Polyhedron最新文献

英文中文

Development of tripeptide-cyclotriphosphazene derivatives: In vitro cytotoxicity, genotoxicity studies and molecular docking analysis within ovarian and prostate cancer cell line receptors 开发三肽-环三磷酸嗪衍生物：卵巢癌和前列腺癌细胞系受体的体外细胞毒性、遗传毒性研究和分子对接分析

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-10-22 DOI: 10.1016/j.poly.2024.117261

Alpaslan Kaplan , Eray Çalışkan , İrfan Çapan , Suat Tekin , Mohammad N. Hassan , Mohammed T. Qaoud , Kenan Koran , Süleyman Sandal , Ahmet Orhan Görgülü

Peptide-phosphazene compounds are important compounds of growing interest in biomedical research and have potential therapeutic effects. The tripeptide-cyclotriphosphazenes conjugates were synthesized and analyzed for their molecular docking analysis, visualizing their binding profiles within various cancer cell line receptors and tested in vitro cytotoxic and genotoxic properties. Determining in vitro cytotoxic studies of obtained compounds displayed cytotoxic effect against two selected human cancer cell lines, including ovarian (A2780) and prostate (PC-3), cancer cells. The compound DTAP demonstrated significantly higher efficacy at 100 µM in the PC-3 cancer cell line compared to the reference drug docetaxel at 50 µM. Among the tripeptide-phosphazene conjugtates, DTGG demonstrates the most promising anticancer activity with a logIC₅₀ of 1.23 µM, forming five hydrogen bonds and a favorable salt bridge interaction, along with several hydrophobic interactions, thereby stabilizing its binding within the human ovarian tumor domain based on molecular docking analysis. The derivative DTGP emerges as the most potent among the DTG derivatives, achieving a ΔG model value of −108 kcal/mol, primarily due to a π-cationic interaction with the LYS204 amino acid in chain C, which significantly enhances its binding affinity. Additionally, DNA damage studies on human ovarian and prostate cancer cell lines determined that cell death due to DNA damage was the basis of the decrease in cell viability. These results support the evaluation of the compounds as potential drug candidates.

肽-膦氮化合物是生物医学研究中越来越受关注的重要化合物，具有潜在的治疗作用。我们合成了三肽-环三膦烯共轭物，并对其进行了分子对接分析，观察了它们在各种癌细胞系受体中的结合情况，并对其进行了体外细胞毒性和基因毒性测试。所获化合物的体外细胞毒性研究显示，它们对两种选定的人类癌细胞系（包括卵巢癌细胞系（A2780）和前列腺癌细胞系（PC-3））具有细胞毒性作用。与参考药物多西他赛（50 µM）相比，化合物 DTAP 在 PC-3 癌细胞系中 100 µM 的药效明显更高。根据分子对接分析，在三肽-膦氮化合物共轭物中，DTGG 的抗癌活性最高，其对数半数致死浓度（logIC50）为 1.23 µM，形成了五个氢键和一个有利的盐桥相互作用，以及若干疏水相互作用，从而稳定了其在人类卵巢肿瘤结构域内的结合。衍生物 DTGP 是 DTG 衍生物中最有效的一种，其 ΔG 模型值为 -108 kcal/mol，这主要是由于它与 C 链中的 LYS204 氨基酸发生了 π 阳离子相互作用，从而显著增强了其结合亲和力。此外，对人类卵巢癌和前列腺癌细胞系进行的 DNA 损伤研究确定，DNA 损伤导致的细胞死亡是细胞活力下降的基础。这些结果支持将这些化合物作为潜在候选药物进行评估。

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引用次数: 0

A hexanuclear Iridium(III) cluster for histidine-induced singlet oxygen and superoxide radicals generation 组氨酸诱导单线态氧和超氧自由基生成的六核铱(III)团簇

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-10-22 DOI: 10.1016/j.poly.2024.117264

