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1.
《中国化学会会志》2018,65(5):554-560
Some less hindered 2,4,6‐tri‐aryloxy‐s‐triazines were synthesized through the reaction of the corresponding phenols as a starting materials with cyanogen bromide (BrCN) to obtain the corresponding arylcyanates and then trimerized. Unexpectedly, 2,4‐di‐tert‐butyl‐1‐cyanatobenzene derived from 2,4‐di‐tert‐butylphenol did not trimerize but, indeed, yielded bis(2,4‐di‐tert‐butylphenyl) carbonate. The structures of 2,4,6‐tri‐aryloxy‐s‐triazines and bis(2,4‐di‐tert‐butylphenyl) carbonate were characterized by means of IR, 1H, and 13C NMR spectroscopies. Also the structure of the latter compound was studied by X‐ray crystallography. 相似文献
2.
Copper complexes of chiral quinolinyl‐oxazoline have been studied as the catalysts for enantioselective allylic oxidation of cycloalkenes with tert‐butyl perbenzoate. Using 5 mol% of these chiral catalysts, optical active allylic benzoates were obtained in moderate enantiomeric excesses. CuOTf prepared in situ, CuClO4 and CuPF6 were found to be good precatalysts in acetone. 相似文献
3.
Michael P. Bubnov Nina A. Skorodumova Alexey A. Zolotukhin Alla V. Arapova Evgenii V. Baranov Anika Stritt Alper Ünal Andreas Grohmann Frank W. Heinemann Artem S. Bogomyakov Natal'a N. Smirnova Vladimir K. Cherkasov Gleb A. Abakumov 《无机化学与普通化学杂志》2014,640(11):2177-2182
Tris‐o‐semiquinonato cobalt complexes react with a tetrapodal pyridine‐derived ligand to form dinuclear cobalt compounds of general formula (OMP)[CoQ2]2, where OMP = 2,2′‐(pyridine‐2,6‐diyl)bis(N1,N1,N3,N3‐tetramethylpropane‐1,3‐diamine), Q = mono‐ or dianion of 3,6‐di‐tert‐butyl‐o‐benzoquinone (complex 1 ) and it derivatives: 3,6‐di‐tert‐butyl‐4,5‐N,N′‐piperazino‐o‐benzoquinone (complex 2 ), and 3,6‐di‐tert‐butyl‐4‐Cl‐o‐benzoquinone (complex 3 ). Single crystal X‐ray crystallography of 1 and 3 indicates two bis‐quinonato cobalt units bound by an OMP ligand, which acts as a bridge. Each central cobalt atom is chelated by one N1,N1,N3,N3‐tetramethylpropane‐1,3‐diamine and two o‐quinonato fragments. The nitrogen atom of the pyridine ring is uncoordinated. All complexes were characterized by NIR‐IR and EPR spectroscopy, precise adiabatic vacuum calorimetry, and by variable‐temperature magnetic susceptibility measurements. All data indicate a reversible thermally driven redox‐isomeric (valence tautomeric) transformation in the solid state for all complexes. 相似文献
4.
Catalytic Enantioselective Reaction of α‐Aminoacetonitriles Using Chiral Bis(imidazoline) Palladium Catalysts
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Masaru Kondo Tomoki Nishi Prof. Dr. Tsubasa Hatanaka Prof. Dr. Yasuhiro Funahashi Prof. Dr. Shuichi Nakamura 《Angewandte Chemie (International ed. in English)》2015,54(28):8198-8202
The catalytic enantioselective reaction of diphenylmethylidene‐protected α‐aminoacetonitriles with imines has been developed. Good yields and diastereo‐ and enantioselectivities were observed for the reaction of various imines using chiral bis(imidazoline)/Pd catalysts. The reaction of α‐aminonitriles with di‐tert‐butyl azodicarboxylate afforded chiral α,α‐diaminonitriles in high yields with high enantioselectivities. 相似文献
5.
