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.

注：ドラフト内でのすべての合成を実行し、適切な安全性の問題が同定されており、対策がそれらから保護するために撮影した後にのみ。個人用保護具は、白衣、手袋、安全ゴーグルを含み、常に着用する。 N、N、N &#39; -トリス（diphenylphosphinomethylene）アミン、N（CH 2のPPh 2）3（N -triphos のPh）（1）の合成1 <ol><li> 200ミリリットルにオーブンのシュレンクフラスコに、デュアルマニホールドシュレンクライン上の3つの連続真空-窒素サイクルを経由して、窒素下ジフェニル（ヒドロキシメチレン）ホスホニウムクロリド11（6.99グラム、24.7ミリモル）と場所を追加し乾燥した。 </li><li>脱気したメタノール（30ml）およびトリエチルアミン（9.5ミリリットル、68.1ミリモル）を追加し、hydroxymetheneホスフィンの塩化ホスホニウム塩への変換を確実にするために室温で1時間撹拌する。次に、メタノール（2 M、4.1ミリリットル、8.2ミリモル）の脱気したアンモニア溶液を加える。 </li><li>還流下で2時間反応混合物を加熱、その間リガンドが白色固体として沈殿する。 </li><li> N -triphos Phはリガンドが短時間にわたって空気中で酸化に対して安定であるが、最適な純度を、窒素下でカニューレ濾過26を介して溶媒を除去し、分析的に純粋な生成物を得るために、脱気したメタノール（3×10ml）ですすぎ、及び窒素雰囲気下で保存する。 </li></ol> 2.合成の[Ru（CO）2 {N（CH 2のPPh 2）3}-κ3 P]（2） <ol><li> 200ミリリットルのオーブン乾燥したシュレンクフラスコに、N -Triphos のPh（1.0グラム、1.63ミリモル）との[Ru 3（CO）12]（347ミリグラム、0.54ミリモル）、及び上の3つの連続真空-窒素サイクルを介して窒素下に場所を追加するデュアルマニホールドシュレンクライン。 </li><li>乾燥、脱気したトルエン30mlを加え、12時間還流混合物をもたらす。 </li><li>この12時間の還流後、2番目のシュレンクフラスコにカニューレを介してソリューションをフィルタリング反応の過程で形成する金属ルテニウムの少量を削除します。 </li><li>複合体の沈殿を誘導するために、トラップを冷却し、液体窒素を取り付けデュアルマニホールドシュレンクラインを用いて真空下で約10mlまで溶媒の体積を減少させる。 </li><li>油浴から熱を除去するが、シュレンクフラスコに沈めたままにさせることによってRTに完全な再溶解が発生するまで、油浴中で穏やかに（80〜90℃）に加熱し、その後ゆっくりと冷却することによって沈殿物を再結晶化。オレンジ色の固体結晶性を与えるために、O / Nのままにしておきます。 </li><li>別のオーブンに上清のカニューレ濾過によりX線回折に適したオレンジ色の結晶を分離するには、シュレンクフラスコに乾燥した。次に、 真空下 O / N で乾燥し、脱気トルエン（2×5ml）および乾燥の結晶をすすぐ。独立したシュレンクフラスコ中で組み合わせた上澄みと洗浄液を保存します。 </li><li>組み合わせた上清およびリンス溶液から結晶の第二のバッチを取得ステップ2.5および2.6と同様の再結晶法によるのは、反応の全収率を改善する。 </li><li>空気への暴露が酸化炭酸塩複合体（下記参照）にゆっくり転換につながるように、窒素下で複雑に保管してください。 </li></ol> 3.合成の[Ru（CO 3）（CO）{N（CH 2のPPh 2）3}-κ3 P]（3） <ol><li> 200ミリリットルのシュレンクフラスコに、部分的に溶解したオレンジ色の懸濁液を生成するために、2（280ミリグラム、0.364ミリモル）およびトルエン5mlを加える。 </li><li> 10分間反応混合物を通して毎秒2-3気泡の割合でサスペンションとバブル酸素への酸素のバルーンに取り付けられた針を挿入します。 </li><li>オレンジ色の沈殿物が形成されるように、空気中で濾過することにより、それを収集し、空気中で安定であった自由流動性のオレンジ色の粉末を真空中でトルエン（2×5ml）およびジエチルエーテル（2×5ml）および乾燥で洗浄した。 </li><li> X線DIFFRに適した結晶を成長させるためにアクションは、ゆっくりとバイアルの側面を下に実行するには、この溶剤を可能にすることにより、上部のバイアルとレイヤ3ミリリットルのトルエンに3ミリリットルのジクロロメタンに3 100mgを溶解させる。 <ol><li>結晶を得るために、このO / Nのままにしておきます。上清をデカントし、そしてトルエン（2×3ml）およびジエチルエーテル（2×3 ml）で洗浄することにより結晶を単離する。デュアルマニホールドシュレンクライン上で真空中で乾燥。 </li></ol></li></ol> 4.合成の[Ru（H）2（CO）{N（CH 2のPPh 2）3}-κ3 P]（4） <ol><li>乾燥した20mlの3（763ミリグラム、0.953ミリモル）の溶液を調製し、THFを脱ガスし、窒素の正圧（0.2バール）下、100ミリリットルのオートクレーブエンジニアの高圧反応器に注入する。 </li><li> 100％の水素を反応器のヘッドスペースガスを変更し、2時間攪拌しながら100℃まで熱その後、RTで15バールに加圧する。 注意！すべての安全手順を確認し、高い使用する際に接着されています圧力システム！ </li><li> RTに冷却後、慎重に反応器のヘッドスペースを窒素への変化に過剰な水素ガスを通気。 </li><li>窒素下で100ミリリットルのシュレンクフラスコに反応液を移し、デュアルマニホールドシュレンクラインに再接続した後、カニューレを経由してフィルタし、乾燥、脱気したメタノール20mlで希釈する。 </li><li>液体窒素を取り付けデュアルマニホールドシュレンクラインを用いて真空下で溶媒を除去し、オレンジ色の粉末を得トラップを冷却した。乾燥、脱気メタノール（3×5ml）で乾燥して、このオレンジ色の粉末を洗って、ジエチルエーテル（3×5ml）で、真空下で乾燥し脱気した。 </li><li>飽和ドライからX線回折分析O / Nに適した結晶を成長させ、乾燥した等量の量で4層状のトルエン溶液を脱気し、メタノールの脱気した。 </li><li>窒素下で複雑に保管してください。 </li></ol> RUH 2（CO）{N（CH 2のPPh 2）3}-κ3 P [5.反応]（4）NH 4 PF 6、レブリン酸と<ol><li>ドライ2mlの4（48.4 mgの、65.2マイクロモル）の溶液を準備し、シュレンクフラスコを乾燥したオーブンでトルエンを脱気し、そしてアセトニトリル中でNH 4 PF 6（10.6ミリグラム、65.0マイクロモル）の撹拌溶液にシリンジを介して追加する（2 ml）を別々のオーブンでシュレンクフラスコを乾燥させた。 </li><li>室温で2時間反応混合物を撹拌した。後に、液体窒素を取り付けデュアルマニホールドシュレンクラインを用いて、真空中で溶媒を除去する（中間複合体[RUH（CO）（MeCN中）{N（CH 2のPPh 2）3}-κ3 P]を得るためにトラップを冷却5）。 </li><li>乾燥で洗浄し、褐色粉末として錯体5を分離し、真空下で 、ヘキサン（3×3ml）および乾燥し脱気した。 </li><li> 5 0.5 mlの溶液に脱ガスしたアセトン-d 6の0.5ミリリットルでレブリン酸（10.8 mgの、93.0マイクロモル、1.43当量）を追加し、アセトン-d 6を脱気した。使用して2分間、反応混合物を撹拌しボルテックス撹拌機。 </li><li>レコード1 H及び30 P {1 H}反応16時間、反応を観察するための時間ごとのNMRスペクトル。27 </li></ol>