Dan Yang , Meng Zhong , Zhiguo Zhou , Xu Chen

Photosensitizers (PSs) play key roles in photodynamic therapy (PDT). PDT is typically reliant on the local concentration of oxygen. A big challenge for PSs is to develop oxygen-independent photosensitizers, which can work well in hypoxic tumor microenvironment. In this piece of work, a hexanuclear Ir(III) cluster (Ir6) is highly selective towards histidine and histidine-rich (His-rich) proteins to form mononuclear Ir(III) complexes of [Ir(bpy)₂(His)]. After the selective response to histidine or his-rich proteins, [Ir(bpy)₂(His)] generates both singlet oxygen(¹O₂) and superoxide (O₂⁻). This work opens an avenue for the potential application of Ir6 for type Ι and ΙΙ synergic photodynamic therapy.

光敏剂（PSs）在光动力疗法（PDT）中发挥着关键作用。光动力疗法通常依赖于局部的氧气浓度。光敏剂面临的一大挑战是开发不依赖氧气的光敏剂，这种光敏剂能在缺氧的肿瘤微环境中发挥良好作用。在这项研究中，六核 Ir(III) 簇（Ir6）对组氨酸和富含组氨酸（His-rich）的蛋白质具有高度选择性，形成 [Ir(bpy)2(His)] 的单核 Ir(III) 复合物。在对组氨酸或富含组氨酸的蛋白质产生选择性反应后，[Ir(bpy)2(His)] 会产生单线态氧（1O2）和超氧（O2-）。这项工作为 Ir6 在Ι型和ΙΙ型协同光动力疗法中的潜在应用开辟了一条途径。

引用次数: 0

Predictive calculation of the stability constants of silver(I) ion with pyridine and 2,2′-bipyridyl in a solvent environment 银（I）离子与吡啶和 2,2′-联吡啶在溶剂环境中的稳定常数的预测计算

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-10-22 DOI: 10.1016/j.poly.2024.117265

Irina A. Kuz’mina , Mariia A. Kovanova , Svetlana O. Nikiforova (Perova)

In the present study, the stability constants of silver(I) coordination compounds with 2,2′-bipyridyl (bpy, L) in mixed methanol–acetonitrile solvents (MeOH-AN, χ_AN = 0.0 ÷ 1.0 mol fr.) were determined by the potentiometric method at 25.0 °C. The influence of reagents solvation on the change in stability of [Ag(bpy)]⁺ and [Ag(bpy)₂]⁺ complexes upon changing the composition of the solvent MeOH→(MeOH-AN) was analyzed. It has been established that the determining factor in the shift of the complex formation equilibrium along the first and second steps of coordination with a change in the composition of the solvent is the contribution from the central ion resolvation. The obtained results and data on the thermodynamics of complex formation reactions of Ag⁺ with bpy and pyridine (py, L) in a few binary non-aqueous solvents were compared. The possibility of carrying out an estimated calculation of the stability constants of [Ag(L)]⁺ in non-aqueous solvents was confirmed.

本研究采用电位法测定了 2,2′-联吡啶（bpy，L）与银（I）配位化合物在甲醇-乙腈混合溶剂（MeOH-AN，χAN = 0.0 ÷ 1.0 mol fr.）中于 25.0 ℃下的稳定性常数。分析了试剂溶解度对改变溶剂 MeOH→（MeOH-AN）组成时 [Ag(bpy)]+ 和 [Ag(bpy)2]+ 复合物稳定性变化的影响。结果表明，随着溶剂成分的改变，络合物形成平衡在第一步和第二步配位过程中发生变化的决定因素是中心离子解析的贡献。我们比较了 Ag+ 与铋和吡啶（py, L）在一些二元非水溶剂中形成络合物反应的热力学结果和数据。证实了对非水溶剂中[Ag(L)]+ 的稳定常数进行估计计算的可能性。

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引用次数: 0

Investigation of the homonuclear and polynuclear complexes of FeIII of pentadentate dipodal s-triazine Schiff base ligand 五正齿二极 s-三嗪希夫碱配体的 FeIII 同核和多核配合物研究

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-10-22 DOI: 10.1016/j.poly.2024.117268