Maria Kitamura Prof. Yoshimi Hirokawa Prof. Dr. Naoyoshi Maezaki Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(38):9911-9917
We have accomplished highly enantioselective [2,3]‐Wittig rearrangements of functionalized allyl benzyl ethers in the presence of a chiral di‐tBu‐bis(oxazoline) ligand. In various oxygenated benzylic ethers, the reactions proceeded with excellent diastereo‐ and enantioselectivities, although the presence of a methoxy substituent at the ortho‐position on the benzyl group drastically decreased the enantioselectivity. Conversely, o‐ethyl and o‐phenyl substituents had no significant effect on the selectivity. We found that the C2‐substituent of the allylic moiety played an important role in producing high enantioselectivity. Highly enantioselective [2,3]‐Wittig rearrangement in the presence of catalytic amounts of the chiral ligands is also described. 相似文献
6.
Maria‐Evgenia Kourti Georgios C. Vougioukalakis Nikos Hadjichristidis Marinos Pitsikalis 《Journal of polymer science. Part A, Polymer chemistry》2011,49(11):2520-2527
The cationic ring‐opening polymerization of 2‐methyl‐2‐oxazoline and 2‐phenyl‐2‐oxazoline was efficiently used using bis(η5‐cyclopentadienyl)dimethyl zirconium, Cp2ZrMe2, or bis(η5‐tert‐butyl‐cyclopentadienyl)dimethyl hafnium in combination with either tris(pentafluorophenyl)borate or tetrakis(pentafluorophenyl)borate dimethylanilinum salt as initiation systems. The evolution of polymer yield, molecular weight, and molecular weight distribution with time was examined. In addition, the influence of the initiation system and the monomer on the control of the polymerization was studied. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 000: 000–000, 2011 相似文献
7.
Shyam Sundar Mondal Manosree Chatterjee Ranjay K. Tiwari J.N. Behera Nripen Chanda Sourav Biswas Tanmoy Kumar Saha 《应用有机金属化学》2019,33(8)
A unique hexanuclear zinc(II) ( 1 ) and two mononuclear copper(II) ( 2 and 3 ) complexes anchored with imino phenol ligand HL 1 and HL 2 were synthesized with good yield and purity (where HL 1 = 4‐tert‐butyl‐2,6‐bis((mesitylimino)methylphenol and HL 2 = 5‐tert‐butyl‐2‐hydroxy‐3‐((mesitylimino)methyl)benzaldehyde). These complexes were characterized by utilizing various spectroscopic protocols like NMR, FTIR, UV as well as ESI‐Mass spectrometry, elemental analysis and single crystal X‐ray diffraction studies. Their potential to bind calf thymus DNA (CT‐DNA) was tested utilizing different techniques such as UV–visible and fluorescence spectroscopy. The experiment implies that they interact with CT‐DNA via non‐intercalative mode with moderate capabilities (Kb ~ 104 M?1). On the other hand, these complexes have high capabilities to quench the fluorescence of bovine serum albumin (BSA) following the static pathway. In addition, they are active catalysts for the oxidation reaction of 3,5‐di‐tert‐butylcatechol (3,5‐DTBC) to 3,5‐di‐tert‐butylquinone (3,5‐DTBQ) under aerobic condition. From the recorded EPR signals of all complexes, it has been concluded that the oxidation reaction proceeds via ligand oriented radical pathway instead of metal based redox participation. Kinetic studies using 1 – 3 indicate that it follows Michaelis–Menten type of equation with moderate to high turnover number (kcat). Apart from these aspects, complexes 1 – 3 were screened for their cytotoxic behavior towards HeLa cells (human cervical carcinoma) and found quite active with comparable IC50 values to cisplatin. 相似文献
8.
