AP is grateful to Imperial College London for a PhD studentship via the Frankland Chair endowment. Johnson Matthey plc are also thanked for the loan of the precious metal salts used in this work.

참고 : 흄 후드에서 모든 합성을 수행, 단지 적절한 안전 문제가 확인되었습니다하고 조치들을 방지하기 위해 촬영 후. 개인 보호 장비는 실험실 코트, 장갑과 보안경을 포함하고 항상 착용해야합니다. N, N 1. 합성, N 트리스 (diphenylphosphinomethylene) 아민, N (CH 2 PPH 2) 3 (N -triphos 박사) (1) <ol><li> (200)는 오븐 건조 ml의 슈 렝크 플라스크 이중 매니 폴드 쉬 렌크 라인에 3 개의 연속 진공 질소 사이클을 질소 하에서 디 페닐 (하이드 록시 메틸렌) 포스 염화 (11) (6.99 g, 24.7 mmol)을과 장소를 추가합니다. </li><li> hydroxymethene에 포스 포늄 클로라이드 염으로 전환을 위해 1 시간 동안 실온에서 탈기 된 메탄올 (30 ㎖) 및 트리 에틸 아민 (9.5 ㎖, 68.1 밀리몰)를 첨가하고, 교반한다. 이어서, 메탄올 (2 M, 4.1 ㎖, 8.2 밀리몰)를 탈기 된 암모니아 용액을 첨가. </li><li> 환류하에 2 시간 동안 반응 혼합물을 가열되는 동안 리간드 백색 고체로서 침전된다. </li><li> N -triphos 박사 리간드 최적 순도 단시간 위에 공기에서 산화에 안정하지만, 질소 하에서 캐뉼라 여과 (26)을 통해 용매를 제거하고, 분석적으로 순수한 생성물을 수득 탈기 된 메탄올 (3 × 10 ㎖)로 세정 하고, 질소 분위기하에 저장한다. </li></ol> 2. 합성의 Ru (CO) 2 {N (CH 2 PPH 2) 3} -κ 3 P] (2) <ol><li> (200) 오븐 건조 ㎖로 쉬 렌크 플라스크에, 세 개의 연속 진공 질소 사이클을 질소 하에서 N -Triphos 박사 (1.0 g, 1.63 mmol)을 [의 Ru 3 (CO) 12] (347 ㎎, 0.54 mmol)을 첨가하고, 장소를 추가 이중 매니 폴드 쉬 렌크 라인. </li><li> 건조, 탈기 톨루엔 30 ML을 추가하고 12 시간 동안 환류 혼합물을 가지고. </li><li> 이 12 시간 환류 한 후, 두 번째 쉬 렌크 플라스크에 캐 뉼러를 통해 솔루션을 필터링반응 과정 중에 형성 금속 루테늄의 소량을 제거합니다. </li><li> 단지의 침전을 유도하기 위해, 트랩을 냉각 액체 질소가 장착 된 듀얼 매니 폴드 쉬 렌크 줄을 사용하여 진공 상태에서 약 10 ml의 용매의 양을 줄일 수 있습니다. </li><li> 완전한 재용가 발생할 때까지 오일 욕에서 부드럽게 (80-90 °의 C)를 가열하여 침전물을 재결정하고, 쉴 렌크 플라스크를 오일 욕으로부터 열을 제거하지만, 허용함으로써 RT 후속의 서냉은 잠긴 상태로 유지. 주황색 고체 결정 성을 제공하는 O / N을 남겨주세요. </li><li> 다른 오븐 상등액 캐뉼라 여과를 통해 X 선 회절에 적합한 주황색 결정이 쉬 렌크 플라스크를 건조 격리. 다음에, 진공 O / N에서 건조하고, 탈기 톨루엔 (2 X 5 mL)과 함께 건조 된 결정을 헹군다. 별도의 슈 렝크 플라스크에 결합 된 상층 액과 세척액을 저장합니다. </li><li> 결합 된 상층 액과 세척 용액에서 결정의 두 번째 배치를 구합니다단계 2.5 및 2.6과 유사한 방법에 의해 재결정 S 반응의 전체 수율을 향상시킬 수있다. </li><li> 공기에 노출이 산화 된 탄산 복잡한 느린 변환에 이르게으로 질소에서 복잡한 저장 (아래 참조). </li></ol> 3. 합성의 Ru (CO 3) (CO) {N (CH 2 PPH 2) 3} -κ 3 P] (3) <ol><li> 200㎖의 쉬 렝크 플라스크에 부분적으로 용해 된 오렌지색 현탁액을 생성하기 위해 2 (280 ㎎, 0.364 mmol) 및 톨루엔 5 mL를 추가한다. </li><li> 10 분 동안 반응 혼합물을 통해 초당 2-3 방울의 속도로 상기 현탁액과 기포 산소로 산소 벌룬에 부착 된 바늘을 삽입한다. </li><li> 오렌지색 침전물이 형성됨으로, 공기에서 여과하여 수집하고 공기 중에서 안정 자유 유동 오렌지색 분말을 수득 진공에서 톨루엔 (2 X 5 mL) 및 디 에틸 에테르 (2 × 5 ml) 및 건조로 세척 하였다. </li><li> X 선 diffr 적합한 결정을 성장하기 위해서는동작은 천천히 유리 병의 측면을 실행하려면이 용매를 허용하여 위에 유리 병 및 레이어 3 ㎖ 톨루엔 3 ㎖ 디클로로 메탄 (3) 100 mg을 용해. <ol><li> 결정을 취득하기 위해서이 O / N을 남겨주세요. 상등액을 경사 분리하고, 톨루엔 (2 × 3 mL) 및 디 에틸 에테르 (2 × 3 ml)로 세척하여 결정을 분리. 이중 매니 폴드 쉬 렌크 라인에 진공 건조. </li></ol></li></ol> 4. 합성의 Ru (H) 2 (CO) {N (CH 2 PPH 2) 3} -κ 3 P] (4) <ol><li> 건조 20ml에 3 (763 ㎎, 0.953 밀리몰)의 용액을 준비 THF를 탈기시키고 질소의 양압 (0.2 바)하에 100 ㎖ 오토 클레이브 엔지니어 고압 반응기를 주입. </li><li> 100 % 수소 원자로 헤드 스페이스 가스를 변경하고 2 시간 동안 교반하면서 100 ° C로 다음, 실온에서 15 줄에 열을 가압. 주의! 모든 안전 절차를 확인 높은 사용하는 경우에 부착 된압력 시스템! </li><li> RT로 냉각시킨 후, 조심스럽게 반응기 헤드 스페이스에 과량의 수소 기체를 배기하고 질소로 변경. </li><li> 질소하에 100 ㎖ 쉬 렌크 플라스크에, 반응 용액을 전송하고, 캐 뉼러를 통해 이중 매니 폴드 쉬 렌크 라인 필터의 재접속 후에 건조 20 ㎖로 희석시키고, 메탄올 탈기. </li><li> 액체 질소 장착 이중 매니 폴드 쉬 렌크 라인을 사용하여, 진공하에 용매를 제거는 오렌지색 분말을 수득 트랩을 냉각시켰다. 건조, 탈기 된 메탄올 (3 × 5 ml) 및 건조하여 오렌지색 분말이 세탁, 디 에틸 에테르 (3 × 5 ㎖) 건조시키고, 진공에서 탈기. </li><li> X 선 회절 분석에 적합한 결정을 O 성장 / N의 건조 등 체적 량 계층화 (4)의 건조 포화 탈기 톨루엔 용액으로부터 메탄올을 탈기. </li><li> 질소에서 복잡한을 저장합니다. </li></ol> RUH 2 (CO) {N (CH 2 PPH 2) 3} -κ 3 P [5. 반응(4) NH 4 PF (6)과 레 불린 산으로 <ol><li> 건조 2ml의 4의 용액 (48.4 ㎎, 65.2 μmol)을 준비, 오븐에서 톨루엔을 쉴 렌크 플라스크를 건조시키고, (아세토 니트릴 (65.0 μmol, 10.6 mg)을 NH 4 PF (6)의 교반 용액에 주사기를 통해 추가 2 탈기 ml)에 별도의 오븐에서 쉬 렌크 플라스크를 건조. </li><li> 2 시간 동안 실온에서 반응 혼합물을 교반한다. 이후, (착체 중간체 [RUH (CO) (의 MeCN) {N (CH 2 PPH 2) 3} -κ 3 P]를 수득 트랩을 액체 질소 장착 이중 매니 폴드 쉬 렌크 라인을 냉각 된 사용, 용매를 진공하에 제거하여 5). </li><li> 건조로 세척, 갈색 분말로서 복소 5를 분리 진공에서 헥산 (3 x 3 mL) 및 무수 탈기. </li><li> (5) 0.5 ml의 용액에 아세톤 - 탈기 D (6)의 0.5 ml의 (93.0 μmol, 1.43 당량. 10.8 ㎎)을 레 불린 산을 추가 아세톤 D-6 탈기. 사용하여 2 분 동안 반응 혼합물을 교반소용돌이 교반기. </li><li> 기록 1 H 30 P {1} H 반응 16 시간 반응을 관찰하기위한 모든 시간의 NMR 스펙트럼. (27) </li></ol>

