Structure and Reactivity of Organopalladium Complexes Bearing Unusual Oxidation State of Pd

具有 Pd 异常氧化态的有机钯配合物的结构和反应活性

• 批准号: 09490022
• 负责人: KUROSAWA Hideo
• 金额: $ 4.42万
• 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: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09490022/
• 关键词: Pd(IV) Complex; Pd(I) Complex; Organopalladium; Pd(IV); 有機パラジウム錯体

The aim of this project is i) to synthesize a number of organopalladium complexes having a formal oxidation state of Pd(I) or Pd(IV), ii) to elucidate their molecular and electronic structures, and iii) to explore some reactivities characteristic of such structures.The principal findings obtained follow.1) Transformations proceeding through Pd(IV) complexesPI-Allyl complex containing the chloromethyl group at 2-position of the allyl framework, [Pd(CH_2C(CH_2Cl)CH_2)(C_5H_5)] afforded C-C bond formation product, [Pd(CH_2C(CH_2G_5H_5)CH_2)Cl] via a Pd(IV)-metallacycle [Pd(CH_2C(=CH_2)CH_2)(C_5H_5)] ^+. Other than the C_5H_5 ligand, the SPh group of [Pd(CH_2C(CH_2CL)CH_2)SPh] also enabled an analogous transformation via the Pd(IV) intermediate, giving rise to [Pd(CH_2C(CH_2SPh)CH_2)CI].2) Synthesis and structure of Pd(I) complexesA general method of synthesizing Pd(I)-Pd(I) dinuclear complexes has been developed by making use of coupling between Pd(0) and Pd(II) species with butadiene playing a template role. Thus, employing some ligands on Pd(II) (Cl, Br, I) and diene ligands led to selective synthesis of anionic, [Pd_2X_3(diene)], neutral, [Pd_2X_2(PPh_3)(diene)], and cationic, [Pd_2X(PPh_3)_2(diene)] ^+ dinuclear complexes. X-Ray structure determinations confirmed the s-trans bridging diene ligand. The diene ligands so coordinating included anionic dienolate. The structure determination also revealed unusually long Pd-Pd distance (3.19 A) in [Pd_2(PPh_3) _2(diene) _2] ^<2+>, a value much longer than the previously reported Pd-Pd length (-2.83 A). MO calculations indicated that such elongated Pd-Pd length is attributed to back donation of electron densities from the Pd-Pd bond to LUMO of the diene. The unusual dicationic dipalladium complex reacted with acetonitrile or acetylene to result. in liberation of two or one diene molecule, respectively.

本项目的目的是i）合成具有Pd（I）或Pd（IV）形式氧化态的多种有机钯配合物，ii）阐明它们的分子和电子结构，（3）探讨了这些结构的反应特性，主要结果如下：1）通过Pd（IV）配合物--在2-位含有氯甲基的PI-烯丙基配合物进行的转化[Pd（CH_2C（CH_2Cl）CH_2）（C_5H_5）]通过Pd（IV）-金属配合物[Pd（CH_2C（=CH_2）CH_2）（C_5H_5）] ^+得到C-C键形成产物[Pd（CH_2C（CH_2G_5H_5）CH_2）Cl]。除C_5H_5配体外，[Pd]的SPh基团（CH_2C（CH_2CL）CH_2）SPh]也能通过Pd（IV）中间体进行类似的转化，产生[Pd（CH_2C（CH_2SPh）CH_2）Cl]。2）Pd（I）配合物的合成与结构与丁二烯起模板作用的物种。因此，在Pd（II）（Cl，Br，I）和二烯配体上使用一些配体，可以选择性地合成阴离子[Pd_2X_3（diene）]、中性[Pd_2X_2（PPh_3）（diene）]和阳离子[Pd_2X（PPh_3）_2（diene）] ^+双核配合物。X-射线结构测定证实了s-反式桥连二烯配体。如此配位的二烯配体包括阴离子二烯醇化物。结构测定还揭示了[Pd_2（PPh_3）_2（diene）_2] ^<2+>中异常长的Pd-Pd距离（3.19 A），该值比先前报道的Pd-Pd长度（-2.83 A）长得多。分子轨道计算表明，这种延长的Pd-Pd长度归因于从Pd-Pd键到二烯的LUMO的电子密度的反馈。这种罕见的双阳离子二钯配合物与乙腈或乙炔反应生成。分别释放两个或一个二烯分子。

项目成果

T.Murahashi,H.Kurosawa: "Synthesis and Structure of 1,3-Dienolate (CH_2C(O)CH=CH_2) Complex of Dipalladium(I)Moiety" J.Organomet. Chem.574. 142-147 (1999)

T.Murahashi,H.Kurosawa：“二钯(I)部分的 1,3-二烯醇盐 (CH_2C(O)CH=CH_2) 配合物的合成和结构”J.Organomet。

Shigeyosi Sakaki, Kaori Takeuchi, Manabu Sugimoto and Hideo Kurosawa: "Geometries, Bonding Nature, and Relative Stabilities of Dinuclear Palladium(I)pi-Allyl and Mononuclear Palladium(II)pi-Allyl Complexes." Organometallics. 16. 2995 (1997)

Shigeyosi Sakaki、Kaori Takeuchi、Manabu Sugimoto 和 Hideo Kurosawa：“双核钯(I)pi-烯丙基和单核钯(II)pi-烯丙基配合物的几何结构、键合性质和相对稳定性。”

T.Murahashi,H.Kurosawa他: "Remarkably Wide Range of Bond Distance Adjustment of d^8-d^9 Pd-Pd Interaction to change in Coordination Enviroment" J.Am.Chem.Soc.,. 120. 4536-4537 (1998)

T.Murahashi, H.Kurosawa 等人：“d^8-d^9 Pd-Pd 相互作用的键距调整显着变化，以改变配位环境”J.Am.Chem.Soc., 120. 4536 -4537 (1998)

S.Watanabe,H.Kurosawa: "Substitution of Cl Atom in(2-Chloromethylallyl)palladium Complexes with Soft and Hard Nucleophiles" Bull.Chem.Soc.Jpn.71. 877-881 (1998)

S.Watanabe，H.Kurosawa：“用软和硬亲核试剂取代（2-氯甲基烯丙基）钯配合物中的 Cl 原子”Bull.Chem.Soc.Jpn.71。

Saisuke Watanabe, Hiroshi Hiraike and Hideo Kurosawa: "Substitution of Cl Atom in (2-Chlormetylallyl) palladium Complexes with Soft and Hard Nucleophiles." Bull.Chem.Soc.Jpn.71. 877 (1998)

Saisuke Watanabe、Hiroshi Hiraike 和 Hideo Kurosawa：“用软和硬亲核试剂取代 (2-氯甲基烯丙基) 钯配合物中的 Cl 原子。”