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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Phosphine-ligated induced formation of thallium(I) 'full' Pt3TlPt3 sandwich versus 'open-face' TlPt3 sandwich with triangular Pt3(mu(2)-CO)(3)(PR3)(3) units: synthesis and structural/spectroscopic analysis of triphenylphosphine [mu(3)-Tl)Pt-3(mu(2)-C
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Phosphine-ligated induced formation of thallium(I) 'full' Pt3TlPt3 sandwich versus 'open-face' TlPt3 sandwich with triangular Pt3(mu(2)-CO)(3)(PR3)(3) units: synthesis and structural/spectroscopic analysis of triphenylphosphine [mu(3)-Tl)Pt-3(mu(2)-C

机译：磷化氢诱导的formation的形成（I）“完整” Pt3TlPt3三明治与带有三角形Pt3（mu（2）-CO）（3）（PR3）（3）单元的“开放式” TlPt3三明治：合成和结构/光谱三苯基膦[mu（3）-Tl）Pt-3（mu（2）-C的分析

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This research constitutes an operational test to assess the influence of platinum-attached phosphine ligands in the formation process of "open-face" TlPt3 or "full" Pt(3)Tlpt(3) sandwich clusters. Accordingly, the reaction of TIPF6, with triphenylphosphine Pt-4(mu(2)-CO)(5)(PPh3)(4), under essentially identical boundary conditions originally used to prepare (90% yield) the triethylphosphine "full" Pt3TlPt3 sandwich, [(mu(6)-Tl)Pt-6(mu(2)-CO)(6)(PEt3)(6)](+) (3) ([PF6](-) Salt), from Pt-4(mu(2)-CO)(5)(PEt3)(4) was carried out to see whether it would likewise afford the unknown triphenylphosphine Pt3TlPt3 sandwich analogue of 3 or whether the change of phosphine ligands from sterically smaller, more basic PEt3 to PPh3 would cause the product to be the corresponding unknown triphenylphosphine "open-face" TlPt3 sandwich that would geometrically resemble the known bulky tricyclohexylphosphine [(mu(3)-Tl)Pt-3(mu(2)-CO)(3)(PCy3)(3)](+) sandwich (2a). Both the structure and composition of the resulting "open-face" sandwich product, [(mu(3)-Tl)Pt-3(mu(2)-CO)(3)(PPh3)(3)](+) (1a) ([PF6](-) salt), were unequivocally established from a low-temperature CCD X-ray crystallographic determination. The calculated Pt/Tl atom ratio (3/1) of 75%/25% is in excellent agreement with that of 72(3)%/28(5)% obtained from energy-resolved measurements on a single crystal with a scanning electron microscope. Crystals (80% yield) of the orange-red 1a were characterized by solid-state/solution IR and variable temperature Tl-205 and P-31{H} NMR spectra; the P-31{H-1} spectra provide convincing evidence that la is exhibiting dynamic behavior at room temperature in CDCl3 solution. The corresponding new "open-face" (mu(3)-AuPPh3)Pt-3 sandwich, [(mu(3)-AuPPh3)Pt-3(mu(2)-CO)(3)(PPh3)(3)](+) (1b) ([PF6](-) salt), was quantitatively obtained from la by reaction with AuPPh3Cl and spectroscopically characterized by IR and P-31{H-1} NMR spectra. A comparative geometrical evaluation of the observed steric dispositions of the platinum-attached PR3 ligands in the "open-face" (mu(3)-Tl)Pt-3 sandwiches of 1a (with PPh3) and the known 2a (with PCy3) and in the known "full" Pt3TlPt3 sandwich of 3 (with PEt3) along with the considerably different observed steric dispositions of the PR3 ligands in the known "open-face" (mu(3)-AuPCy3)Pt-3 sandwich of 2b (with PCy3) and in the known "full" Pt3AuPt3 sandwich of 4 (with PPh3) has been performed.
机译：这项研究构成了一项操作测试，以评估铂连接的膦配体在“敞开式” TlPt3或“全” Pt（3）Tlpt（3）夹心簇形成过程中的影响。因此，TIPF6与三苯基膦Pt-4（mu（2）-CO）（5）（PPh3）（4）的反应在基本上用于最初制备（90％产率）三乙基膦“全” Pt3TlPt3的相同边界条件下进行三明治，[（mu（6）-Tl）Pt-6（mu（2）-CO）（6）（PEt3）（6）]（+）（3）（[PF6]（-）盐），来自Pt进行了-4（mu（2）-CO）（5）（PEt3）（4），以查看是否同样可以得到未知的三苯基膦Pt3TlPt3三明治类似物，或者膦配体的变化是否从空间上更小，更碱性PEt3至PPh3将导致该产物成为相应的未知三苯基膦“敞开式” TlPt3三明治，其几何形状类似于已知的笨重的三环己基膦[[mu（3）-Tl）Pt-3（mu（2）-CO）（3 ）（PCy3）（3）]（+）三明治（2a）。所得“敞开式”三明治产品[[mu（3）-Tl）Pt-3（mu（2）-CO）（3）（PPh3）（3）]（+）的结构和组成通过低温CCD X射线晶体学测定明确地确定了1a）（[PF6]（-）盐）。计算得出的Pt / Tl原子比（3/1）为75％/ 25％，与通过对具有扫描电子的单晶进行能量分辨测量获得的72（3）％/ 28（5）％的结果非常吻合显微镜。橘红色1a的晶体（产率为80％）通过固态/溶液红外光谱和可变温度Tl-205和P-31 {H} NMR光谱进行表征。 P-31 {H-1}光谱提供了令人信服的证据，表明La在CDCl3溶液中在室温下表现出动态行为。相应的新“开放式”（mu（3）-AuPPh3）Pt-3三明治，[（mu（3）-AuPPh3）Pt-3（mu（2）-CO）（3）（PPh3）（3）通过与AuPPh3Cl反应从la中定量获得]（+）（1b）（[PF6]（-）盐），并通过IR和P-31 {H-1} NMR光谱进行表征。 1a（使用PPh3）和已知2a（使用PCy3）的“敞开式”（mu（3）-Tl）Pt-3三明治中与铂连接的PR3配体的空间位置比较几何比较评估在已知的3的“完整” Pt3TlPt3三明治中（带有PEt3），以及在已知的2b的“敞开面”（mu（3）-AuPCy3）Pt-3三明治中PR3配体的明显不同的空间位置PCy3）和已知的“完整” Pt3AuPt3三明治4（带有PPh3）已被执行。

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