Development of complexes with a Multiple Bond between Transition Metal and Phosphor us

过渡金属和磷之间具有多重键的配合物的开发

• 批准号: 10440195
• 负责人: MIYOSHI Katsuhiko
• 金额: $ 8.58万
• 依托单位: Hiroshima University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10440195/
• 关键词: Phosphenium Complex; Phosphide Complex; Double Bond; Migration Reaction; Stannylene Complex; One Electron Reduction; OR引き抜き反応; タングステン錯体

The reaction of [Cp(CO)ィイD22ィエD2(SnィイD1nィエD1BuィイD23ィエD2)W{PN(Me)CHィイD22ィエD2CHィイD22ィエD2NMe(OMe)}] with a Lewis acid revealed the formation of a phosphenium complex, followed by migration of a ィイD1nィエD1BU group from Sn to P to give a stannylene complex. If the reaction takes place in the presence of NaBPhィイD24ィエD2, a phosphi de complex, Cp(CO)ィイD22ィエD2W{PN(Me)CHィイD22ィエD2CHィイD22ィエD2NMe} is formed. This unprecedented reaction is considered to be a W-P bond order increment by one with elimination of a stannyl and a methoxy group. The reaction proceeds with one electron reducti on of a phosphenium complex by NaBPh4, followed by stannyl radical elimination.The reaction of a Lewis acid with a ruthenium complex, [Cp(CO)(ERィイD23ィエD2)Ru-{PN(Me)CHィイD22ィエD2CHィイD22ィエD2NMe(OMe)}] (where E = C, Si , Ge, Sn), which has both diamino-substituted phosphite and a group 14 element ligand was examined. Irrespective of the kind of E, an OMe group on the phosphorus is abstracted as an anion to give a phosphenium complex. The following reaction depends on the kind of E. If ERィイD23ィエD2 is an alkyl group, the ligand migrates from Ru to the phospheni um phosphorus, whereas if ERィイD23ィエD2 is a silyl or a germyl group, no migration reaction takes place. If ERィイD23ィエD2 is a stannyl group, an al kyl group on the tin migrates to the phosphenium phosphorus to give a stannylene complex, which has a double bond between Ru and Sn.The reaction of a Lewis acid with [Cp(CO)(SiMeィイD22ィエD2OMe)Fe{PN(Me)CHィイD22ィエD2CHィイD22ィエD2-NMe(OMe)}] containing an OR group on both coordinating P and Si atoms revealed that selective OR abstraction from Si occurs to give a silylene complex.

的反应(Cp (CO)ィイD22摊位ィエD2 (SnィイD1nィエD1Buィイc15ィエD2) W {PN(我)CHィイD22摊位ィエD2CHィイD22摊位ィエD2NMe(当地)})和路易斯酸透露phosphenium复杂的形成,紧随其后的是迁移的ィイD1nィエD1Bu从Sn组P stannylene复杂。如果反应发生在NaBPh的存在下，则形成一个磷酸复合物Cp(CO) D22 D2W{PN(Me) D22 D2CH D22 D2NMe}。这一前所未有的反应被认为是W-P键序增加了一个，消除了一个斯坦基和一个甲氧基。该反应以NaBPh4单电子还原磷配合物，然后消除锡基自由基进行。钌的路易斯酸的反应复杂,(Cp (CO) (ERィイc15ィエD2) Ru - {PN(我)CHィイD22摊位ィエD2CHィイD22摊位ィエD2NMe(当地)}](E = C,如果通用电气、Sn),这既有diamino-substituted亚磷酸盐和一群14元素配位体检查。不管E的种类是什么，磷上的一个OMe基团被抽象为阴离子，得到一个磷络合物。下面的反应取决于e的种类。如果ER γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ。如果ER γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ。在配位的P原子和Si原子上，Lewis酸与含有OR基团的[Cp(CO)(SiMe D22 D2OMe)Fe{PN(Me) D22 d2d22 D2-NMe(OMe)}]的反应表明，Si发生选择性的OR萃取得到硅烯配合物。

项目成果

Hiroshi Nakazawa: "Syntheses,Structure,and Berry Pseudorotatin of Ruthenium-Phosphorane Complexes"Organometallics. 18. 2961-2969 (1999)

Hiroshi Nakazawa：“钌-磷烷配合物的合成、结构和贝里假旋转”有机金属化合物。

Katsuhiko Miyoshi: "Selective Abstraction of an OR Group in the Reaction of(C_5H_5)(CO)Fe{SiMe_2(OR)}{PN(Me)CH_2CH_2NMe(OR^2)}with a Lewis Acid:Preferential Formation of a Silylene Complex over a Phosphenium, Complex" Organometallics. (accepted).

Katsuhiko Miyoshi：“(C_5H_5)(CO)Fe{SiMe_2(OR)}{PN(Me)CH_2CH_2NMe(OR^2)}与路易斯酸反应中OR基团的选择性抽象：优先形成硅烯络合物

Hiroshi Nakazawa: "Reactivity of a Catiotic Phosphenium Complex of Tungsten Containing Aklyl or a Stannyl Group"Phosphorus,Sulfur,and Silicon. 144. 45-48 (1999)

Hiroshi Nakazawa：“含烷基或甲锡烷基的钨的阳离子磷锍配合物的反应性”磷、硫和硅。

Kazumori Kawamura: "Selective Abstraction of an OR Group in the Reaction of (CィイD25ィエD2HィイD25ィエD2) (CO)Fe{SiMeィイD22ィエD2(ORィイD11ィエD1)}{PN(Me)CHィイD22ィエD2CHィイD22ィエD2NMe(ORィイD12ィエD1)} with a Lewis Acids: Preferential Formation of a Silylene Complex over a Pho

Kazumori Kawamura：“(C-D25-D2H-D25-D2) (CO)Fe{SiMe-D22-D2 (OR-D11-D1) }{PN(Me)CHD22D2CHD22D2NMe( ORD12D1)} 与路易斯酸：相对于 Pho 优先形成亚硅基络合物

Tsutomu Mizuta: "A Selective Enforced Bent Form of an Edge-Sharing Dipalladium(II) Complex Attained by a Linked-Bisphosphido Bridge"Inorganic Chemistry. 38. 4361-4364 (1999)

Tsutomu Mizuta：“通过连接双磷桥实现的边缘共享二钯（II）络合物的选择性强制弯曲形式”无机化学。