<ol>
	<li>Bruneau, C., Dixneuf, P. H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Ruthenium Catalysis and Fine Chemicals. , (2004).</li><li>Naota, T., Takaya, H., Murahashi, S. -. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ruthenium-Catalyzed+Reactions+for+Organic+Synthesis.">Ruthenium-Catalyzed Reactions for Organic Synthesis.</a> Chem. Rev. 98 (7), 2599-2660 (1998).</li><li>Arockaim, P. B., Bruneau, C., Dixneuf, P. H. <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)-Catalyzed+C-H+Bond+Activation+and+Functionalization.">Ruthenium(II)-Catalyzed C-H Bond Activation and Functionalization.</a> Chem. Rev. 112 (11), 5879-5918 (2012).</li><li>Trost, B. M., Toste, F. D., Pinkerton, A. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Non-metathesis+ruthenium-catalyzed+C-C+bond+formation.">Non-metathesis ruthenium-catalyzed C-C bond formation.</a> Chem. Rev. 101 (7), 2067-2096 (2001).</li><li>Vougioukalakis, G. C., Grubbs, R. H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ruthenium-Based+Heterocyclic+Carbene-Coordinated+Olefin+Metathesis+Catalysis.">Ruthenium-Based Heterocyclic Carbene-Coordinated Olefin Metathesis Catalysis.</a> Chem. Rev. 110 (3), 1746-1787 (2010).</li><li>Lozano-Vila, A. M., Monsaert, S., Bajek, A., Verpoort, F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ruthenium-based+olefin+metathesis+catalysts+derived+from+alkynes.">Ruthenium-based olefin metathesis catalysts derived from alkynes.</a> Chem. Rev. 110 (8), 4865-4909 (2010).</li><li>Samojlowicz, C., Bieniek, M., Grela, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ruthenium-based+olefin+metathesis+catalysts+bearing+N-heterocyclic+carbene+ligands.">Ruthenium-based olefin metathesis catalysts bearing N-heterocyclic carbene ligands.</a> Chem. Rev. 109 (8), 3708-3742 (2009).</li><li>Alcaide, B., Almedros, P., Luna, A. G. r. u. b. b. s. &. #. 8. 2. 1. 7. ;. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ruthenium-Carbenes+Beyond+the+Metathesis+Reaction:+Less+Conventional+Non-Metathetic+Utility.">Ruthenium-Carbenes Beyond the Metathesis Reaction: Less Conventional Non-Metathetic Utility.</a> Chem. Rev. 109 (8), 3817-3858 (2009).</li><li>Conley, B. L., Pennington-Boggio, M. K., Boz, E., Discovery Williams, T. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Applications,+and+Catalytic+Mechanisms+of+Shvo&#8217;s+Catalyst.">Applications, and Catalytic Mechanisms of Shvo&#8217;s Catalyst.</a> Chem. Rev. 110 (4), 2294-2312 (2010).</li><li>Miller, P. W., White, A. J. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+preparation+of+multimetallic+complexes+using+sterically+bulky+N-centered+tipodal+dialkyl+phosphine+ligands.">The preparation of multimetallic complexes using sterically bulky N-centered tipodal dialkyl phosphine ligands.</a> J. Organomet. Chem. 695 (8), 1138-1145 (2010).</li><li>Hanton, M. J., Tin, S., Boardman, B. J., Miller, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ruthenium-catalysed+hydrogenation+of+esters+using+tripodal+phosphine+ligands.">Ruthenium-catalysed hydrogenation of esters using tripodal phosphine ligands.</a> J. Mol. Catal. A. 346 (1-2), 70-78 (2012).</li><li>Phanopoulos, A., Brown, N. J., White, A. J. P., Long, N. J., Miller, P. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis,+Characterization,+and+Reactivity+of+Ruthenium+Hydride+Complexes+of+N-Centered+Triphosphine+Ligands.">Synthesis, Characterization, and Reactivity of Ruthenium Hydride Complexes of N-Centered Triphosphine Ligands.</a> Inorg. Chem. 53 (7), 3742-3752 (2014).</li><li>Jin, G. Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=N.N.N-tris(phosphinomethylen)amine+N.N.N&#8217;-tris(phosphinomethylene)hydrazine+N.N.N&#8217;.N&#8217;-tetra(phosphinomethylene)hydrazine.">N.N.N-tris(phosphinomethylen)amine N.N.N&#8217;-tris(phosphinomethylene)hydrazine N.N.N&#8217;.N&#8217;-tetra(phosphinomethylene)hydrazine.</a> Tetrahedron Lett. 22 (12), 1105-1108 (1981).</li><li>Walter, O., Huttner, G., Kern, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Preparation+and+Characterisation+of+N(CH2PPh2)3.+N(CH2PPh2)3Mo(CO)3+and+[HN(CH2PPh2)3Mo(CO)3]BF4.">Preparation and Characterisation of N(CH2PPh2)3. N(CH2PPh2)3Mo(CO)3 and [HN(CH2PPh2)3Mo(CO)3]BF4.</a> Z. Naturforsch. 51b, 922-928 (1996).</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., Kruckenberg, A., Mader, S., 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=Ruthenium+&#951;4-Trimethylenemethane+Complexes+Containing+Tripodal+Phosphanomethylamine+Ligands.">Ruthenium &#951;4-Trimethylenemethane Complexes Containing Tripodal Phosphanomethylamine Ligands.</a> Organometallics. 31 (19), 7024-7027 (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>Geilen, F. M. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Selective+and+Flexible+Transformation+of+Biomass-Derived+Platform+Chemicals+by+a+Multifunctional+Catalytic+System.">Selective and Flexible Transformation of Biomass-Derived Platform Chemicals by a Multifunctional Catalytic System.</a> Angew. Chem. Int. Ed. 49 (32), 5510-5514 (2010).</li><li>Geilen, F. M. A., Engendahl, B., H&#246;lscher, M., 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=Selective+Homogeneous+Hydrogenation+of+Biogenic+Carboxylic+Acids+with+[Ru(TriPhos)H]+:+A+Mechanistic+Study.">Selective Homogeneous Hydrogenation of Biogenic Carboxylic Acids with [Ru(TriPhos)H]+: A Mechanistic Study.</a> J. Am. Chem. Soc. 133 (36), 14349-14358 (2011).</li><li>Van Engelen, M. C., Teunissen, H. T., de Vries, J. G., Elsevier, C. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Suitable+ligands+for+homogeneous+ruthenium-catalyzed+hydrogenolysis+of+esters.">Suitable ligands for homogeneous ruthenium-catalyzed hydrogenolysis of esters.</a> J. Mol. Catal. 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.

