diffraction techniques. The two compounds form similar polycyclic, centrosymmetrical assemblies of metal atoms bridged by chlorine or nitrogen atoms. While in the case of the cobalt compound Co is pentacoordinated by three chlorine and two nitrogen atoms, in the zinc derivative Zn is almost tetrahedrally coordinated by three chlorine atoms and one nitrogen atom. The iron derivative [Me(2)Si(NtBu)(2)Sn.FeCl(2)](2)
Oxidative addition reactions of dialkylchalcogenanes R2E2 and [Me2Si(Nt-Bu)2]Ge 1 yielded bis(alkylchalcogeno)germanes Me2Si(Nt-Bu)2Ge(ER)2 (R = Et, E = S 2, Se 3; R = Me, E = Se 4) and digermanes [Me2Si(Nt-Bu)2Ge(EEt)]2 (E = S 5, Se 6). The reaction of 1 with Et2Te2 proceeds with formation of Me2Si(Nt-Bu)2Ge(TeEt)27, which slowly converts into the Te-bridged complex [Me2Si(Nt-Bu)2GeTe]28. 1-6 and
二烷基硫属元素烷R2E2和[Me2Si(Nt-Bu)2] Ge 1的氧化加成反应生成双(烷基硫属元素基)锗烷Me2Si(Nt-Bu)2Ge(ER)2(R = Et,E = S 2,Se 3; R = Me,E = Se 4)和二茂铁[Me 2 Si(Nt-Bu)2 Ge(EEt)] 2(E = S 5,Se 6)。1与Et2Te2的反应会继续形成Me2Si(Nt-Bu)2Ge(TeEt)27,该反应缓慢转化为Te-桥联络合物[Me2Si(Nt-Bu)2GeTe] 28。通过单晶X射线衍射表征1-6和8。
Reactions of Germylenes and Stannylenes with Halo(hydrocarbyl)- and Chloro(amino)phosphines: Oxidative Addition versus Ligand Transfer
作者:Joseph K. West、Lothar Stahl
DOI:10.1021/acs.inorgchem.7b01275
日期:2017.11.6
faster than germylenes, and these reactions are first-order in both reactants and slowed by stericbulk. Kinetic data and the structures of intermediates and products had suggested an adduct/insertion mechanism for these reactions. To gain further insight into these transformations, the work presented herein was extended to chloro(hydrocarbyl)phosphines with varying organic substituents. These studies
氧化加成(OA)是化学中一个重要的基本步骤,但主要在过渡金属催化的反应环境中进行了研究,并且主要在碳X底物(X =卤素,H)中进行了研究。相比之下,主要的金属化合物经历OA的报道很少,而涉及磷-卤素底物的报道仍然很少。无环和环状的二氮杂亚甲基和-亚锡烷基在氧化加成产物的中间与氯(烃基)膦反应。亚苯乙烯的反应速度比亚甲基苯还快,并且这些反应在两种反应物中都是一阶反应,并且由于空间体积而减慢。动力学数据以及中间体和产物的结构表明了这些反应的加合物/插入机理。为了进一步了解这些转变,本文提出的工作扩展到具有不同有机取代基的氯(烃基)膦。这些研究证实了有关立体空间速率降低作用的先前结论,并且速率对离去基团的依赖性似乎也暗示加合物/插入或S N 2机制。重要的是,这些新数据现在也指向关联的分解途径。在研究过程中,发现脂肪族氯(氨基)膦与卡宾类似物的反应不同,从而为亚二甲苯生成了氧化加成产物,但为亚苯乙烯生成了易位反应。
Reactions of Heterodinuclear Fe−Pt and Fe−Pd Complexes with Cyclic Bis(amino)germylenes and -stannylenes: A Bridging Metal(II) Amide Unit between Two Different Transition Metal Centers and Donor Stabilization of Terminal Germylene and Stannylene Ligands by Si(OMe)<sub>3</sub>
the germylene complex 3a, the tetranuclear complex [(OC)3Feμ-GeNtBuSiMe2NtBu}(μ-dppm)Pt GeNtBuSiMe2NtBu}](Fe−Pt) (4) was formed, which is in equilibrium with 3a. The heterobimetallic Si(OMe)3-substituted complexes mer-[(OC)3Feμ-Si(OMe)2(OMe)}(μ-dppm)M(Me)](Fe−M) (M = Pd, Pt) react with ENtBuSiMe2NtBu (E = Ge, Sn) by opening of the four-membered Fe−Si−O−M ring to give the complexes mer-[(OC)3Fe
Insertions of Cyclic and Acyclic Germanium and Tin Heterocarbenoids into Phosphorus–Chlorine Bonds: Syntheses, Structures, and Reactivities
作者:Joseph K. West、Lothar Stahl
DOI:10.1021/om3000168
日期:2012.3.12
Chloro(organo)phosphines are important precursors to diphosphenes and cyclic oligophosphines. Although chloro(organo)phosphines are commonly reduced with bulk metals (e.g., Na, Mg, and Zn), these reactions are much more selective when done homogeneously. To test whether group 14 heterocarbenoid reductions yield isolable insertion products, the mono- and dichloro(organo)phosphines PhPCl2 (A), Ph2PCl