Andrey I. Poddel’sky Prof. Dr. Alexander V. Piskunov Nikolay O. Druzhkov Georgii K. Fukin Vladimir K. Cherkasov Gleb A. Abakumov 《无机化学与普通化学杂志》2009,635(15):2563-2571
The treatment of di‐o‐quinone 4,4′‐(ethane‐1,2‐diyl)‐bis(3,6‐di‐tert‐butyl‐o‐benzoquinone) (Q–CH2–CH2–Q, 1 ) leads to its rearrangement to form di‐p‐quinomethide 4,4′‐(ethane‐1,2‐diylidene)bis(2‐hydroxy‐3,6‐di‐tert‐butyl‐cyclohexa‐2,5‐dienone) ( 2 ). The subsequent oxidation of 2 by an alkaline solution of K3[Fe(CN)6] yielded the new di‐o‐quinone 4,4′‐(ethene‐1,2‐diyl)bis(3,6‐di‐tert‐butyl‐o‐benzoquinone) (Q–CH=CH–Q, 3 ), which contains an ethylene bridge. The formation of mono‐ and poly‐reduced derivatives of 2 and 3 with potassium, thallium was studied by EPR technique. The dinuclear thallium derivative of 3 , Tl(SQ–CH=CH–SQ)Tl, was found to exist in the diamagnetic quinomethide form. The most stable derivatives of 2 and 3 are triphenyltin(IV) bis‐p‐quinomethide‐phenolate ( 4 ) and triphenylantimony(V) bis‐catecholate ( 5 ), which have been synthesized and isolated. The molecular structures of 2 , 3 , and 5 were characterized by single‐crystal X‐ray diffraction. 相似文献
9.
The reaction of 3,8‐bis(diazo)‐2,2,4,4,7,7,9,9‐octamethyldecane ( 5 ) with elemental selenium in 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) at 130°C yielded 1,2‐di‐tert‐butyl‐3,3,6,6‐tetramethylcyclohexene ( 1 ) (64%) and trans‐3,8‐di‐tert‐butyl‐4,4,7,7‐tetramethyl‐1,2‐diselenocane ( 8 ) (13%), while that of 5 with elemental sulfur in DBU gave trans‐3, 8‐di‐tert‐butyl‐4,4,7,7‐tetramethyl‐1,2‐dithiocane ( 9 ) (77%). The reaction of 3,9‐bis(diazo)‐2,2,4,4,8,8,10,10‐octamethylundecane ( 6 ) with elemental selenium in DBU at 80°C gave a cyclic triselenide, cis‐4,10‐di‐tert‐butyl‐5,5,9,9‐tetramethyl‐1,2,3‐triselenecane ( 11 ), in 15% yield as the only identifiable product. The structures of 9 and 11 were confirmed by X‐ray crystallography. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:351–356, 2002; Published online in Wiley Interscience (www.interscience.wiley.com). DOI 10.1002/hc.10046 相似文献
10.
Amino‐ and halofunctional Siloxititanes Amino‐di‐tert‐butylsilanol reacts with tetrabutoxititane in a molar ratio of 2:1 to give di‐n‐butoxi(bis(di‐tert‐butyl‐n‐butoxi)siloxi)titane, (C4H9OSi(CMe3)2‐O)2Ti(OC4H9)2 ( 1 ), and lithium‐di‐tert‐butylchlorosilanolate in a molar ratio of 3:1 to give n‐butoxi(tris(di‐tert‐butyl‐n‐butoxi)siloxi)titane, (H9C4OSi(CMe3)2‐O)3TiOC4H9 ( 2 ). The amino‐di‐tert‐butylsilanol substitutes the four chloroatoms of TiCl4 in the presence of triethylamine as HCl‐acceptor. The tetrakis(amino‐di‐tert‐butyl)siloxititane ( 3 ) is formed. The lithium salt of di‐tert‐butylfluorosilanol reacts with TiCl4 in a molar ratio of 2:1 to give 1, 1, 3, 3‐tetra‐tert‐butyl‐1‐fluoro‐3‐trichlorotitoxi‐1, 3‐disiloxane, FSi(CMe3)2‐O‐Si(CMe3)2‐O‐TiCl3 ( 4 ). In the reaction of di‐tert‐butyl‐chlorosilanol and TiCl4, the anion [chlorosiloxi‐octa(tri‐μ2‐chlorotitanate)]— ( 5 ) with protonated diethylether as counterion is obtained by using diethylether as HCl‐acceptor. The crystal structure determinations of 3 and 5 are reported. 相似文献
11.