Remziye Beyza Arslan, Ziya Erdem Koc

An efficient synthesis of a new class of “Dipodal s-triazine Schiff base ligand” has been developed based on high-yielding amines substitutions of 2-vinyl-4,6-diamino-1,3,5-triazine (acryloguanamine) (VDAT) by salicylaldehyde. A new compound characterized by a dipodal s-triazine pentadentate Schiff base with 2-vinyl-4,6-N,N’-bis(2,4-dihydroxybenzylidine)-1,3,5-triazine [VDAT24] has been developed. The obtained [VDAT24] was polymerized to obtain poly(2-vinyl-4,6-N,N’-bis(2,4-dihydroxybenzylidine)-1,3,5-triazine) [PVDAT24]. Subsequently, s-Triazine-centered Fe(III) homonuclear complexes [VDAT24Fe], and polynuclear complexes [PVDAT24Fe] were obtained derived. As a result, the ligand obtained by elemental analysis, ICP-AES, TGA, FTIR, ¹H NMR and ¹³C NMR. Isolated ligand complex, FTIR, TGA, and were illuminated structures on the magnetic susceptibility. The resulting two different polymeric ligands and certain complexes of FTIR, TGA, and Ostwald Viscometer elucidated the structures of magnetic susceptibility.

基于水杨醛对 2-乙烯基-4,6-二氨基-1,3,5-三嗪（丙烯酰胍胺）（VDAT）的高产胺取代，开发了一种新型 "二极 s-三嗪希夫碱配体 "的高效合成方法。我们开发出了一种新化合物，其特征是 2-乙烯基-4,6-N,N'-双（2,4-二羟基苄基啶）-1,3,5-三嗪与 2-乙烯基-4,6-N,N'-双（2,4-二羟基苄基啶）-1,3,5-三嗪形成了二极 s-三嗪五价席夫碱[VDAT24]。将得到的[VDAT24]进行聚合，得到聚(2-乙烯基-4,6-N,N'-双(2,4-二羟基苄基)-1,3,5-三嗪)[PVDAT24]。随后，又衍生出了以 s-三嗪为中心的铁(III)同核配合物[VDAT24Fe]和多核配合物[PVDAT24Fe]。因此，通过元素分析、ICP-AES、TGA、傅立叶变换红外光谱、1H NMR 和 13C NMR 获得了配体。分离出的配体复合物、傅立叶变换红外光谱（FTIR）、热重分析仪（TGA）和磁感应强度都显示了其结构。由此产生的两种不同的聚合物配体和某些络合物的傅立叶变换红外光谱、热重分析和奥斯特瓦尔德粘度计阐明了磁感应强度的结构。

引用次数: 0

Heteronuclear coordination polymers with imidazole ligand: Synthesis, characterization and alcohol oxidation activities 含咪唑配体的异核配位聚合物：合成、表征和酒精氧化活性

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-10-22 DOI: 10.1016/j.poly.2024.117263

Güneş Süheyla Kürkçüoğlu , Okan Zafer Yeşilel , Telvin Mwanza , Seray Kekeç , Hakan Ünver , Onur Şahin

Two new heteronuclear Cd(II)/Pd(II) coordination polymers, [Cd₂(µ-im)₂(Him)₄Pd(µ-CN)₄]_n (1) and [Cd(Him)₂Pd(µ-CN)₄]_n (2) (Him: imidazole), have been synthesized under different conditions and characterized using elemental analysis, thermal analysis, FT-IR and Raman spectroscopy, single-crystal and powder X-ray diffraction techniques. In 1, the Cd(II) ions are bridged by imidazolate ligands to generate 1D chain structure. Neighbouring 1D chains were linked by [Pd(CN)₄]^2- ions to form 3D framework. In 2, the metal ions are bridged by cyanide ligands to generate 2D [Cd₂Pd₂(µ-CN)₄]_n network. Catalytic peroxidative oxidation activity of 1 and 2 was examined on the oxidation of benzyl alcohol using tertiary-butyl hydroperoxide (t-BuOOH) as the oxygen source. The compound 1 exhibited over 90 % product conversion at 80 °C in 24-hour reaction time. In addition, the catalyst exhibited high selectivity towards benzaldehyde and no over-oxidation product (benzoic acid) was detected.

