Synthetic Control of Heteroatonvcontaining Dynamic Complexes by Taking Advantage of Kinetic Stabilization

利用动力学稳定性合成控制含杂原子的动态配合物

• 批准号: 14078213
• 负责人: TOKITOH Norihiro
• 金额: $ 15.87万
• 依托单位: Kyoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14078213/
• 关键词: Steric Protection; Platinum-Sulfur double bond; zero-valent platinum complex; bidentate phosphine ligand; β-diketiminato ligand; group 4 metal; imido complex; C-H結合活性化; C-Si結合活性化; 速度論的安定化; 白金; カルコゲン; ホスフィン; ジカルコゲニド錯体; リチウム; かさ高い置換基; 二重結合化合

The main purposes of this project are the development of novel ligands bearing steric protection group and their application toward the synthesis and isolation of novel dynamic complexes bearing unique chemical bonds between heteroatoms. We have succeeded in the synthesis of the extremely bulky bidentate ligand, {Bbt(Me)PCH_2}_2 (1), and its platinum complex, [PtCl_2(1)](2). In this year, we attempted to synthesize the corresponding zero valent platinum complex, [Pt(1)](3), which should be a good precursor for the unprecedented platinum complex bearing a Pt=S double bond, [PtS(1)]. Although reduction of 2 using sodium shot or lithium naphthalenide was attempted, no evidence for the generation of 3 was observed. On the other hand, we succeeded in the synthesis of a new lithium β-diketiminate bearing Tbt and mesityl (Mes) groups, [Li{TbtNC(Me)CHC(Me)NMes}] (4), which is the first heteroatomrdonor-free monomeric lithium β-diketiminate. Lithium β-diket-iminate 4 reacted with MCl_4(thf)_2 (M = Ti, Zr, Hf) to give the corresponding group 4 metal complexes [M{TbtNC(Me)CHC(Me)NMes}(thf)n] (5a : M = Ti, n = 0, 5b : M = Zr, n = 1, 5c : M = Hf, n = 1), respectively. The reduction of 5a-c with KC_8 in the presence of tmeda and LiCl was found to afford unexpected imido complexes [M(NTbt)-{MesNC(Me)CHC(Me)}(μ-Cl)_2Li(tmeda)] (6a : M = Ti, 6b : M = Zr, 6c : M = Hf) in good yields. The treatment of hafnium complex 6c in benzene with KC_8 gave imido complex [HfCl(NTbt)- {MesNC(Me)CHC(Me)}(thf] (7c) in 82% yield in the absence of additives. These imido complexes 6a-c and 7c are most likely formed via the corresponding divalent group 4 metal complexes.

本项目的主要目的是开发具有空间位阻保护基团的新型配体，并将其应用于合成和分离具有独特的杂原子间化学键的新型动态配合物。我们成功地合成了一个体积极大的双齿配体{Bbt（Me）PCH_2}_2（1）及其铂配合物[PtCl_2（1）]（2）。在今年，我们尝试合成相应的零价铂配合物[Pt（1）]（3），这应该是前所未有的带有Pt=S双键的铂配合物[PtS（1）]的良好前体。虽然尝试了使用钠丸或萘锂还原2，但没有观察到产生3的证据。另一方面，我们成功地合成了一种新的β-双烯酮亚胺锂化合物[Li{TbtNC（Me）CHC（Me）NMes}]（4），这是第一个不含杂原子给体的单体β-双烯酮亚胺锂化合物。β-双酮亚胺锂4与MCl_4（thf）_2（M = Ti，Zr，Hf）反应，得到相应的第4族金属配合物[M{TbtNC（Me）CHC（Me）NMes}（thf）n]（5a：M = Ti，n = 0; 5 b：M = Zr，n = 1; 5c：M = Hf，n = 1）。在tmeda和LiCl存在下，用KC_8还原5a-c，以良好的产率得到了非预期的亚胺配合物[M（NTbt）-{MesNC（Me）CHC（Me）}（μ-Cl）_2Li（tmeda）]（6a：M = Ti，6 b：M = Zr，6c：M = Hf）。铪配合物6c在苯中用KC_8处理，在无添加剂的条件下，以82%的产率得到亚胺配合物[HfCl（NTbt）- {MesNC（Me）CHC（Me）}（thf）]（7 c）。这些亚氨基络合物6a-c和7 c最可能通过相应的二价第4族金属络合物形成。

项目成果

21世紀の有機ケイ素化学-機能性物質科学の宝庫

21世纪有机硅化学——功能材料科学的宝库

• 发表时间: 2004
• 作者: Keisho Umesaki;et al.;関口 章
• 通讯作者: 関口 章

Photophysical and photochemical processes of 9,10-dihydro-9-silaphenanthrene derivatives : photochemical formation and electronic structure of 9-silaphenanthrenes.

9,10-二氢-9-硅菲衍生物的光物理和光化学过程：9-硅菲的光化学形成和电子结构。

• 发表时间: 2006
• 期刊: J.Phys.Chem.A 110
• 作者: H.Hiratsuka;H.Horiuchi;Y.Furukawa;H.Watanabe;A.Ishihara;T.Okutsu;S.Tobita;T.Yoshinaga;A.Shinohara;N.Tokitoh;M.Oba;K.Nishiyama
• 通讯作者: K.Nishiyama

Insertion of an Overcrowded Silylene into Hydro- and Haloboranes : A Novel Sysnthesis of Silylborane Derivatives and Their Properties

将过度拥挤的硅烯插入氢硼烷和卤硼烷中：甲硅烷基硼烷衍生物的新合成及其性质

• 发表时间: 2004
• 期刊: Organometallics 23
• 作者: Takashi Kajiwara

Norihiro Tokitoh: "Systematic Studies on Homo-and Heteronuclear Doubly Bonded Compounds of Heavier Group 15 Elements"Phosphorus, Sulfur and Silicon. 177. 1473-1476 (2002)

Norihiro Tokitoh：“第 15 族重元素”磷、硫和硅的同核和异核双键化合物的系统研究。

Synthesis and Structure of a Stable 1,3-Dihydrotriphosphane and Its Thermal Decomposition Leading to the Formation of the Corresponding Phosphine and Diphosphene

稳定的 1,3-二氢三膦的合成和结构及其热分解导致相应的膦和二膦的形成

• 发表时间: 2005
• 期刊: Organometallics 24
• 作者: N.Nishi;T.Kawakami;F.Shigematsu;M.Yamamoto;T.Kakiuchi;D.Shimizu;T.Tajima;Y.Sugiyama;N.Nagahora;Y.Mizuhata;T.Sasamori;T.Sasamori;T.Tajima;T.Sasamori;A.Shinohara;N.Nagahora
• 通讯作者: N.Nagahora