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A. 206 (1-2), 185-192 (2003).</li><li>Wesselbaum, S., vom Stein, T., Klankermayer, J., Leitner, W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Hydrogenation+of+Carbon+Dioxide+to+Methanol+by+Using+a+Homogeneous+Ruthenium&#8211;Phosphine+Catalyst.">Hydrogenation of Carbon Dioxide to Methanol by Using a Homogeneous Ruthenium&#8211;Phosphine Catalyst.</a> Angew. Chem. Int. Ed. 51 (30), 7499-7502 (2012).</li><li>Fillol, J. L., Kruckenberg, A., Scherl, P., Wadepohl, H., Gade, L. H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Stitching+Phospholanes+Together+Piece+by+Piece:+New+Modular+Di-+and+Tridentate+Stereodirecting+Ligands.">Stitching Phospholanes Together Piece by Piece: New Modular Di- and Tridentate Stereodirecting Ligands.</a> Chem. Eur. J. 17 (50), 14047-14062 (2011).</li><li>Rodr&#237;guez, L. -. I., Roth, T., Fillol, J. L., Wadepohl, H., Gade, L. H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+More+Gold&#8211;The+More+Enantioselective:+Cyclohydroaminations+of+&#947;-Allenyl+Sulfonamides+with+Mono+Bis-,+and+Trisphospholane+Gold(I)+Catalysts.">The More Gold&#8211;The More Enantioselective: Cyclohydroaminations of &#947;-Allenyl Sulfonamides with Mono Bis-, and Trisphospholane Gold(I) Catalysts.</a> Chem. Eur. J. 18 (12), 3721-3728 (2012).</li><li>Scherl, P., Wadepohl, H., Gade, L. H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Hydrogenation+and+Silylation+of+a+Double-Cyclometalated+Ruthenium+Complex:+Structures+and+Dynamic+Behavior+of+Hydrido+and+Hydridosilicate+Ruthenium+Complexes.">Hydrogenation and Silylation of a Double-Cyclometalated Ruthenium Complex: Structures and Dynamic Behavior of Hydrido and Hydridosilicate Ruthenium Complexes.</a> Organometallics. 32 (15), 4409-4415 (2013).</li><li>Bennett, B. K., Richmond, T. G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=An+Inexpensive,+Disposable+Cannula+Filtration+Device.">An Inexpensive, Disposable Cannula Filtration Device.</a> J. Chem. Educ. 75 (8), 1034 (1998).</li><li>Judd, C. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Proton+NMR+Basics.">Proton NMR Basics.</a> J. Chem. Educ. 72 (8), 706 (1995).</li><li>Rhodes, L. F., Venanzi, L. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ruthenium(II)-Assisted+Borohydride+Reduction+of+Acetonitrile.">Ruthenium(II)-Assisted Borohydride Reduction of Acetonitrile.</a> Inorg. Chem. 26 (16), 2692-2695 (1987).</li><li>Bakhmutov, V. I. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=In-depth+NMR+and+IR+study+of+the+proton+transfer+equilibrium+between+[{MeC(CH2PPh2)3}Ru(CO)H2]+and+hexafluoroisopropanol.">In-depth NMR and IR study of the proton transfer equilibrium between [{MeC(CH2PPh2)3}Ru(CO)H2] and hexafluoroisopropanol.</a> Can. J. Chem. 79, 479-489 (2001).</li></ol>

