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1,2,3,4,5,6-Hexaalkyl-1,4-dibora-2-cyclohexene의 생성과 착물 생성
엄재국,안희원,Uhm, Jae-Koouk,An, Hee-Won 대한화학회 1997 대한화학회지 Vol.41 No.11
1,2,3,4,5,6-hexaalkyl-1,4-dibora-2-cyclohexene은 $B_2Cl_4$로부터 제조할 수 있었으나, 보통실험실에서는 이것을 제조하기 어렵기 때문에 다른 방법에 의한 생성을 시도하였다. 즉,1,4-dimethyl-2,3-diethyl-1,4-dibora-2-cyclohexene, 1 유도체를 potassium과 methyl iodide에 의한 환원${\cdot}$산화반응을 시켜주므로 2,3-dietyl-1,4,5,6-tetramethyl-1,4-dibora-2-cyclohexene, 2를 얻을 수 있었다. 또 이 유도체와 ($({\eta}5-C_5H_5Co(C_2H_4)_2$를 반응시켜 코발트 sandwich 착물인 두 종류의 double-decker, 6 그리고 7, 또 한 종류의 triple-decker, 8을 생성하였다. 1,2,3,4,5,6-Hexaalkyl-1,4-dibora-2-cyclohexene was not produced by the general preparation method in our laboratory because of difficulties in the preparation of $B_2Cl_4.$ 2,3-Dietyl-1,4,5,6-tetramethyl-1,4-dibora-2-cyclohexene, 2 was synthesized by the reduction-oxidation reaction of potassium and methyliodide from 1,4-dimethyl-2,3-diethyl-1,4-dibora-2-cyclohexene, 1 as a substrate. Cobalt sandwich-complexes, 6, 7 and 8 were synthesized by the reaction of 2,3-diethyl-1,4,5,6-tetramethyl-1,4-dibora-2-cyclohexene with $({\eta}5-C_5H_5Co(C_2H_4)_2.$.
$C_2$ 손대칭 리간드를 배위하는 $\pi$-Allyl-Cobalt, Palladium, Platinum 착물의 생성
엄재국,이종오,안희원,Uhm, Jae Kook,Lee, Jong O,An, Hee Won 대한화학회 1998 대한화학회지 Vol.42 No.2
C2-손대칭 리간드(chiral ligand)의 한 종류인 (+)-11S,12S-bis [2,2'-(diphenylphosphino)benzanilido]-9,10-dihydro-9,10-ethanoanthracene과 백금과 코발트를 포함하는 착물과 각각 반응시켜, 세 종류의 새로운 착물인 $\pi$-allyl Pt(+)-11S,12S-bis[2'-(diphenylphosphino)benzanilido]-9,10-dihydro-9,10-ethanoanthracene perchlorate, $\pi$-allyl Pt(+)-11S,12S-bis[2,2'-(diphenylphosphino)benzanilido]-9,10-dihydro-9,10-ethanoanthracene chloride, (${\eta}$5-cyclopentadienyl) Co -(+)-11S,12S-bis[2,2'-(diphenylphosphino)benzanilido]-9,10-dihydro-9,10-ethanoanthracene를 얻었다. 그리고 (${\eta}$3-cyclohexenyl) Pd 착물과 대칭리간드인 1,2-bis(diphenylphosphino)ethane 과 반응시켜 새로운 착물, (${\eta}$3-cyclohexenyl) Pd1,2-bis(diphenylphosphino)ethane perchlorate를 생성하였다. 이들 착물은 NMR-, IR-, Mass-spectrometer, 원소분석등의 각종 화학분석기기에 의해 각각 확인되었다. By the reactions of a $C_{2}$-chiral ligand, (+)-11S,12S-bis[2,2'-(diphenylphosphino)benzanilido]-9,10-dihydro-9,10-ethanoanthracene(6) with $[\pi-allyl chloroplatinum(II)]_4$, and $CpCo(CO)_2$ respectively, three new complexes, ($\pi$-allyl)platinum(II)(+)-11S,12S-bis[2,2'-(diphenylphosphino)benzanilido]-9,10-dihydro-9,10-ethanoanthracene perchlorate(1), ($\pi$-allyl)platinum(II)(+)-11S,12S-bis[2,2'-(diphenylphosphino)benzanilido]-9,10-dihydro-9,10-ethanoanthracene chloride(2), ($\eta^5$-cyclopentadienyl)cobalt(I)-(+)-11S,12S-bis[2,2'-(diphenylphosphino)benzanilido]-9,10-dihydro-9,10-ethanoanthracene(3) were prepared. $\eta^3$-Cyclohexenyl)palladium(II)1,2-bis(diphenylphosphino)ethane perchlorate(4) was obtained by the reaction of ($\eta^3$-cyclohexenyl)palladium(II) chloride dimer with a symmetric ligand, 1,2-bis(diphenylphosphino)ethane and lithium perchlorate. These complexes were identified by NMR-, IR-, and Mass-Spectrophotometers and elemental analyzer.