在不同条件下合成了两种新的异核镉(II)/钯(II)配位聚合物：[Cd2(µ-im)2(Him)4Pd(µ-CN)4]n (1) 和 [Cd(Him)2Pd(µ-CN)4]n (2)（Him：咪唑），并利用元素分析、热分析、傅立叶变换红外光谱和拉曼光谱、单晶和粉末 X 射线衍射技术对其进行了表征。在 1 中，镉（II）离子通过咪唑配体桥接，生成一维链结构。相邻的一维链由 [Pd(CN)4]2- 离子连接，形成三维框架。在 2 中，金属离子通过氰配体桥接，生成二维 [Cd2Pd2(µ-CN)4]n 网络。以叔丁基过氧化氢（t-BuOOH）为氧源，考察了 1 和 2 在苯甲醇氧化过程中的催化过氧化活性。化合物 1 在 80 °C、24 小时反应时间内的产物转化率超过 90%。此外，该催化剂对苯甲醛具有高选择性，且未检测到过氧化产物（苯甲酸）。

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引用次数: 0

Chiral and racemic BINOL spiroborate anions and radical-cation salt with BEDT-TTF 手性和外消旋 BINOL 螺硼酸阴离子和 BEDT-TTF 自由基阳离子盐

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-10-22 DOI: 10.1016/j.poly.2024.117262

Joseph O. Ogar, Toby J. Blundell, Rifna Usman, Marek Vavrovič, Lee Martin

Sodium salts of the spiroborate anion bis[(1,1′-binaphthalene)-2,2′-diolato-O,O’]borate in enantiopure and racemic forms have been obtained through reaction of BORAX (sodium tetraborate hexahydrate) with the corresponding stereoisomers of BINOL [(1,1′-binaphthalene)-2,2′-diol]. Electrocrystallisation of these salts with BEDT-TTF produces single crystals of a 1:1 radical-cation salt, (BEDT-TTF){B[1,1′-bis(BINOL)]₂}•THF, with the racemic spiroborate anion whilst no crystals were obtained with the enantiopure forms.

通过 BORAX（六水合四硼酸钠）与 BINOL [(1,1′-联萘)-2,2′-二醇] 的相应立体异构体反应，获得了对映体和外消旋体形式的螺硼酸阴离子双[(1,1′-联萘)-2,2′-二醇-O,O']硼酸钠盐。用 BEDT-TTF 对这些盐进行电结晶，可得到带有外消旋螺硼酸阴离子的 1:1 自由基阳离子盐 (BEDT-TTF){B[1,1′-bis(BINOL)]2}-THF 单晶，而对映体则没有晶体。

引用次数: 0

Density functional theory investigation for noble gases adsorption on B3C2H5 structure B3C2H5 结构对惰性气体吸附的密度泛函理论研究

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-10-21 DOI: 10.1016/j.poly.2024.117266

Esraa Kareem Sehen Bany Mshatat , Morteza Rouhani , Hamid Saeidian

Quantum chemical calculations were performed to study the binding affinity of the B₃C₂H₅ cluster with noble gases. The results indicate that noble gas atoms especially the heavier ones such as Xe and Kr can form stable complexes with this cluster. Detailed analysis of the interaction mechanism reveals that the noble gas atoms serve as donor fragments in the formation of Ng@B₃C₂H₅, 2Ng@B₃C₂H₅, and 3Ng@B₃C₂H₅ donor–acceptor complexes.

