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.

该项目的主要目的是开发具有空间保护组的新型配体及其在杂原子之间具有独特化学键的新型动态复合物的合成和隔离的应用。我们已经成功地合成了极笨重的边界，{bbt（me）pCH_2} _2（1）及其铂综合体[ptcl_2（1）]（2）。在今年，我们试图合成相应的零Valent铂络合物[PT（1）]（3），这应该是前所未有的铂型复合物PT = S双键的良好先驱，[PTS（1）]。尽管尝试使用钠射击或萘化锂减少2次，但未观察到3产生的证据。另一方面，我们成功地合成了新的锂β-二键型轴承轴承tbt和Mesityl（MES）组，[li {li {tbtnc（me）chc（me）nMes}]（4），这是第一个无杂质的无heteroatomrdonor heteroatomrdonor-breemrdonor-monomeric-monomeric lithiumβ-diketimate。 Lithium β-diketimate 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.发现在TMEDA和LICL存在下使用KC_8的5A-C减少了意外的Imido Complexes [M（NTBT） - {Mesnc（Me）CHC（Me）chc（me）}（μ-CL）_2LI（TMEDA）（TMEDA）]（6A：6A：M = TI，6B：M = ti，6b：m = Zr，6c：6c：M = hf）。用KC_8在苯中的Hafnium复合物的处理给出了Imido复合物[HFCL（NTBT） - {Mesnc（Me）CHC（Me）}（Me）}（7C）（7C）（7C）（7C）在没有添加剂的情况下，产量为82％。这些Imido Complectes 6A-C和7C最可能通过相应的分区组合4 Metal Sivelent 4 Metal 4 Metal 4 Metal Sivelents组成。

项目成果

Systematic Studies on Redox Behavior of Homonuclear Double-bond Compounds of Heavier Group 15 Elements

重15族元素同核双键化合物氧化还原行为的系统研究

• 发表时间: 2005
• 期刊: Chem.Lett. 34
• 作者: Takahiro Sasamori

Structure and Properties of an Overcrowded 1,2-Dibromodigermene

拥挤的 1,2-二溴二甲烯的结构和性质

• 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;T.Sasamori
• 通讯作者: T.Sasamori

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

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

Kazuto Nagata: "Synthesis, Structure, and Properties of the First Disulfur and Diselenium Complexes of Platinum"Bull.Chem.Soc.Jpn.. 76. 1577-1587 (2003)

Kazuto Nagata：“铂的第一个二硫和二硒配合物的合成、结构和性能”Bull.Chem.Soc.Jpn.. 76. 1577-1587 (2003)