Dr. Jian‐Bo Xie Prof. Jian‐Hua Xie Xiao‐Yan Liu Qian‐Qian Zhang Prof. Qi‐Lin Zhou 《化学:亚洲杂志》2011,6(3):899-908
The iridium complexes of chiral spiro aminophophine ligands, especially the ligand with 3,5‐di‐tert‐butylphenyl groups on the P atom ( 1c ) were demonstrated to be highly efficient catalysts for the asymmetric hydrogenation of alkyl aryl ketones. In the presence of KOtBu as a base and under mild reaction conditions, a series of chiral alcohols were synthesized in up to 97 % ee with high turnover number (TON up to 10 000) and high turnover frequency (TOF up to 3.7×104 h−1). Investigation on the structures of the iridium complexes of ligands (R)‐ 1a and 1c by X‐ray analyses disclosed that the 3,5‐di‐tert‐butyl groups on the P‐phenyl rings of the ligand are the key factor for achieving high activity and enantioselectivity of the catalyst. Study of the catalysts generated from the Ir‐(R)‐ 1c complex and H2 by means of ESI‐MS and NMR spectroscopy indicated that the early formed iridium dihydride complex with one (R)‐ 1c ligand was the active species, which was slowly transformed into an inactive iridium dihydride complex with two (R)‐ 1c ligands. A plausible mechanism for the reaction was also suggested to explain the observations of the hydrogenation reactions. 相似文献
12.
The synthesis and characterization of aluminum alkoxide and alkyl complexes stabilized by piperazidine‐bridged bis(phenolate) ligands are described. Treatment of ligand precursors H2[ONNO]1 {H2[ONNO]1=1,4‐bis(2‐hydroxy‐3‐tert‐butyl‐5‐methylbenzyl)piperazidine} and H2[ONNO]2 {H2[ONNO]2=1,4‐bis(2‐hydroxy‐3,5‐di‐tert‐butylbenzyl)piperazidine} with AlEt2(OCH2Ph) and AlEt2(OPr‐i), which were generated in situ by the reactions of AlEt3 with equivalent of the corresponding alcohols, in a 1:1 molar ratio in THF gave the corresponding aluminum alkoxide complexes [ONNO]1Al(OCH2Ph) ( 1 ) and [ONNO]2Al(OPr‐i) ( 2 ), respectively. The reaction of H2[ONNO]1 with AlEt2(OCH2Ph) in a 1:2 molar ratio in THF afforded a mixture of monometallic aluminum ethyl complex [ONNO]1AlEt ( 3 ) and complex 1 , which can be isolated by stepwise crystallization. Similarly, H2[ONNO]2 reacted with AlEt2(OPr‐i) in a 1:2 molar ratio in THF to give a mixture of aluminum ethyl complex [ONNO]2AlEt ( 4 ) and complex 2 . Complexes 1 and 2 were also available via treatment of complexes 3 and 4 with 1 equiv. of benzyl alcohol and isopropyl alcohol, respectively. All of these complexes were fully characterized including X‐ray structural determination. It was found that complexes 1 to 4 can initiate the ring‐opening polymerization of ε‐caprolactone, and complexes 1 and 2 showed higher catalytic activity in comparison with complexes 3 and 4 . 相似文献
13.
Lanthanide(II) Complexes Supported by N,O‐Donor Tripodal Ligands: Synthesis,Structure, and Ligand‐Dependent Redox Behavior
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Julie Andrez Dr. Gülay Bozoklu Dr. Grégory Nocton Dr. Jacques Pécaut Dr. Rosario Scopelliti Dr. Lionel Dubois Dr. Marinella Mazzanti 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(43):15188-15200
The preparation and characterization of a series of complexes of the Yb and Eu cations in the oxidation state II and III with the tetradentate N,O‐donor tripodal ligands (tris(2‐pyridylmethyl)amine (TPA), BPA? (HBPA=bis(2‐pyridylmethyl)(2‐hydroxybenzyl)amine), BPPA? (HBPPA=bis(2‐pyridylmethyl)(3.5‐di‐tert‐butyl‐2‐hydroxybenzyl)amine), and MPA2? (H2MPA=(2‐pyridylmethyl)bis(3.5‐di‐tert‐butyl‐2‐hydroxybenzyl)amine) is reported. The X‐ray crystal structures of the heteroleptic Ln2+ complexes [Ln(TPA)I2] (Ln=Eu, Yb) and [Yb(BPA)I(CH3CN)]2, of the Ln2+ homoleptic [Ln(TPA)2]I2 (Ln=Sm, Eu, Yb) and [Eu(BPA)2] complexes, and of the Ln3+ [Eu(BPPA)2]OTf and [Yb(MPA)2K(dme)2] (dme=dimethoxyethane) complexes have been determined. Cyclic voltammetry studies carried out on the bis‐ligand complexes of Eu3+ and Yb3+ show that the metal center reduction occurs at significantly lower potentials for the BPA? ligand as compared with the TPA ligand. This suggests that the more electron‐rich character of the BPA? ligand results in a higher reducing character of the lanthanide complexes of BPA? compared with those of TPA. The important differences in the stability and reactivity of the investigated complexes are probably due to the observed difference in redox potential. Preliminary reactivity studies show that whereas the bis‐TPA complexes of Eu2+ and Yb2+ do not show any reactivity with heteroallenes, the [Eu(BPA)2] complex reduces CS2 to afford the first example of a lanthanide trithiocarbonate complex. 相似文献
14.