The authors have nothing to disclose.

여기서 우리는 세자리 포스 핀 리간드의 합성 및 루테늄 착체의 효율적인 합성을위한 일련의 과정을 설명 하였다. N -triphos 박사 리간드 (1)을 용이하게 최소한의 워크 - 업 과정과 고 수율로 제조 할 수있다. 이러한 유형의 리간드를 합성하는 데 사용이 인계 니히 반응은 매우 일반적이며, P-R-원자에 상이한기를 갖는 다른 유도체 리간드에 사용될 수있다. 10-12,15-18</su...

루테늄 포스 계 복합체는 가장 널리 연구 및 화학적 다목적 분자량 촉매의 일부이다. 1-9는 일반적으로 루테늄 촉매 복합체의 전자 sterics, 형상 및 용해도를 지시 모노 - 또는 바이 덴 테이트 리간드를 포함하고있는 뿌리깊은 촉매 활성에 미치는 영향. 그들은 금속 중심 인 여러 도너의 더 큰 효과로 인해 킬레이트 금속 중심에 더 큰 안정성을 부여하는 것으로 알려진대로 다 자리 포스 시스템은 널리 이하, 촉매 작용을 위해 연구되었다. 이러한 안정화 촉매의 무결성을 보장 유리할 수있다 가혹한 반응 조건 (높은 온도와 압력) 같은 리간드의 복잡한 안정화 특성에 따라, 그러나, 촉매에 대한 바람직하지 않을 수 있습니다. 우리 10-12 및 13-18 등이 복잡한 얼굴 COOR 안정성을 부여하기위한 하나의 이러한 조사 하였다 다 자리 포스 핀 리간드 시스템dination 형상은 세 포스 아암이 잠재적 세자리 리간드를 형성 혀끝 브리징 질소 원자에 부착되는 소위 N -triphos 리간드 시리즈이다. 이들 특정 리간드에 주요 특징 중 하나는, 따라서, 그들이 기반 인 쉽게 구할 차 포스 발 니히 반응 (도 1)을 통해 합성 될 수 있다는 것을 용이 한 방법이다 높은 수율로 보통 제조 할 수있는 R-기의 다양한 포스 최소한의 작업 위로. 이 방법의 전반적인 목표는 다음 촉매 응용 프로그램에 액세스 할 수 있습니다 N -triphos 리간드를 갖춘 디 하이드 단지를 루테늄있는 손쉬운 경로를 제공하는 것이다. 최근, RU-triphos 계 복합체는 레 불린 산, 19, 20 11, 21 바이오 에스테르 및 높은 가치 화학 이산화탄소 22 바이오 매스 유래 제품의 수소화 반응을위한 촉매로서 주목 받고있다. 유리할 것이다로, 또는 이미 그들은 같은 N -triphos 리간드로, 액세스 합성 쉽게 특히,보고 시스템보다 더 적극적 중 하나입니다 RU-triphos 파생 상품의 범위를 확장합니다. 대부분의 연구 탄소 중심의 아날로그은 일반적으로 상대적으로 낮은 합성을 앓고 및 준비 적응력 쉽게 N -triphos 리간드는 달리, 높은 공기에 민감한 금속 붕소 시약을 포함한다. 10-18 N -triphos 리간드는 몰리브덴, 텅스텐, 루테늄, 로듐 및 금 단지 9 개의 출판물에서보고 된로, 상대적으로 과소 조사 남아있다. 이 독특한 화합물의 큰 숫자와 함께 각각 50과 900의 기사가되는 붕소 및 탄소 중심의 유사체, 완전히 대조적이다. 우리 같은 프로 키랄 올레핀 (23)의 비대칭 촉매 수소화에 그럼에도 불구하고, 단지를 포함하는 N의 -triphos 찾은 응용 프로그램LL N의 비대칭 cyclohydroamination는 γ-알레 닐 설폰 아미드를 -protected. (24) 또한, 부분 조정 phospholane를 특징으로 부피가 큰 N -triphos 리간드에 의해 조정 루테늄 착체는 실란, 유기 규소 화학의 발전에 중요한 단계를 활성화하는 것으로 확인되었다. (25) 촉매의 지속적인 연구 프로그램의 일환으로, 우리는 루테늄 N -triphos 박사의 precatalysts의 범위를 준비하고 자신의 화학 양 론적 반응과 촉매 가능성을 조사하기 위해 노력했다. N -triphos 박사가 처음 25 년 전에보고 된 몰리브덴 단지, 자신의 응용 프로그램에도 불구하고 촉매하거나 조사하지 않았습니다. 이 작품은 일반적으로 저개발에도 불구하고, 복잡한 안정성 많은 바람직한 특징을 가지고 N -triphos 발판의 적용 가능성을 보여줍니다. 여기에서 우리는 합성 경로 및 특성의에보고촉매 수소화 반응에 응용 프로그램을 찾을 수 있습니다 루테늄 N -triphos 박사 단지의 시리즈.