为了研究 B3C2H5 团簇与惰性气体的结合亲和力，我们进行了量子化学计算。结果表明，惰性气体原子，尤其是 Xe 和 Kr 等较重的惰性气体原子，可以与该簇形成稳定的络合物。对相互作用机理的详细分析表明，惰性气体原子在形成 Ng@B3C2H5、2Ng@B3C2H5 和 3Ng@B3C2H5 供体-受体复合物的过程中充当供体片段。

引用次数: 0

An extensive review on transition metal catalyzed indole CH activation: Catalyst selection and mechanistic insights 关于过渡金属催化吲哚 CH 活化的广泛综述：催化剂的选择和机理认识

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-10-16 DOI: 10.1016/j.poly.2024.117260

C.J. Ann Mary , Devipriya Vasudevan , Prasiddha Nagarajan , S. Suhas , Ajesh Vijayan , K.V. Radhakrishnan , Y.N. Sudhakar

The present review article explores the expansive synthetic methodologies facilitated by CH activation of indoles using transition metal catalysts. The strategic utilization of catalysts such as palladium, rhodium, iridium, ruthenium, and manganese has revolutionized organic synthesis by enabling selective alkynylation, acylation, and annulation reactions. These transformations are pivotal in pharmaceuticals, particularly in the synthesis of antihistamines and potential antiviral drugs against SARS-CoV-2. Additionally, these catalysts play a crucial role in perfumery and other chemical industries, enhancing the efficiency and precision of compound synthesis. The choice of transition metal catalysts is informed by their affordability and compatibility with both traditional analytical methods and innovative techniques like microwave synthesis and LED irradiation. Furthermore, this review underscores the interdisciplinary impact of transition metal-catalyzed CH activation on indoles, highlighting its significance in advancing both fundamental organic chemistry and applied sciences essential for modern technological advancements and drug discovery efforts.

本综述文章探讨了利用过渡金属催化剂对吲哚进行 CH 活化所促进的扩展合成方法。钯、铑、铱、钌和锰等催化剂的战略性使用，使选择性炔化、酰化和环化反应成为可能，从而彻底改变了有机合成。这些转化反应在制药领域，尤其是在合成抗组胺药和潜在的抗 SARS-CoV-2 病毒药物方面，具有举足轻重的作用。此外，这些催化剂在香水和其他化学工业中也发挥着至关重要的作用，可提高化合物合成的效率和精确度。选择过渡金属催化剂的依据是它们的经济性以及与传统分析方法和创新技术（如微波合成和 LED 照射）的兼容性。此外，本综述还强调了过渡金属催化 CH 活化对吲哚的跨学科影响，突出了其在推进基础有机化学和应用科学方面的重要意义，而基础有机化学和应用科学对于现代技术进步和药物发现工作至关重要。

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引用次数: 0

In situ Grignard metalation method (iGMM) for the preparation of alkynyl magnesium and calcium compounds 原位格氏金属化法（iGMM）制备炔基镁和钙化合物

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-10-14 DOI: 10.1016/j.poly.2024.117256

Simon Sengupta, Phil Liebing, Matthias Westerhausen

In the in situ Grignard Metalation Method (iGMM), intermediately formed ethylmagnesium bromide as well as ethylcalcium and ethylstrontium iodide metalate trialkylsilylethyne in THF. For Me₃SiCCMgBr (1a) a temperature-dependent Schlenk equilibrium is operative and this heteroleptic compound coexists with the homoleptic congeners Mg(CCSiMe₃)₂ (1b) and MgBr₂. The reaction enthalpy ΔH and entropy ΔS adopt characteristic values. Initially formed Me₃SiCCCaI (2a) is quantitatively converted to the homoleptic compound Ca(CCSiMe₃)₂ (2b) and CaI₂. With increasing size of the alkaline-earth metal increasing amounts of the degradation product Me₃SiCCSiMe₃ hamper isolation of analytically pure compounds of strontium and barium. The molecular structures of [(thf)₃Mg(CCSiMe₃)₂] (1b) and [(thf)₃Ca(µCCSiMe₃)I]₂ (2a) have been determined by single-crystal X-ray diffraction.