Bernd Schetter 《无机化学与普通化学杂志》2004,630(7):1074-1078
Reaction Behaviour of Several Carbodiimides with 1, 1'‐Ferrocenedicarboxylic Acid 1, 1'‐bis‐(1, 3‐dicyclohexylureidocarbonyl)‐ferrocene ( 1 ), 1, 1'‐bis‐(1, 3‐diisopropylureidocarbonyl)‐ferrocene ( 2 ) and ferrocene‐1, 1'‐bis‐N‐p‐tolylcarboxamide ( 6 ) were synthesized by melting down 1, 1'‐ferrocenedicarboxylic acid ( 7 ) together with N, N'‐dicyclohexylcarbodiimide (DCC), N, N'‐diisopropylcarbodiimide (DIC) or N, N'‐di‐p‐tolylcarbodiimide ( 8 ), respectively, without application of any solvent in a short space of time. Substance 1 , 2 , 1, 1'‐bis‐(1‐ethyl‐3‐tert‐butylureidocarbonyl)‐ferrocene ( 3 ), 1‐(1‐tert‐butyl‐3‐ethylureidocarbonyl)‐1'‐(1‐ethyl‐3‐tert‐butylureidocarbonyl)‐ferrocene ( 4 ) and 1, 1'‐bis‐(1‐tert‐butyl‐3‐ethylureidocarbonyl)‐ferrocene ( 5 ) were obtained in good yield by reacting 7 DCC, DIC, or N‐tert‐butyl‐N'‐ethylcarbodiimide ( 9 ), respectively, with in ethyl acetate for weeks. Transannular 1, 1'‐ferrocenedicarboxylic anhydride was not detectable or isolable in these reactions. All new compounds were characterized by 1H‐NMR, 13C‐NMR, IR, MS and elementar analysis. In the case of 1 a single crystal structure analysis was made. 相似文献
15.
The asymmetric Friedel–Crafts alkylation of electron‐rich N‐containing heterocycles with nitroalkenes under catalysis of diphenylamine‐tethered bis(oxazoline) and bis(thiazoline)‐ZnII complexes was investigated. In the reaction of indole derivatives, the complex of ligand 4 f with trans‐diphenyl substitutions afforded better results than previously published ligand 4 e with cis‐diphenyl substitutions. Excellent yields (up to greater than 99 %) and enantioselectivities (up to 97 %) were achieved in most cases. The complex of ligand 4 d bearing tert‐butyl groups gave the best results in the reactions of pyrrole. Moderate to good yields (up to 91 %) and enantioselectivities (up to 91 %) were achieved in most cases. The origin of the enantioselectivity was attributed to the NH–π interaction between the catalyst and the incoming aromatic system in the transition state. Such an interaction was confirmed through comparison of the enantioselectivity and the absolute configuration of the products in the reactions catalyzed by designed ligands. 相似文献
16.