<table border="0" cellpadding="0" cellspacing="0">
	<tbody>
		<tr>
			<td>Methanol</td>
			<td rowspan="5">&#8211;</td>
			<td rowspan="5">&#8211;</td>
			<td rowspan="5">Obtained from in-house solvent purification system: Innovative Technology, inc &#34;pure solv&#34; drying tower. Stored in ampules over activated molecular sieves under nitrogen.</td>
		</tr>
		<tr>
			<td>Toluene</td>
		</tr>
		<tr>
			<td>Diethyl Ether</td>
		</tr>
		<tr>
			<td>Tetrahydrofuran (THF)</td>
		</tr>
		<tr>
			<td>Acetonitrile</td>
		</tr>
		<tr>
			<td>d6-Acetone</td>
			<td>VWR</td>
			<td>VWRC87152.0011</td>
			<td>Store in fridge</td>
		</tr>
		<tr>
			<td>Triethylamine</td>
			<td>Sigma-Aldrich</td>
			<td>TO886-1L</td>
			<td>Distilled and stored over activated molecular sieves under N2</td>
		</tr>
		<tr>
			<td>2M Ammonia solution in methanol</td>
			<td>Sigma-Aldrich</td>
			<td>341428-100ML</td>
			<td>Solution comes in a &#34;Sure-Seal&#34; bottle</td>
		</tr>
		<tr>
			<td>NH4PF6</td>
			<td>Sigma-Aldrich</td>
			<td>216593-5G</td>
			<td>Store in desiccator</td>
		</tr>
		<tr>
			<td>Levulinic Acid</td>
			<td>Acros Organics</td>
			<td>125142500</td>
			<td>Solid but melts close to room temperature</td>
		</tr>
		<tr>
			<td>3 &#197; Molecular sieves</td>
			<td>Alfa Aesar</td>
			<td>LO5359</td>
			<td>Activate by heating over night under vacuum</td>
		</tr>
		<tr>
			<td>Schlenk flasks</td>
			<td>GPE</td>
			<td>Custom design</td>
			<td>&#8211;</td>
		</tr>
		<tr>
			<td>Dual-manifold Schlenk line</td>
			<td>GPE</td>
			<td>Custom design</td>
			<td>Dual-manifold of i) N2 that has been passed through a silica drying column and ii) vacuum.</td>
		</tr>
		<tr>
			<td>Rotary vacuum pump</td>
			<td>Edwards</td>
			<td>RV3 A652-01-903</td>
			<td>&#8211;</td>
		</tr>
		<tr>
			<td>100 ml Autoclave Engineer&#39;s high pressure reactor</td>
			<td>Autoclave Engineer</td>
			<td>Custon design</td>
			<td>&#8211;</td>
		</tr>
		<tr>
			<td>Vortex Stirrer</td>
			<td>VWR</td>
			<td>444-1378</td>
			<td>&#8211;</td>
		</tr>
	</tbody>
</table>

the synthesis, characterization and reactivity of a series of ruthenium n-triphosph complexes