本明細書で我々は、三座ホスフィン配位子及びルテニウム錯体の一連の合成のための効率的な合成手順を記載している。 N -triphos Phのリガンド （1）を容易に最小限のワークアップ手順を高収率で製造することができる。リガンドのこれらのタイプを合成するために使用されるこのリン系マンニッヒ反応は、非常に一般的であり、P原子上のR基が異なる?...

ルテニウムホスフィンベースの複合体は、最も広く研究され、化学的に汎用性分子触媒の一部である。1-9は、典型的には、このようなルテニウム触媒は、錯体の電子、立体構造、ジオメトリ、および溶解度を決定する単環または二座配位子のいずれかを含む、かつ深く触媒活性に影響を与える。多座ホスフィン系は少なく広く、それらが金属中心に複数のリンドナーの大きなキレート効果により金属中心に高い安定性を付与することが知られているように、触媒作用のために研究されている。このような安定化は、触媒の完全性を確保する上で有利となり得る厳しい反応条件（より高い温度および圧力）そのようなリガンドの複合体安定化特性の下で、しかし、触媒作用のために望ましくないことがある。我々 10-12と他人13-18は、複雑な安定性と顔の COORを付与するために研究しているそのような多座ホスフィン配位子システムdinationジオメトリ三ホスフィンアームは、潜在的に、三座配位子を形成する頂端架橋窒素原子に結合している、いわゆるN -triphosリガンドシリーズ。これらの特定のリガンドへの主要な機能の1つは、それらが容易に入手できる二ホスフィン（ 図1）からのリンベースのマンニッヒ反応を介して合成することができることを容易な方法であり、したがって、R基の種々のホスフィン高収率で通常調製することができる。と最小限のワークアップと。この方法の全体的な目標は、N -triphosリガンドを特色ルテニウム二水素錯体は、その後の触媒用途のためにアクセスすることのできる容易なルートを提供することである。近年、ルテニウム-トリホスベースの複合体は、より高い価値の化学物質へのそのようなレブリン酸などのバイオマス由来製品、19,20バイオエステル11,21および二酸化炭素22の水素化反応のための触媒として注目されている。それは有利であろうとして、またはすでに彼らがそのようなN -triphosリガンドとして、アクセスに合成が容易である場合は特に、報告されたシステムよりもアクティブのどちらかであるのRu-トリホス誘導体の範囲を拡大する。最も研究炭素中心アナログは、典型的には、低収量合成に苦しんでいると非常に空気に敏感な金属リン化物試薬を含み、より適応と準備をする方が簡単ですN -triphosリガンドとは異なり。10-18 N -triphosリガンドは唯一のモリブデン、タングステン、ルテニウム、ロジウム、金錯体は9出版物から報告されたと、比較的アンダー調査したまま。これはユニークな化合物が多数で、それぞれ、約50および900の記事がありますいるホウ素と炭素中心類似体、全く対照的である。それにもかかわらず、複合体を含むN個の -triphosは、私たちのように、プロキラルオレフィン23の触媒的不斉水素化に応用されているllのNの非対称cyclohydroaminationはγ-アレニルスルホンアミド-保護24はまた、部分配ホスホランを特徴とバルキーN -triphos配位子によって配位ルテニウム錯体は、シラン、有機化学の開発における重要なステップを活性化することが見出された。25 触媒反応で進行中の研究プログラムの一環として、当社は、ルテニウムの範囲N -triphos のPhプレ触媒を準備し、それらの化学量論的反応や触媒の可能性を調査しようとした。最初の25年以上前に報告されたN -triphos のPhのモリブデン錯体にもかかわらず、彼らのアプリケーションは、触媒的またはその他の方法で調査されていない。この作品は、一般的に未発達であるにもかかわらず、このような複雑な安定性などの多くの望ましい特徴を保有するN -triphos足場の適用可能性を示している。 。ここで我々は、への合成経路および特性を報告接触水素化反応に用途を見出すことができるルテニウムN -triphos Phの複合体の一連。

