New Transformations of Unsaturated Hydrocarbons with Polynuclear Complexes of Pd (I)

Pd(I)多核配合物对不饱和烃的新转化

• 批准号: 11490023
• 负责人: KUROSAWA Hideo
• 金额: $ 1.15万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11490023/
• 关键词: Pd (I) Complex; Sandwich complex; Bridge complex; 袈橋配位子; 親電子攻撃; アルキン2量化

Increasing attention has been paid to rapid progress in the field of organic synthesis by means of palladium complex based catalyst. In most of the catalysis, key intermediates are believed to have the oxidation state of Pd (0) and Pd(II). However, there is an urgent need to revolutionize this methodology. The aim of the present project is to lay a molecular level basis for the synthetic method of the next generation by studying preparation, structure and reactions of polynuclear Pd (I) complexes containing bridging ligands such as allyl, propargyl, vinyl, alkynyl, and carbene. First of all, the Pd (I)-Pd (I) complexes containing 4 and 6 acetonitrile ligands, which can readily be replaced by weak ligands such as unsaturated hydrocarbons, have been prepared. X-ray structure determination established coordination of two PPh_3 ligands to the Pd (I)-Pd (I) unit having four acetonitrile ligands. This complex reacted with two equiv. phenylacetylene to give the Pd-Pd complex containing the bridging butenediylidene ligand made by head-to-tail dimerization of the acetylene. The Pd (I)-Pd (I) complex having six acetonitrile ligands reacted with 1, 8-diphenyloctatetraene in the presence of Pd (0) complex to give novel sandwich complex made by two tetraen ligands coordinating to the linear Pd_4 chain. Next the Pd (I)-Pd (I) complexes containing bridging diene and allene ligands were synthesized, and their structures determined by NMR and X-ray analysis as well as by MO calculation. These studies established that considerable electron density flows from the Pd-Pd σ orbital to the antibonding MO of the organic ligand through back bonding interaction.

钯配合物基催化剂在有机合成领域的快速发展受到越来越多的关注。在大多数催化中，关键中间体被认为具有Pd(0)和Pd(II)的氧化态。然而，迫切需要彻底改变这一方法。本项目的目的是通过研究含有烯丙基、丙叉基、乙烯基、炔基和卡宾等桥联配体的多核Pd(I)配合物的制备、结构和反应，为下一代合成方法奠定分子水平的基础。首先，合成了含4和6个乙腈配体的Pd(I)-Pd(I)配合物，这些配体很容易被不饱和碳氢化合物等弱配体取代。X-射线结构测定确定了两个PPh_3配体与具有四个乙腈配体的Pd(I)-Pd(I)单元配位。该络合物与两个当量的化合物反应。苯乙炔得到的Pd-Pd络合物含有通过乙炔头尾二聚得到的桥联丁烯二叉配体。具有6个乙腈配体的Pd(I)-Pd(I)络合物在Pd(0)络合物的存在下与1，8-二苯基四氢呋喃反应，得到了由两个四烯配体与Pd_4链配位的新型夹心络合物。其次，合成了含桥联双烯和联烯配体的Pd(I)-Pd(I)配合物，并通过核磁共振、X-射线分析和分子轨道计算确定了它们的结构。这些研究表明，相当大的电子密度通过回键作用从Pd-Pd的σ轨道流向有机配体的反键MO。

项目成果

T.Murahashi, E.Mochizuki, Y.Kai, H.Kurosawa: "Organometallic Sandwich Chains Made of Conjugated Polyenes and Metal-Metal Chains"J.Am.Chem.Soc.. 121. 10660-10661 (1999)

T.Murahashi、E.Mochizuki、Y.Kai、H.Kurosawa：“由共轭多烯和金属-金属链制成的有机金属三明治链”J.Am.Chem.Soc.. 121. 10660-10661 (1999)

S.Ogoshi, T.Nishida, K.Tsutsumi, M.Ooi, H.Kurosawa: "Carbon-Carbon Bond Formation by Electrophilic Addition at Central Carbon of μ-η^3-Allenyl/propargyl Ligand on Pd-Pd Bond."J.Am.Chem.Soc.. 123 (in press). (2001)

S.Ogoshi、T.Nishida、K.Tsutsumi、M.Ooi、H.Kurosawa：“通过在 Pd-Pd 键上的 μ-η^3-丙二烯基/炔丙基配体的中心碳上亲电加成形成碳-碳键。” J.Am.Chem.Soc.. 123（印刷中）（2001 年）。

T.Murahashi,T.Otani,T.Okuno,H.Kurosawa: "Coupling of Alkynes on Pd-Pd to Generate an Electrophilic μ-Butenediylidene Moiety"Angew.Chem.Int.Ed.Engl.. 39. 537-540 (2000)

T.Murahashi、T.Otani、T.Okuno、H.Kurosawa：“在 Pd-Pd 上偶联炔烃以生成亲电 μ-丁烯二亚基部分”Angew.Chem.Int.Ed.Engl.. 39. 537-540（ 2000）

T.Murahashi, T.Nagai, T.Okuno, T.Matsutani, H.Kurosawa: "Synthesis and Ligand Substitution Reaction of Homoleptic Acetonitrile Dipalladium (I) Complex."J.Chem.Soc., Chem, Comm.. 1689-1690 (2000)

T.Murahashi、T.Nagai、T.Okuno、T.Matsutani、H.Kurosawa：“均配乙腈二钯 (I) 复合物的合成和配体取代反应”。J.Chem.Soc.、Chem、Comm.. 1689-

S.Ogoshi,T.Nishida,K.Tsutsusmi,M.Doi,H.Kurosawa: "Carbon-Carbon Bond Formation by Electrophilic Addition at the Central Carbon of the -3-Allenyl/Propargyl Ligand on the Pd-Pd Bond"J.Am.Chem.Soc.. 123(印刷中). (2001)

S. Ogoshi、T. Nishida、K. Tsutsusmi、M. Doi、H. Kurosawa：“通过在 Pd-Pd 键上的 -3-丙二烯基/炔丙基配体的中心碳上亲电加成形成碳-碳键”J .Am.Chem.Soc..123（印刷中）（2001）。