여기서 우리는 질소 대기 하에서 메탄올 중 암모니아와 hydroxylmethylene 포스 전구체의 인계 니히 반응을 통해 세자리 포스 핀 리간드 N (CH 2 PPH 2) 3 (N -triphos 박사) (1)의 합성을보고한다. N -triphos 박사 리간드 환류의 약 1 시간 후 상기 용액으로부터 석출 질소하에 캐뉼라 여과 간단한 절차를 통해 분석적으로 순수 분리 할 수있다. 환류 [의 Ru 3 (CO) 12]과 N -triphos 박사 리간드의 반응은 리간드 복합체에 CO 가스의 진화를 보여 깊은 붉은 솔루션을 제공한다. 복잡한 [의 Ru (CO) 2 {N (CH 2 PPH 2) 3} -κ 3 P] (2) 실온으로 냉각에 고립 된 오렌지 결정. P 31} {1 H NMR 스펙트럼은 더 낮은 주파수에서 단일 피크 특성을 보였다자유 리간드에 비해. 산소와의 복합체 (2)의 톨루엔 용액의 반응은 탄산 착체 [Ru로 (CO 3) (CO) {N (CH 2 PPH 2) 3} -κ 3 P]의 순시 침전 결과 (3) 공기 안정로서 고체 오렌지. 고압 반응기에서의 수소 3~15 하에서 바이어서 수소화 디히 착체 [RUH 2 (CO) {N (CH 2 PPH 2) 3} -κ 3 P (4), 완전히 X으로 특성화되었다 준 γ 선 결정학 및 NMR 스펙트럼에 의해 행 하였다. 단지 3 및도 4는 잠재적으로 레 불린 산 (LA) 등의 바이오 매스 유래의 제품을 포함하는 수소화 반응의 범위에 유용한 촉매 전구체이다. 단지 4 깔끔하게 NH 4 PF 6 - ({N을 [Ru로 수득 (CO) 양성자 공급원 첨가제의 존재하에 반응 LA였다CH 2 PPH 2) 3} -κ 3 P {CH 3 CO (CH 2) 2 CO 2 H} -κ 2 O] (PF 6) (6).

N -triphos 박사 리간드 (1) 및 루테늄 착체 시리즈 :의 Ru (CO) 2 {N (CH 2 PPH 2) 3} -κ 3 P (2), [Ru로 (CO 3) (CO) {N (CH 2 PPH 2) 3} -κ 3 P] (3) [Ru로 (H) 2 (CO) {N (PPH 2 CH 2) 3} -κ 3 P] (4) 1 H를 통해 특징으로하고, 13 C {...

Watch this Scientific Journal Video about The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes at JoVE.com

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

루테늄 포스 핀 복합체는 널리 균질 촉매 수소화 반응에 사용된다. N -triphos 리간드 N (CH 2 PPH 2) (3)을 담지 세자리 신규 한 루테늄 착물의 시리즈의 합성이보고되어있다. 또한, 레 불린 산 디히 Ru- N -triphos 착체의 화학 양 론적 반응을 설명한다.

루테늄의 시리즈의 합성, 특성 및 반응성<em&gt; N</em&gt; -triphos<sup&gt; 박사</sup&gt; 단지

Herein we report the synthesis of a tridentate phosphine ligand N(CH2PPh2)3 (N-triphosPh) (1) via a phosphorus based Mannich reaction of the ...

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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

12.1K 조회수.  Imperial College London.  루테늄 포스 핀 복합체는 널리 균질 촉매 수소화 반응에 사용된다. N -triphos 리간드 N (CH 2 PPH 2) (3)을 담지 세자리 신규 한 루테늄 착물의 시리즈의 합성이보고되어있다. 또한, 레 불린 산 디히 Ru- N -triphos 착체의 화학 양 론적 반응을 설명한다. 

비디오: The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

Isolation and Chemical Characterization of Lipid A from Gram-negative Bacteria

Lipopolysaccharide (LPS) is the major cell surface molecule of gram-negative bacteria, deposited on the outer leaflet of the outer membrane bilayer. LPS can be subdivided into three domains: the distal O-polysaccharide, a core oligosaccharide, and the lipid A domain consisting of a lipid A molecular species and 3-deoxy-D-manno-oct-2-ulosonic acid residues (Kdo). The lipid A domain is the only component essential for bacterial cell survival. Following its synthesis, lipid A is chemically modified in response to environmental stresses such as pH or temperature, to promote resistance to antibiotic compounds, and to evade recognition by mediators of the host innate immune response. The following protocol details the small- and large-scale isolation of lipid A from gram-negative bacteria. Isolated material is then chemically characterized by thin layer chromatography (TLC) or mass-spectrometry (MS). In addition to matrix-assisted laser desorption/ionization-time of flight (MALDI-TOF) MS, we also describe tandem MS protocols for analyzing lipid A molecular species using electrospray ionization (ESI) coupled to collision induced dissociation (CID) and newly employed ultraviolet photodissociation (UVPD) methods. Our MS protocols allow for unequivocal determination of chemical structure, paramount to characterization of lipid A molecules that contain unique or novel chemical modifications. We also describe the radioisotopic labeling, and subsequent isolation, of lipid A from bacterial cells for analysis by TLC. Relative to MS-based protocols, TLC provides a more economical and rapid characterization method, but cannot be used to unambiguously assign lipid A chemical structures without the use of standards of known chemical structure. Over the last two decades isolation and characterization of lipid A has led to numerous exciting discoveries that have improved our understanding of the physiology of gram-negative bacteria, mechanisms of antibiotic resistance, the human innate immune response, and have provided many new targets in the development of antibacterial compounds.

