• 제목/요약/키워드: Tridentate ligands

검색결과 29건 처리시간 0.023초

(N-C-N) 세자리 리간드를 가지는 니켈 착물 (Nickel Complexes Having (N-C-N) Tridentate Ligands)

  • 이동환;박순흠
    • 대한화학회지
    • /
    • 제51권6호
    • /
    • pp.499-505
    • /
    • 2007
  • 세자리 비스(이미노)알릴 (N,C,N-집게발) 리간드를 가진 단핵 Ni(II) 착물을 발표하고자 한다. 새로운 착물(2,6-(ArN=CH)2C6H3)NiBr (Ar=2,6-dimethylphenyl (1), 2,6-diisopropylphenyl (2))은 산화성 첨가반응에 의해 Ni(COD)2 (COD=1,5-cyclooctadiene)와 1,3-(ArN=CH)2C6H3Br (bis(N-Ar)-2-bromoisophthalaldimine: Ar=Ph-2,6-Me2, Ph-2,6-iPr2) 으로부터 높은 수율로 합성하였다. 리간드와 니켈 착물에 대한 개선된 합성경로에 대하여 설명하고자 한다. 니켈(II) 착물 1, 2는 적외선 분광학, 수소-핵자기공명, 그리고 원소분석에 의해 구조를 밝혔다. 합성한 니켈 착물을 촉매로 사용하여 에틸렌 중합반응을 시도하였으나 목적하는 에틸렌고분자는 얻어지지 않고 소량의 올리고머가 형성되었다. 본 연구에서 합성한 니켈 착물이 에틸렌고분자 촉매반응에 활성을 보이지 않는 이유는 아마도 집게발 착물의 높은 경직성과 리간드의 비치환성 때문에 반응에 필요한 적합한 조건을 제공하지 못 했다고 사료된다.

Manipulation of Absorption Maxima by Controlling Oxidation Potentials in Bis(tridentate) Ru(II) N-Heterocyclic Carbene Complexes

  • Kim, Hyeong-Mook;Jeong, Daero;Noh, Hee Chang;Kang, Youn K.;Chung, Young Keun
    • Bulletin of the Korean Chemical Society
    • /
    • 제35권2호
    • /
    • pp.448-456
    • /
    • 2014
  • A series of seven Ru(II) complexes bearing NHC ligands have been synthesized. The electronic structures of these complexes were analysed by spectroscopic and electrochemical methods and further examined by theoretical calculations. Data show that absorption maxima are dependent on the HOMO level rather than the HOMO-LUMO gaps.

Structures and Magnetic Properties of Monomeric Copper(II) Bromide Complexes with a Pyridine-Containing Tridentate Schiff Base

  • Kang, Sung Kwon;Yong, Soon Jung;Song, Young-Kwang;Kim, Young-Inn
    • Bulletin of the Korean Chemical Society
    • /
    • 제34권12호
    • /
    • pp.3615-3620
    • /
    • 2013
  • Two novel copper(II) bromide complexes with pyridine containing Schiff base ligands, $Cu(pmed)Br_2$ and $Cu(pmed)Br_2$ where pmed = N'-((pyridin-2-yl)methylene)ethane-1,2-diamine (pmed) and dpmed = N,N-diethyl-N'-((pyridin-2-yl)methylene)ethane-1,2-diamine (dpmed) were synthesized and characterized using X-ray single crystal structure analysis, optical and magnetic susceptibility measurements. Crystal structural analysis of $Cu(pmed)Br_2$ showed that the copper(II) ion has a distorted square-pyramidal geometry with the trigonality index of ${\tau}=0.35$ and two intermolecular hydrogen bonds, which result in the formation of two dimensional networks in the ab plane. On the other hand, $Cu(pmed)Br_2$ displayed a near square-pyramidal geometry with the value of ${\tau}=0.06$. In both compounds, the NNN Schiff base and one Br atom occupy the basal plane, whereas the fifth apical position is occupied by the other Br atom at a greater Cu-Br apical distance. The reported complexes show $g_{\mid}$ > $g_{\perp}$ > 2.0023 with a $d_{x2-y2}$ ground state and a penta-coordinated square pyramidal geometry. Variable temperature magnetic susceptibility measurements showed that the developed copper(II) complexes follow the Curie-Weiss law, that is there are no magnetic interactions between the copper(II) ions since the Cu--Cu distance is too far for magnetic contact.

