2-（I）三羰基配合物与（2-羟基苯基）二苯基膦作为PO双齿配体,Inorganic Chemistry

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2-（I）三羰基配合物与（2-羟基苯基）二苯基膦作为PO双齿配体
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2017-06-28 00:00:00 , DOI: 10.1021/acs.inorgchem.7b00894
Antonio Shegani , Charalampos Triantis , Berthold A. Nock , Theodosia Maina , Christos Kiritsis , Vassilis Psycharis , Catherine Raptopoulou , Ioannis Pirmettis , Francesco Tisato ₁ , Minas S. Papadopoulos

Affiliation

在目前的工作中，我们研究了潜在的手段，以获得含有（2-羟基苯基）二苯基膦（POH）双齿的中性三羰基混合配体fac- [M（CO）₃ L ¹ L ² ]配合物（M = Re，^99m Tc）配体（L ¹ H）和一系列单齿配体（L ²）。首先，通过POH和[Et ₄ N] ₂ [Re（CO）₃ Br _3的反应合成fac- [Re（CO）₃（PO）（H ₂ O）]，1。在室温下，以等摩尔量在MeOH中洗脱。有趣的是，在过量的POH的情况下，该反应提供了fac- [Re（CO）₃（PO）（POH）]，2，而POH既充当二齿也充当单齿配体。由于存在不稳定的水族配体（可以很容易地被各种单齿配体替代），因此将1进一步用作前体以生成所需fac- [M（CO）₃ L ¹ L ² ]配合物的小文库。具体而言，通过（PPH三苯基膦的反应₃），咪唑（IM），吡啶（PY），环己基胩（CISC），和叔丁基异氰酸酯（tbi），可以轻松获得以下产品，收率很好（92％–95％）：fac- [Re（CO）₃（PO）（PPh ₃）]，3，fac- [Re（CO）₃（PO）（IM）]，4，FAC - [的Re（CO）₃（PO）（PY）]，5，FAC - [的Re（CO）₃（PO）（CISC）]，6，和FAC - [Re（CO）₃（PO）（tbi）]，7。所有化合物均通过元素分析，IR和NMR光谱以及电喷雾电离（+）质谱进行了全面表征。通过X射线晶体学阐明了它们的固态结构。相当大的兴趣的是，相应的事实2' - 7'是在容易接近^99米POH的反应和相应的单齿配位体L后，以定量产率的Tc-示踪剂级别²用FAC - [ ^99米TC（CO）₃（H ₂ O）₃ ] ⁺在MeOH水溶液中洗脱，通过采用双光度法和放射线检测模式的比较色谱方法进行了验证。所有^99m Tc配合物在组氨酸和半胱氨酸激发试验期间显示出的高稳定性强调了fac- [M（CO）₃（PO）L ² ]系统在放射性药物开发中的适用性。

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Rhenium(I) Tricarbonyl Complexes with (2-Hydroxyphenyl)diphenylphosphine as PO Bidentate Ligand

In the present work, we investigated potential means to obtain neutral tricarbonyl mixed-ligand fac-[M(CO)₃L¹L²] complexes (M = Re, ^99mTc) containing the (2-hydroxyphenyl)diphenylphosphine (POH) bidentate ligand (L¹H) and a series of monodentate ligands (L²). First, fac-[Re(CO)₃(PO)(H₂O)], 1, was synthesized by reaction of POH and [Et₄N]₂[Re(CO)₃Br₃] in equimolar amounts in MeOH at room temperature. Interestingly, with excess of POH this reaction afforded fac-[Re(CO)₃(PO)(POH)], 2, with POH operating both as a bidentate and as a monodentate ligand. Owing to the presence of the labile aqua ligand, which can be readily replaced by various monodentate ligands, 1 was further used as a precursor to generate a small library of the desired fac-[M(CO)₃L¹L²] complexes. Specifically, by reaction of triphenylphosphine (PPh₃), imidazole (im), pyridine (py), cyclohexyl isocyanide (cisc), and tert-butyl isocyanide (tbi), the following products were readily obtained in excellent yields (92%–95%): fac-[Re(CO)₃(PO)(PPh₃)], 3, fac-[Re(CO)₃(PO)(im)], 4, fac-[Re(CO)₃(PO)(py)], 5, fac-[Re(CO)₃(PO)(cisc)], 6, and fac-[Re(CO)₃(PO)(tbi)], 7. All compounds were fully characterized by elemental analysis, IR and NMR spectroscopies, and electrospray ionization(+) mass spectrometry. Their solid-state structure was elucidated by X-ray crystallography. Of considerable interest is the fact that the corresponding 2′–7′ were easily accessible at the ^99mTc-tracer level in quantitative yields after reaction of POH and the respective monodentate ligand L² with fac-[^99mTc(CO)₃(H₂O)₃]⁺ in aqueous MeOH, as verified by comparative chromatographic methods adopting dual photo- and radiometric detection modes. The high stability displayed by all ^99mTc complexes during histidine and cysteine challenge assays underscored the suitability of the fac-[M(CO)₃(PO)L²] system for radiopharmaceutical development purposes.

更新日期：2017-06-28

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