Isolation and characterization of the lipid A domain of lipopolysaccharide (LPS) from gram-negative bacteria provides insight into cell surface based mechanisms of antibiotic resistance, bacterial survival and fitness, and how chemically diverse lipid A molecular species differentially modulate host innate immune responses.

그람 음성 박테리아에서 분리 및 지질의 화학 특성

Lipopolysaccharide (LPS) is the major cell surface molecule of gram-negative bacteria, deposited on the outer leaflet of the outer membrane bilayer. LPS ...

연구

화학

Anticancer Metal Complexes: Synthesis and Cytotoxicity Evaluation by the MTT Assay

Titanium (IV) and vanadium (V) complexes are highly potent anticancer agents. A challenge in their synthesis refers to their hydrolytic instability; therefore their preparation should be conducted under an inert atmosphere. Evaluation of the anticancer activity of these complexes can be achieved by the MTT assay.
The MTT assay is a colorimetric viability assay based on enzymatic reduction of the MTT molecule to formazan when it is exposed to viable cells. The outcome of the reduction is a color change of the MTT molecule. Absorbance measurements relative to a control determine the percentage of remaining viable cancer cells following their treatment with varying concentrations of a tested compound, which is translated to the compound anticancer activity and its IC50 values. The MTT assay is widely common in cytotoxicity studies due to its accuracy, rapidity, and relative simplicity.
Herein we present a detailed protocol for the synthesis of air sensitive metal based drugs and cell viability measurements, including preparation of the cell plates, incubation of the compounds with the cells, viability measurements using the MTT assay, and determination of IC50 values.

A method for synthesis of air-sensitive titanium and vanadium anticancer agents is described, along with the evaluation of their cytotoxic activity towards human cancer cell line by the MTT Assay.

MTT의 분석에 의해 합성 및 세포 독성 평가 : 항암 금속 합성물

Titanium (IV) and vanadium (V) complexes are highly potent anticancer agents. A challenge in their synthesis refers to their hydrolytic instability; ...

Split-and-pool Synthesis and Characterization of Peptide Tertiary Amide Library

Peptidomimetics are great sources of protein ligands. The oligomeric nature of these compounds enables us to access large synthetic libraries on solid phase by using combinatorial chemistry. One of the most well studied classes of peptidomimetics is peptoids. Peptoids are easy to synthesize and have been shown to be proteolysis-resistant and cell-permeable. Over the past decade, many useful protein ligands have been identified through screening of peptoid libraries. However, most of the ligands identified from peptoid libraries do not display high affinity, with rare exceptions. This may be due, in part, to the lack of chiral centers and conformational constraints in peptoid molecules. Recently, we described a new synthetic route to access peptide tertiary amides (PTAs). PTAs are a superfamily of peptidomimetics that include but are not limited to peptides, peptoids and N-methylated peptides. With side chains on both &#945;-carbon and main chain nitrogen atoms, the conformation of these molecules are greatly constrained by sterical hindrance and allylic 1,3 strain. (Figure 1) Our study suggests that these PTA molecules are highly structured in solution and can be used to identify protein ligands. We believe that these molecules can be a future source of high-affinity protein ligands. Here we describe the synthetic method combining the power of both split-and-pool and sub-monomer strategies to synthesize a sample one-bead one-compound (OBOC) library of PTAs.

Peptide tertiary amides (PTAs) are a superfamily of peptidomimetics that include but are not limited to peptides, peptoids and N-methylated peptides. Here we describe a synthetic method which combines&#160;both split-and-pool and sub-monomer strategies to synthesize a one-bead one-compound library of PTAs.

분할 및 풀 합성 펩타이드 급 아미드 도서관의 특성

Peptidomimetics are great sources of protein ligands. The oligomeric nature of these compounds enables us to access large synthetic libraries on solid ...

Nucleoside Triphosphates - From Synthesis to Biochemical Characterization

The traditional strategy for the introduction of chemical functionalities is the use of solid-phase synthesis by appending suitably modified phosphoramidite precursors to the nascent chain. However, the conditions used during the synthesis and the restriction to rather short sequences hamper the applicability of this methodology. On the other hand, modified nucleoside triphosphates are activated building blocks that have been employed for the mild introduction of numerous functional groups into nucleic acids, a strategy that paves the way for the use of modified nucleic acids in a wide-ranging palette of practical applications such as functional tagging and generation of ribozymes and DNAzymes. One of the major challenges resides in the intricacy of the methodology leading to the isolation and characterization of these nucleoside analogues.
	
	In this video article, we present a detailed protocol for the synthesis of these modified analogues using phosphorous(III)-based reagents. In addition, the procedure for their biochemical characterization is divulged, with a special emphasis on primer extension reactions and TdT tailing polymerization. This detailed protocol will be of use for the crafting of modified dNTPs and their further use in chemical biology.

The protocol described herein aims to explain and abridge the numerous obstacles in the way of the intricate route leading to modified nucleoside triphosphates. Consequently, this protocol facilitates both the synthesis of these activated building-blocks and their availability for practical applications.

뉴 클레오 사이드 트리 포스페이트 - 합성에서 생화학 적 특성에

The  traditional strategy for the introduction of chemical functionalities is the  use of solid-phase synthesis by appending suitably modified ...