Synthesis of New VO(II), Co(II), Ni(II) and Cu(II) Complexes with Isatin-3-Chloro-4-Floroaniline and 2-Pyridinecarboxylidene-4-Aminoantipyrine and their Antimicrobial Studies

  • Mishra, Anand P.;Mishra, Rudra;Jain, Rajendra;Gupta, Santosh
    • Mycobiology
    • /
    • 제40권1호
    • /
    • pp.20-26
    • /
    • 2012
  • The complexes of tailor made ligands with life essential metal ions may be an emerging area to answer the problems of multi drug resistance. The coordination complexes of VO(II), Co(II), Ni(II) and Cu(II) with the Schiff bases derived from isatin with 3-chloro-4-floroaniline and 2-pyridinecarboxaldehyde with 4-aminoantipyrine have been synthesized by conventional as well as microwave methods. These compounds have been characterized by elemental analysis, molar conductance, electronic spectra, FT-IR, FAB mass and magnetic susceptibility measurements. FAB mass data show degradation of complexes. Both the ligands behave as bidentate and tridentate coordinating through O and N donor. The complexes exhibit coordination number 4, 5 or 6. The Schiff base and metal complexes show a good activity against the bacteria; $Staphylococcus$ $aureus$, $Escherichia$ $coli$ and $Streptococcus$ $fecalis$ and fungi $Aspergillus$ $niger$, $Trichoderma$ $polysporum$, $Candida$ $albicans$ and $Aspergillus$ $flavus$. The antimicrobial results also indicate that the metal complexes are better antimicrobial agents as compared to the Schiff bases. The minimum inhibitory concentrations of the metal complexes were found in the range 10-40 ${\mu}g/mL$.

$[M(II)O_3N_3]$$[Ni(II)O_2N_4]$ 형태착물의 쌍극자 모멘트에 대한 리간드의 cis 및 trans 구조의 영향 (The Effects of the cis and trans Configurations of Ligands on the Calculated Dipole Moments for $[M(II)O_3N_3]$ and $[Ni(II)O_2N_4]$ Type Complexes)

  • 안상운;박의서;최창진
    • 대한화학회지
    • /
    • 제27권2호
    • /
    • pp.83-94
    • /
    • 1983
  • EHT calculation의 고유함수를 사용하여 $[M(II)O_3N_3]$$[Ni(II) O_2N_4]$ 형태착물[M(II) = Co(III), Ni(II) 및 Cu(II)]의 쌍극자 모멘트에 대한 cis 및 trans 구조의 영향을 고찰하였다. cis$[M(Ⅱ)O_3N_3]$ 형태착물의 계산한 쌍극자 모멘트가 trans착물의 계산한 쌍극자 모멘트 값보다 큰 값을 가지며 trans 착물의 쌍극자 모멘트 값이 실험치 범위안에 들었다. 그러나 $[Ni(II) O_2N_4]$ 착물의 경우 cis 착물의 쌍극자 모멘트 값이 실험치 범위안에 들었다. 이 결과는 $[Co(III)O_3N_3]$ 형태착물이 trans 구조, $[Ni(II) O_2N_4]$ 형태착물은 cis 구조를 가졌음을 암시하며 이는 실험결과와 일치한다. $[M(II)O_3N_3]$ 형태착물에서 세개의 두자리 (O-N)리간드가 금속이온에 배위되어 있으며 $[Ni(II) O_2N_4]$형태 착물에서는 두개의 세자리(O-N-N) 리간드가 Ni(II) 이온에 배위되어 있음).

  • PDF

Synthesis and Crystal Structures of Copper(II) Complexes with Schiff Base Ligands: [Cu2(acpy-mdtc)2(HBA)(ClO4)]·H2O and [Cu2(acpy-phtsc)2(HBA)]·ClO4

  • Koo, Bon Kweon
    • Bulletin of the Korean Chemical Society
    • /
    • 제34권11호
    • /
    • pp.3233-3238
    • /
    • 2013
  • Two new Cu(II) complexes, $[Cu_2(acpy-mdtc)_2(HBA)(ClO_4)]{\cdot}H_2O$ (1) (acpy-mdtc- = 2-acetylpyridine S-methyldithiocarbamate and $HBA^-$ = benzilic acid anion) and $[Cu_2(acpy-phtsc)_2(HBA)]{\cdot}ClO_4$ (2) (acpy-$phtsc^-$ = 2-acetylpyridine 4-phenyl-3-thiosemicarbazate) have been synthesized and characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, and single crystal X-ray diffraction. The X-ray analysis reveals that the structures of 1 and 2 are dinuclear copper(II) complexes bridged by two thiolate sulfur atoms of Schiff base ligand and bidentate bridging $HBA^-$ anion. For 1, each of the two copper atoms has different coordination environments. Cu1 adopts a five-coordinate square-pyramidal with a $N_2OS_2$ donor, while Cu2 exhibits a distorted octahedral geometry in a $N_2O_2S_2$ manner. For 2, two Cu(II) ions all have a five-coordinate square-pyramidal with a $N_2OS_2$ donor. In each complex, the Schiff base ligand is coordinated to copper ions as a tridentate thiol mode.

