当前位置：
X-MOL 学术
›
Organometallics
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
Silylene Complexes of Late 3d Transition Metals Supported by tris-Phosphinoborate Ligands
Organometallics ( IF 2.5 ) Pub Date : 2018-10-22 , DOI: 10.1021/acs.organomet.8b00635 Rex C. Handford 1 , Patrick W. Smith 1 , T. Don Tilley 1
Organometallics ( IF 2.5 ) Pub Date : 2018-10-22 , DOI: 10.1021/acs.organomet.8b00635 Rex C. Handford 1 , Patrick W. Smith 1 , T. Don Tilley 1
Affiliation
|
The complexes [BP3R]MX ([BP3R] = PhB(CH2PR2)3–, R = Ph, iPr; M = Ni, Co, Fe; X = halide) were explored as platforms for generation of first-row metal silylene complexes. Direct silylation of [BP3Ph]NiCl or [BP3iPr]CoCl with (THF)2LiSiHMes2 resulted in formation of the silylene complexes [BP3Ph]Ni(μ-H)(SiMes2) and [BP3iPr]Co(μ-H)(SiMes2), respectively. In contrast, [BP3iPr]FeBr reacted with (THF)2LiSiHMes2 to produce the iron-alkyl [BP3iPr]Fe(CH2-2-(SiH2Mes)-3,5-Me2C6H2), a constitutional isomer of the expected silyl or silylene complex. Preparation of the nickel benzyl complex [BP3Ph]Ni(η2-Bn) allowed for exploration of addition–elimination chemistry for access to silylene complexes from simple primary and secondary silanes. Heating toluene solutions of [BP3Ph]Ni(η2-Bn) in the presence of CySiH3 resulted in the formation of a dimeric μ-silylene complex [Ni(μ-BP2Ph)(μ-SiHCy)]2. In the presence of 4-dimethylaminopyridine (DMAP), these conditions led to exclusive formation of the base-stabilized silylene complex [BP3Ph]Ni(μ-H)[SiHCy(DMAP)].
中文翻译：
三膦硼酸根配体负载的晚3d过渡金属的亚甲硅烷基配合物
探索了[BP 3 R ] MX（[BP 3 R ] = PhB（CH 2 PR 2）3 –，R = Ph，i Pr; M = Ni，Co，Fe; X =卤化物）的配合物作为生成平台第一排金属甲硅烷基络合物的制备。[BP 3 Ph ] NiCl或[BP 3 i Pr ] CoCl与（THF）2 LiSiHMes 2的直接甲硅烷基化导致形成亚甲硅烷基络合物[BP 3 Ph ] Ni（μ-H）（SiMes 2）和[BP 3 i Pr ] Co（μ-H）（SiMes 2）， 分别。相反，[BP 3 i Pr ] FeBr与（THF）2 LiSiHMes 2反应生成烷基铁[BP 3 i Pr ] Fe（CH 2 -2-（SiH 2 Mes）-3,5-Me 2 C 6 H 2），是预期的甲硅烷基或甲硅烷基络合物的结构异构体。镍的制备苄基配合物[BP 3博士]镍（η 2 -Bn）允许加成-消除化学勘探从简单的主要和次要的硅烷获得的亚甲硅烷复合物。加热[BP的甲苯溶液3博士]镍（η 2-Bn）在CySiH存在3导致二聚体μ-亚甲硅烷基络合物[镍（μ-BP的形成2博士）（μ-SiHCy）] 2。在存在4-二甲基氨基吡啶（DMAP）的情况下，这些条件导致形成了碱稳定的亚甲硅烷基络合物[BP 3 Ph ] Ni（μ-H）[SiHCy（DMAP）]。
更新日期：2018-10-23
中文翻译：
三膦硼酸根配体负载的晚3d过渡金属的亚甲硅烷基配合物
探索了[BP 3 R ] MX（[BP 3 R ] = PhB（CH 2 PR 2）3 –，R = Ph，i Pr; M = Ni，Co，Fe; X =卤化物）的配合物作为生成平台第一排金属甲硅烷基络合物的制备。[BP 3 Ph ] NiCl或[BP 3 i Pr ] CoCl与（THF）2 LiSiHMes 2的直接甲硅烷基化导致形成亚甲硅烷基络合物[BP 3 Ph ] Ni（μ-H）（SiMes 2）和[BP 3 i Pr ] Co（μ-H）（SiMes 2）， 分别。相反，[BP 3 i Pr ] FeBr与（THF）2 LiSiHMes 2反应生成烷基铁[BP 3 i Pr ] Fe（CH 2 -2-（SiH 2 Mes）-3,5-Me 2 C 6 H 2），是预期的甲硅烷基或甲硅烷基络合物的结构异构体。镍的制备苄基配合物[BP 3博士]镍（η 2 -Bn）允许加成-消除化学勘探从简单的主要和次要的硅烷获得的亚甲硅烷复合物。加热[BP的甲苯溶液3博士]镍（η 2-Bn）在CySiH存在3导致二聚体μ-亚甲硅烷基络合物[镍（μ-BP的形成2博士）（μ-SiHCy）] 2。在存在4-二甲基氨基吡啶（DMAP）的情况下，这些条件导致形成了碱稳定的亚甲硅烷基络合物[BP 3 Ph ] Ni（μ-H）[SiHCy（DMAP）]。
京公网安备 11010802027423号