Synthesis and Characterization of Functionalized Metal-organic Frameworks

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and technological applications. Their signature property is their ultrahigh porosity, which however imparts a series of challenges when it comes to both constructing them and working with them. Securing desired MOF chemical and physical functionality by linker/node assembly into a highly porous framework of choice can pose difficulties, as less porous and more thermodynamically stable congeners (e.g., other crystalline polymorphs, catenated analogues) are often preferentially obtained by conventional synthesis methods. Once the desired product is obtained, its characterization often requires specialized techniques that address complications potentially arising from, for example, guest-molecule loss or preferential orientation of microcrystallites. Finally, accessing the large voids inside the MOFs for use in applications that involve gases can be problematic, as frameworks may be subject to collapse during removal of solvent molecules (remnants of solvothermal synthesis). In this paper, we describe synthesis and characterization methods routinely utilized in our lab either to solve or circumvent these issues. The methods include solvent-assisted linker exchange, powder X-ray diffraction in capillaries, and materials activation (cavity evacuation) by supercritical CO2 drying. Finally, we provide a protocol for determining a suitable pressure region for applying the Brunauer-Emmett-Teller analysis to nitrogen isotherms, so as to estimate surface area of MOFs with good accuracy.

Synthesis, activation, and characterization of intentionally designed metal-organic framework materials is challenging, especially when building blocks are incompatible or unwanted polymorphs are thermodynamically favored over desired forms. We describe how applications of solvent-assisted linker exchange, powder X-ray diffraction in capillaries and activation via supercritical CO2 drying, can address some of these challenges.

기능화의 합성 및 특성 금속 - 유기 프레임 워크

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and ...

Synthesis and Characterization of Supramolecular Colloids

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical properties for applications in photonics, drug delivery and coating technology. Here we present a new family of colloidal building blocks, coined supramolecular colloids, whose self-assembly is controlled through surface-functionalization with a benzene-1,3,5-tricarboxamide (BTA) derived supramolecular moiety. Such BTAs interact via directional, strong, yet reversible hydrogen-bonds with other identical BTAs. Herein, a protocol is presented that describes how to couple these BTAs to colloids and how to quantify the number of coupling sites, which determines the multivalency of the supramolecular colloids. Light scattering measurements show that the refractive index of the colloids is almost matched with that of the solvent, which strongly reduces the van der Waals forces between the colloids. Before photo-activation, the colloids remain well dispersed, as the BTAs are equipped with a photo-labile group that blocks the formation of hydrogen-bonds. Controlled deprotection with UV-light activates the short-range hydrogen-bonds between the BTAs, which triggers the colloidal self-assembly. The evolution from the dispersed state to the clustered state is monitored by confocal microscopy. These results are further quantified by image analysis with simple routines using ImageJ and Matlab. This merger of supramolecular chemistry and colloidal science offers a direct route towards light- and thermo-responsive colloidal assembly encoded in the surface-grafted monolayer.

A protocol for the synthesis and characterization of colloids coated with supramolecular moieties is described. These supramolecular colloids undergo self-assembly upon the activation of the hydrogen-bonds between the surface-anchored molecules by UV-light.

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical ...

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

The chemical linking or bioconjugation of proteins to fluorescent dyes, drugs, polymers and other proteins has a broad range of applications, such as the development of antibody drug conjugates (ADCs) and nanomedicine, fluorescent microscopy and systems chemistry. For many of these applications, specificity of the bioconjugation method used is of prime concern. The Michael addition of maleimides with cysteine(s) on the target proteins is highly selective and proceeds rapidly under mild conditions, making it one of the most popular methods for protein bioconjugation.
We demonstrate here the modification of the only surface-accessible cysteine residue on yeast cytochrome c with a ruthenium(II) bisterpyridine maleimide. The protein bioconjugation is verified by gel electrophoresis and purified by aqueous-based fast protein liquid chromatography in 27% yield of isolated protein material. Structural characterization with MALDI-TOF MS and UV-Vis is then used to verify that the bioconjugation is successful. The protocol shown here is easily applicable to other cysteine - maleimide coupling of proteins to other proteins, dyes, drugs or polymers.

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

This protocol details the important steps required for the bioconjugation of a cysteine containing protein to a maleimide, including reagent purification, reaction conditions, bioconjugate purification and bioconjugate characterization.

The chemical linking or bioconjugation of proteins to fluorescent dyes, drugs, polymers and other proteins has a broad range of applications, such as the ...

Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level

We demonstrate a method for the synthesis of cyclic polymers and a protocol for characterizing their diffusive motion in a melt state at the single molecule level. An electrostatic self-assembly and covalent fixation (ESA-CF) process is used for the synthesis of the cyclic poly(tetrahydrofuran) (poly(THF)). The diffusive motion of individual cyclic polymer chains in a melt state is visualized using single molecule fluorescence imaging by incorporating a fluorophore unit in the cyclic chains. The diffusive motion of the chains is quantitatively characterized by means of a combination of mean-squared displacement (MSD) analysis and a cumulative distribution function (CDF) analysis. The cyclic polymer exhibits multiple-mode diffusion which is distinct from its linear counterpart. The results demonstrate that the diffusional heterogeneity of polymers that is often hidden behind ensemble averaging can be revealed by the efficient synthesis of the cyclic polymers using the ESA-CF process and the quantitative analysis of the diffusive motion at the single molecule level using the MSD and CDF analyses.

