Linear Triplatinum Tetrahydride Complex Supported by Triphosphine Ligands, [Pt3(μ-H)2(H)2(μ-dpmp)2](BF4)2 {dpmp = bis(diphenylphosphinomethyl)phenylphosphine}
Linear Triplatinum Tetrahydride Complex Supported by Triphosphine Ligands, [Pt3(μ-H)2(H)2(μ-dpmp)2](BF4)2 {dpmp = bis(diphenylphosphinomethyl)phenylphosphine}
复制标题
由三膦配体支持的线性四氢化铂配合物，[Pt3(μ-H)2(H)2(μ-dpmp)2](BF4)2 {dpmp = 双(二苯基膦甲基)苯基膦}
DOI：
10.1002/ejic.201700205
复制
发表时间：
2017
影响因子：
2.3
通讯作者：
Takayuki
中科院分区：
文献类型：
--
作者：
Tanase;Tomoaki;* Yamamoto;Kana; Hatano;Rika; Nakamae;Kanako; Kure;Bunsho; Ura;Yasuyuki; Nakajima;Takayuki
通过处理[Pt 6（µ-H）（H）2（µ-dpmp）4] BH 4 [4，dpmp = bis（二苯基膦基甲基）苯基膦]与过量的HBF 4在N，N-二甲基甲酰胺（DMF）中反应，得到三铂四氢化物配合物[Pt 3（μ-H）2（H）2（μ-dpmp）2]（BF 4）2（5），产率为51%，并通过IR、UV/维斯、1H NMR和31 P {1H} NMR光谱以及ESI质谱进行表征，X射线晶体学和密度泛函理论配合物5由两个dpmp配体{Pt 3（µ-dpmp）2}6+支撑的线性三核铂中心组成，其容纳两个末端和两个桥连的HPtHPtHPtH锯齿形结构。氢化物的位置通过DFT优化与B3 LYP/GD 3BJ泛函确定。在[D 7]DMF中的变温1H {31 P} NMR光谱显示，桥连的取代基表现出流动行为，并通过交换桥连位点沿Pt 3链沿着迁移，而末端取代基不与桥连取代基交换。目前的结果表明，二价线性三铂单元{Pt 3（µ-dpmp）2}2+（Pt 3 II）是构建[Pt 6（µ-H）（H）2（µ-dpmp）4]+（4，Pt 3 IIPt 3 II）的结构单元，形式上作为四电子源通过质子化产生[Pt 3（µ-H）2（H）2（µ-dpmp）2]2+（5，Pt 3VI）。
By treating [Pt6(µ‐H)(H)2(µ‐dpmp)4]BH4[4, dpmp = bis(diphenylphosphinomethyl)phenylphosphine] with an excess amount of HBF4inN,N‐dimethylformamide (DMF), a triplatinum tetrahydride complex, [Pt3(µ‐H)2(H)2(µ‐dpmp)2](BF4)2(5), was obtained in 51 % yield and was characterized by IR, UV/Vis,1H NMR, and31P{1H} NMR spectroscopy in addition to ESI mass spectrometry, X‐ray crystallography, and DFT calculations. Complex5is composed of linear trinuclear platinum centers supported by two dpmp ligands, {Pt3(µ‐dpmp)2}6+, which accommodate two terminal and two bridging hydrides in a HPtHPtHPtH zigzag structure. The hydride positions were determined by DFT optimization with B3LYP/GD3BJ functionals. Variable‐temperature1H{31P} NMR spectroscopy in [D7]DMF revealed that the bridging hydrides exhibit fluxional behavior and migrate along the Pt3chain by switching the bridging site, whereas the terminal hydrides are not exchanged with the bridging ones. The present results suggest that the divalent linear triplatinum unit of {Pt3(µ‐dpmp)2}2+(Pt3II), which is a building block to construct [Pt6(µ‐H)(H)2(µ‐dpmp)4]+(4, Pt3IIPt3II), formally acts as a four‐electron source to result in [Pt3(µ‐H)2(H)2(µ‐dpmp)2]2+(5, Pt3VI) through protonation.