희,감상규
클로로착물 Cp*·Ru(CO)(PR3)Cl(4,Cp*=ㅐ5-C5Me5, PR3=PMe3, PEt3, PMePh2, PPh3, PCy3)을 출발물질로 사용하여 다양한 히드리드화시약(NaBH4, LiAlH4, LiBEt3H)이나 NaOMe를 반응시켜서 대응하는 히드리드착물 Cp*Ru(CO)(PR3)H(5)를 합성하였다. Cp*Ru(CO)(PCy3)H(5)착물의 C6D6용액에 UV를 조사하면 분자간 및 분자내 C-H결합 활성화반응을 통하여 용매의 중수소와 착물의 배위 리간드인 Cp*, PCy3, Ru-H의 수소 사이에 H/D교환반응이 진행되었으며 그반응기구를 설명하였다.

Hydride complexes Cp*Ru(CO)(PR3)H (Cp*=η5-C5Me5, PR3=PMe3, PEt3, PMePh2, PPh3, PCy3)(4a-4f) were synthesized by the reaction of the corresponding chloro complex Cp*Ru(CO)(PR3)Cl (3a-3f) with various hydridic reagent (NaBH4, LiAlH4, LiBEt3H) or NaOMe. Irradiation of Cp*Ru(CO)(PCy3)H (5e) in C6D6 solution with UV light caused H/D exchange reaction between coordinated Cp*, PCy3 and/or Ru-H ligand proton and a deuterium of the deuterated aromatic solvent through a series of inter- and intramolecular C-H activation. The proposed mechanism was described.

645 - 652
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