A protocol for the synthesis and characterization of diffusive motion of cyclic polymers at the single molecule level is presented.

단일 분자 수준에서 순환 고분자의 합성 및 용융 상태에서 그들의 확산 운동의 특성

We demonstrate a method for the synthesis of cyclic polymers and a protocol for characterizing their diffusive motion in a melt state at the single ...

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of Chalcogenidoplumbates(II or IV)

The phases of &#34;PbCh2&#34; (Ch = Se, Te) are obtained from solid-state syntheses (i.e., by the fusion of the elements under inert conditions in silica glass ampules). Reduction of such phases by elemental alkaline metals in amines affords crystalline chalcogenidoplumbate(II) salts comprised of [PbTe3]2- or [Pb2Ch3]2- anions, depending upon which sequestering agent for the cations is present: crown ethers, like 18-crown-6, or cryptands, like [2.2.2]crypt. Reactions of solutions of such anions with transition-metal compounds yield (poly-)chalcogenide anions or transition-metal chalcogenide clusters, including one with a &#181;-PbSe ligand (i.e., the heaviest-known CO homolog).
In contrast, the solid-state synthesis of a phase of the nominal composition &#34;K2PbSe2&#34; by successive reactions of the elements and by the subsequent solvothermal treatment in amines yields the first non-oxide/halide inorganic lead(IV) compound: a salt of the ortho-selenidoplumbate(IV) anion [PbSe4]4-. This was unexpected due to the redox potentials of Pb(IV) and Se(-II). Such methods can further be applied to other elemental combinations, leading to the formation of solutions with binary [HgTe2]2- or [BiSe3]3- anions, or to large-scale syntheses of K2Hg2Se3 or K3BiSe3 via the solid-state route.
All compounds are characterized by single-crystal X-ray diffraction and elemental analysis; solutions of plumbate salts can be investigated by 205Pb and 77Se or 127Te NMR techniques. Quantum chemical calculations using density functional theory methods enable energy comparisons. They further allow for insights into the electronic configuration and thus, the bonding situation. Molecular Rh-containing Chevrel-type compounds were found to exhibit delocalized mixed valence, whereas similar telluridopalladate anions are electron-precise; the cluster with the &#181;-PbSe ligand is energetically favored over a hypothetical CO analog, in line with the unsuccessful attempt at its synthesis. The stability of formal Pb(IV) within the [PbSe4]4- anion is mainly due to a suitable stabilization within the crystal lattice.

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV

The synthesis of chalcogenidoplumbates(II,IV) via the in situ reduction of nominal "PbCh2" (Ch = Chalcogen) and via a solid-state reaction and subsequent solvothermal reactions is presented. Additionally, reactivities of plumbate(II) solutions are portrayed, which yield the heaviest-known CO homolog known to date: the &#181;-PbSe ligand.

고체 및 솔루션 기반의 기술 결합 : 합성 및 Chalcogenidoplumbates의 반응성 (II 또는 IV)

The phases of &#34;PbCh2&#34; (Ch = Se, Te) are obtained from solid-state syntheses (i.e., by the fusion of the elements under inert conditions in silica ...

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from benzimidazolium salts. Detailed and generalized protocols are also presented for testing the catalytic activity of such complexes in arylation and Suzuki-Miyaura cross-coupling reactions. Representative results are shown for the catalytic activity of the four complexes in arylation and Suzuki-Miyaura type reactions. For each of the reactions investigated, at least one of the four complexes successfully catalyzed the reaction, qualifying them as promising candidates for catalysis of many carbon-carbon bond-forming reactions. The protocols presented are general enough to be adapted for the synthesis, purification and catalytic activity testing of new palladium N-heterocyclic carbene complexes.

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from benzimidazolium salts. The complexes were tested for catalytic activity in arylation and Suzuki-Miyaura reactions. For each reaction investigated, at least one of the four complexes successfully catalyzed the reaction.

보장<em&gt; N</em&gt; - 헤테로 사이 클릭 카벤 착물 : 벤즈 이미 다 졸리움 염으로부터의 합성 및 탄소 - 탄소 결합 형성 반응에서의 촉매 활성

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from ...

루테늄의 시리즈의 합성, 특성 및 반응성

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더 많은 비디오 탐색

이 비디오의 챕터

그람 음성 박테리아에서 분리 및 지질의 화학 특성

MTT의 분석에 의해 합성 및 세포 독성 평가 : 항암 금속 합성물

분할 및 풀 합성 펩타이드 급 아미드 도서관의 특성

뉴 클레오 사이드 트리 포스페이트 - 합성에서 생화학 적 특성에

기능화의 합성 및 특성 금속 - 유기 프레임 워크

Synthesis and Characterization of Supramolecular Colloids

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

단일 분자 수준에서 순환 고분자의 합성 및 용융 상태에서 그들의 확산 운동의 특성

고체 및 솔루션 기반의 기술 결합 : 합성 및 Chalcogenidoplumbates의 반응성 (II 또는 IV)

보장