在原位格氏金属化法（iGMM）中，在四氢呋喃中立即形成了乙基溴化镁以及乙基钙和乙基碘化锶金属化三烷基硅烷基乙炔。对于 Me3SiCCMgBr (1a)，与温度有关的 Schlenk 平衡正在起作用，这种异性化合物与同性同系物 Mg(CCSiMe3)2 (1b) 和 MgBr2 共存。反应焓 ΔH 和熵 ΔS 采用特征值。最初形成的 Me3SiCCCaI (2a) 被定量转化为同性化合物 Ca(CCSiMe3)2 (2b) 和 CaI2。随着碱土金属体积的增大，降解产物 Me3SiCCSiMe3 的数量也在增加，这妨碍了锶和钡分析纯化合物的分离。单晶 X 射线衍射测定了 [(thf)3Mg(CCSiMe3)2] (1b) 和 [(thf)3Ca(µCCSiMe3)I]2 (2a) 的分子结构。

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引用次数: 0

Magnesiation and calciation of CH acidic N-alkyl imidazoles 镁化和煅烧 CH 酸性 N-烷基咪唑

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-10-12 DOI: 10.1016/j.poly.2024.117255

Bibian Okokhere-Edeghoghon, Michael S. Hill, Mary F. Mahon

The reactivity of β-diketiminato alkylmagnesium, hydridomagnesium and hydridocalcium bases toward 1-methylimidazole, 1-tert-butylimidazole and 1-methylbenzimidazole enables the C-magnesiation and calciation of this family of N-heterocyclic molecules. Although 1-methylimidazole, 1-tert-butylimidazole, and 1-methylbenzimidazole are deprotonated at their C-2 positions by both the magnesium alkyl and hydride derivatives, these reagents can also leverage a level of regiodivergent kinetic discrimination and resultant C-4 metallation. In contrast to the straightforward C-2-deprotonation of 1-methylbenzimidazole provided by the magnesium hydride, a rapid cascade of apparent deprotonation, imidazole ring opening and twofold CC coupling was induced by the analogous calcium reagent. This process provides a tricalcium species comprising an unprecedented trianionic unit, which may be considered as a trimethylenemethane dianion isostere equipped with a pendent amide donor. While attempted boron functionalisation of the imidazolyl anions of the magnesium derivatives of 1-methylimidazole and 1-methylbenzimidazole with pinacolborane (HBpin) was unsuccessful, the 1-tert-butylimidazolyl analogue provided the C-2-borylated product irrespective of the position of initial C-2 or C-4 deprotonation. Although the calcium congeners resulting from 1-methylimidazole and 1-tert-butylimidazole were deduced to form similarly borylated products, study of their onward reactivity was prevented by their instability toward Schlenk-type redistribution in solution.

β-二酮亚甲基烷基镁、氢化镁和氢化钙碱对 1-甲基咪唑、1-叔丁基咪唑和 1-甲基苯并咪唑的反应性使这一系列 N-杂环分子的 C-镁化和钙化成为可能。虽然 1-甲基咪唑、1-叔丁基咪唑和 1-甲基苯并咪唑的 C-2 位都会被镁的烷基和氢化物衍生物去质子化，但这些试剂也可以利用一定程度的区域差异动力学鉴别，从而实现 C-4 金属化。与氢化镁提供的 1-甲基苯并咪唑直接的 C-2 去质子化不同，类似的钙试剂诱导了明显的去质子化、咪唑开环和两倍 CC 偶联的快速级联反应。这一过程提供了一种由前所未有的三阴离子单元组成的三钙试剂，可将其视为配备了一个悬垂酰胺供体的三亚甲基二元等效物。用频哪醇硼烷（HBpin）对 1-甲基咪唑和 1-甲基苯并咪唑的镁衍生物咪唑阴离子进行硼官能化的尝试并不成功，而 1-叔丁基咪唑类似物则提供了 C-2 硼酰化产物，与最初的 C-2 或 C-4 去质子化位置无关。虽然推断出 1-甲基咪唑和 1-叔丁基咪唑产生的钙同系物也会形成类似的硼烷基化产物，但由于它们在溶液中不稳定的 Schlenk 型再分布，阻碍了对其后续反应性的研究。

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