<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

本明細書において、我々は、窒素雰囲気下で、メタノール中のアンモニアとhydroxylmethyleneホスフィン前駆体のリン系マンニッヒ反応を介して三座ホスフィン配位子N（CH 2のPPh 2）3（N -triphos のPh）（1）の合成を報告している。 N -triphos Phはリガンド還流の約1時間後に溶液から沈殿し、窒素下で単純なカニューレ濾過手順を介して、分析的に純粋な単離することができる。還流下での[Ru 3（CO）12]とN -triphos Phのリガンドの反応は、リガンド錯体におけるCOガスの発生を示した深赤色溶液を得る。錯体の橙色結晶の[Ru（CO）2 {N（CH 2のPPh 2）3}-κ3 P]は （2）RTに冷却して単離した。 31 P {1 H} NMRスペクトルは、低い周波数で特性が単一のピークを示した遊離リガンドと比較した。酸素との複合体2のトルエン溶液の反応は、炭酸塩、複合体の瞬間的な沈殿を生じたの[Ru（CO 3）（CO）{N（CH 2のPPh 2）3}-κ3 P]（3）空気安定としてオレンジ色の固体。高圧反応器中の水素の3 15の下のバーの後続の水素化は、二水素錯体[RUH 2（CO）{N（CH 2のPPh 2）3}-κ3 P]（4）、完全にXによって特徴付けられたγ線結晶学およびNMR分光法。複合体3および4は、潜在的にそのようなレブリン酸（LA）などのバイオマス由来製品を含む水素化反応の範囲のための有用な触媒前駆体である。複合体4は、きれいにRu（CO）{N（[与えるプロトン源の添加剤NH 4 PF 6の存在下でLAと反応することが見出されたCH 2のPPh 2）3}-κ3 P {CH 3 CO（CH 2）2 CO 2 H}-κ2 O]（PF 6）（6）。

N -triphos Phのリガンド （1）及びルテニウム錯体シリーズのRu（CO）2 {N（CH 2のPPh 2）3}-κ3 P]（2）の[Ru（CO 3）（CO）{N （CH 2のPPh 2）3}-κ3 P]（3）との[Ru（H）2（CO）{N（のPPh 2 CH 2）3}-κ3 P]（4）1 H介して特徴付けら?...

