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.

该项目的目的是 i) 合成多种具有 Pd(I) 或 Pd(IV) 形式氧化态的有机钯配合物，ii) 阐明其分子和电子结构，以及 iii) 探索此类结构的一些反应性特征。获得的主要发现如下。1) 通过 Pd(IV) 配合物进行的转化含有氯甲基基团的 PI-烯丙基配合物 烯丙基骨架的2位，[Pd(CH_2C(CH_2Cl)CH_2)(C_5H_5)]通过Pd(IV)-金属环[Pd(CH_2C(=CH_2)CH_2)(C_5H_5)]^+提供C-C键形成产物[Pd(CH_2C(CH_2G_5H_5)CH_2)Cl]。除了C_5H_5配体之外，[Pd(CH_2C(CH_2CL)CH_2)SPh]的SPh基团也可以通过Pd(IV)中间体进行类似的转化，得到[Pd(CH_2C(CH_2SPh)CH_2)CI]。2) Pd(I)配合物的合成和结构一种合成的一般方法 Pd(I)-Pd(I)双核配合物是通过利用Pd(0)和Pd(II)物质之间的偶联以及丁二烯发挥模板作用而开发的。因此，在 Pd(II) (Cl、Br、I) 和二烯配体上使用一些配体导致选择性合成阴离子 [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-反式桥联二烯配体。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)，该值比之前报道的 Pd-Pd 长度 (-2.83 A) 长得多。 MO计算表明，这种拉长的Pd-Pd长度归因于电子密度从Pd-Pd键向二烯的LUMO的反捐赠。不寻常的二价二钯络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。”