Synthesis and Crystal Structure of Manganese(II) Complexes with 2-Acetylpyridine Methyldithiocarbazate

  • 모성종;임우택;구본권
    • Bulletin of the Korean Chemical Society
    • /
    • 제19권11호
    • /
    • pp.1175-1179
    • /
    • 1998
  • The aerobic reaction of 2-(acetylpyridine)-S-methyldithiocarbazate (acpy-mdtcH) and 2-(acetylpyridine)-N-phenylthiosemicarbazate(acpy-phTscH) with manganese(Ⅱ) acetate affords Mn(acpy-mdtc)2 and Mn(acpyphTsc)2, respectively. The spectroscopic data and X-ray structure of Mn(acpy-mdtc)2 are reported. Crystal data for Mn(acpy-mdtc)2; C18H20N6S4Mn, mol wt 503.58, monoclinic crystal system(P21/c) a=12.240(5) Å, b= 10.918(l) Å, c=17.651(3) Å, β=105.93(2), and V=2268(l) Å3, Z=4, 5071 data collected with 0°< 2θ < 52.64°, 2995 data with I > 3σ(I), R= 0.046, Rw= 0.065. The ligands act as tridentate NNS donors. The two Mn-S distances are not equal, and respectively 2.512(2) Å and 2.541(2) Å. The average Mn-N (azomethine) length, 2.242(5) Å, is slightly shorter than the average Mn-N (pyridyl) length, 2.262(5) Å. The coordination environment about MN(Ⅱ) center deviates considerably from octahedral geometry. The manganese(Ⅱ)-manganese(Ⅰ) and manganese(Ⅰ)-manganese(0) reduction potentials of Mn(acpy-mdtc)2 are ∼-l.71 and ∼-l.98 V while those of Mn(acpy-phTsc)2 are ∼-l.87 and ∼-2.11 V vs. Ag/Ag+ in dimethyl sulfoxide, respectively.

p-Nitrophenyl Picolinate의 가수분해에 대한 코발트(Ⅲ) 착물의 촉매효과 (Catalytic Effects of Co(Ⅲ) Complexes on the Hydrolysis of p-Nitrophenyl Picolinate)

  • 노재근;김창석;홍순영
    • 대한화학회지
    • /
    • 제40권4호
    • /
    • pp.254-263
    • /
    • 1996
  • 두 자리 또는 세 자리의 질소 리간드를 갖는 5종류의 코발트(III) 착물을 합성하였다. 이 착물들의 촉매 작용을 질소의 위치가 다른 세 종류의 기질, 즉 P-Nitrophenyl Picolinate, P-Nitrophenyl nicotinate, 및 P-Nitrophenyl isonicotinate의 가수분해 반응에 대하여 자외선 분광법으로 측정하였다. 이 세 가지 기질 중에서 P-Nitrophenyl Picolinate가 촉매에 가장 민감한 반응을 보였으며, 이 화합물의 가수분해 반응은 pquohydroxo형태의 착물이 가장 많이 존재하는 pH 6.5에서 이 촉매들에 의하여 21-40배 촉진 되었다. P-Nitrophenyl Picolinate의 가수분해 반응에 대한 착물의 효과는 $Co(ibpn)(OH)>Co(aepn)(OH)_2(OH_2)>Co(tn)_2(OH)(OH_2)>Co(bpy)_2(OH)(OH_2)>Co(dien)(OH)_2(OH_2)$와 같이 나타났으며 이 가수 분해 반응은 분자내 일반 염기성 촉매 반응이 우세한 과정을 따르며 부분적으로 분자내 친핵성 촉매반응 메카니즘을 따르고 있음을 알 수 있었다.

  • PDF

메틸알루미녹산으로 활성화시킨 고활성 bis(benzimidazolyl)amine 크롬 착물을 이용한 부타디엔 중합에 의한 트랜스 폴리부타디엔 제조 (Highly active and trans-1,4-specific polymerization of 1,3-butadiene catalyzed by bis(benzimidazolyl)amine chromium complexes activated with methylaluminoxane)

  • 문병규;송가영;장린;신진영;장혁철;심상은;윤주호;김일
    • Elastomers and Composites
    • /
    • 제48권1호
    • /
    • pp.61-66
    • /
    • 2013
  • 일반식을 $[N(CH_3)(CH_2)_2(Bm-R)_2]CrCl_3$ [여기에서 Bm = benzimidazolyl, R = H (3a); -Me(3b); -Bn(3c)]으로 나타낼 수 있는 일련의 세 다리 dibenzimidazolyl 리간드를 갖는 크롬(III) 착물을 합성, 메틸알루미녹산으로 활성화시켜 이를 부타디엔의 입체규칙성 중합을 통해 trans-1,4-polybutadiene을 제조하였다. 크롬 착물의 부타디엔 중합 활성은 리간드의 구조에 따라 달라졌으며, 활성은 3a > 3c > 3b 순으로 낮아졌다. 모든 착물을 이용하여 제조된 폴리부타디엔의 미세구조를 조사한 결과 거의 완벽한 trans-1,4 구조를 보였으며, 분자량도 비교적 높게 나타났다.