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

ルテニウムホスフィン錯体が広く水素化のような均質触媒反応のために使用される。 N -triphosリガンドN（CH 2のPPh 2）3を有する新規な三座ルテニウム錯体の一連の合成が報告されている。さらに、レブリン酸と二水素Ru- N -triphos複合体の化学量論反応が記載されている。

ルテニウムのシリーズの合成、キャラクタリゼーションと反応性<em&gt; N</em&gt; -triphos<sup&gt; Phで</sup&gt;錯体

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

the-synthesis-characterization-reactivity-series-ruthenium-n

Research

JoVE Journal

Chemistry

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

12.0K ビュー.  Imperial College London. ルテニウムホスフィン錯体が広く水素化のような均質触媒反応のために使用される。 N -triphosリガンドN（CH 2のPPh 2）3を有する新規な三座ルテニウム錯体の一連の合成が報告されている。さらに、レブリン酸と二水素Ru- N -triphos複合体の化学量論反応が記載されている。 

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

Production of Disulfide-stabilized Transmembrane Peptide Complexes for Structural Studies

Physical interactions among the lipid-embedded alpha-helical domains of membrane proteins play a crucial role in folding and assembly of membrane protein complexes and in dynamic processes such as transmembrane (TM) signaling and regulation of cell-surface protein levels. Understanding the structural features driving the association of particular sequences requires sophisticated biophysical and biochemical analyses of TM peptide complexes. However, the extreme hydrophobicity of TM domains makes them very difficult to manipulate using standard peptide chemistry techniques, and production of suitable study material often proves prohibitively challenging. Identifying conditions under which peptides can adopt stable helical conformations and form complexes spontaneously adds a further level of difficulty. Here we present a procedure for the production of homo- or hetero-dimeric TM peptide complexes from materials that are expressed in E. coli, thus allowing incorporation of stable isotope labels for nuclear magnetic resonance (NMR) or non-natural amino acids for other applications relatively inexpensively. The key innovation in this method is that TM complexes are produced and purified as covalently associated (disulfide-crosslinked) assemblies that can form stable, stoichiometric and homogeneous structures when reconstituted into detergent, lipid or other membrane-mimetic materials. We also present carefully optimized procedures for expression and purification that are equally applicable whether producing single TM domains or crosslinked complexes and provide advice for adapting these methods to new TM sequences.

Biophysical and biochemical studies of interactions among membrane-embedded protein domains face many technical challenges, the first of which is obtaining appropriate study material. This article describes a protocol for producing and purifying disulfide-stabilized transmembrane peptide complexes that are suitable for structural analysis by solution nuclear magnetic resonance (NMR) and other analytical applications.

構造研究のためのジスルフィド安定化膜貫通ペプチド複合体の生産

Physical  interactions among the lipid-embedded alpha-helical domains of membrane  proteins play a crucial role in folding and assembly of membrane ...

化学

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.

グラム陰性菌からの単離とリピドAの化学特性評価

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

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.

MTTアッセイにより合成と細胞毒性の評価：抗がん金属錯体

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.

ペプチド第三級アミドライブラリのスプリット·アンド·プールの合成とキャラクタリゼーション

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.

ヌクレオシド三リン酸 - 合成からの生化学的特徴付けへ

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.

官能化有機金属構造体の合成とキャラクタリゼーション

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.

超分子コロイドの合成とキャラクタリゼーション

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

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.

単一分子レベルでの環状ポリマーの合成と溶融状態におけるそれらの拡散運動のキャラクタリゼーション

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.

組み合わせソリッドステートおよびソリューションベースのテクニック：合成と反応性Chalcogenidoplumbatesの（IIまたは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.

パラジウム<em&gt; N</em&gt; - 複素環カルベン錯体：ベンズイミダゾリウム塩からの合成と炭素 - 炭素結合形成反応における触媒活性

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