Heteroleptic [Bis(oxazoline)](dipyrrinato)zinc(II) Complexes: Bright and Circularly Polarized Luminescence from an Originally Achiral Dipyrrinato Ligand
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Dr. Julius F. Kögel Dr. Shinpei Kusaka Dr. Ryota Sakamoto Toshiki Iwashima Mizuho Tsuchiya Ryojun Toyoda Ryota Matsuoka Dr. Takamasa Tsukamoto Dr. Junpei Yuasa Prof. Dr. Yasutaka Kitagawa Prof. Dr. Tsuyoshi Kawai Prof. Dr. Hiroshi Nishihara 《Angewandte Chemie (International ed. in English)》2016,55(4):1377-1381
Heteroleptic zinc(II) complexes synthesized using achiral dipyrrinato and chiral bis(oxazoline) ligands show bright fluorescence with quantum efficiencies of up to 0.70. The fluorescence originates from the 1π–π* photoexcited state localized exclusively on the dipyrrinato ligand. Furthermore, the luminescence is circularly polarized despite the achirality of the dipyrrinato ligand. Single‐crystal X‐ray structure analysis discloses that the chiral bis(oxazoline) ligand undergoes intramolecular π–π stacking with the dipyrrinato ligand, inducing axial chirality in the dipyrrinato moiety. 相似文献
17.
A mass spectrometric method for rapidly assaying the chiral selectivities of the copper(I) complexes of C2‐symmetric ligands
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A gas‐phase method for rapidly assaying the enantioselectivity of metal‐centered catalysts is presented. It relies on gas‐phase equilibrium measurements in a quadrupole ion trap mass spectrometer. A group of well‐established C2‐symmetric bis‐oxazoline copper(I) complexes was used to identify chiral probe reagents that are capable of profiling the quality of the asymmetric environment provided by the metal complex. The chiral probes were then applied to a wide variety of copper(I) bis‐di‐imine complexes. Complexes based on a BINAM backbone exhibited selectivities that were comparable to the bis‐oxazolines. Taking advantage of the mass selectivity capabilities of the ion trap mass spectrometer, the method was also applied to an un‐purified mix of copper(I) complexes derived from a combinatorial synthesis of bis‐di‐imine ligands. This approach holds promise as a rapid screening tool for potential chiral catalysts. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
18.
Petr Majzlík Ladislav Omelka Renata Superatová Petra Holubcová 《Helvetica chimica acta》2011,94(7):1260-1268
A series of substituted 4‐methylphenols 1 and 2 was oxidized with PbO2 in the presence of nitroso compounds 3 – 10 . The formation of adducts of benzyl radicals with the nitroso spin traps in the reaction mixture was established, suggesting the abstraction of an H‐atom from the methyl substituent of 1 or 2 . In the consecutive steps, the adducts underwent a further rearrangement to the corresponding nitrones. When the starting phenol contained bulky tBu groups in ortho‐position (see 2,6‐di(tert‐butyl)‐4‐methylphenol ( 1a )), the stable 2,6‐di(tert‐butyl)‐4R‐phenoxy radicals (R=? CH?N+(O?)? X) were detected as the final radical products. The indirect evidence of nitrones in the reaction mixture was performed in one case by the reaction with a RO radicals. 相似文献
19.
Pascal C. Leverd Dirk Weber Wolf D. Habicher Martine Nierlich 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(8):997-998
The acyclic tetraphenolic derivative 2,2′‐methylenebis[6‐(3‐tert‐butyl‐2‐hydroxy‐5‐methylbenzyl)‐4‐methylphenol] reacts with excess triethylamine in acetonitrile to form a molecular complex, i.e. triethylammonium 2‐(3‐tert‐butyl‐2‐hydroxy‐5‐methylbenzyl)‐6‐[3‐(3‐tert‐butyl‐2‐hydroxy‐5‐methylbenzyl)‐2‐hydroxy‐5‐methylbenzyl]‐4‐methylphenolate acetonitrile solvate, C6H16N+·C39H47O4?·C2H3N, where the organic HNEt3+ cation is included in the partial cone defined by the aromatic faces of the acyclic polyphenolate. 相似文献
20.
Stable trans isomer as the kinetic and theromodynamic product for the oxidative addition of MeI to cycloplatinated(II) complexes comprising isocyanide ligands
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Hamid R. Shahsavari Reza Babadi Aghakhanpour Mojdeh Hossein‐Abadi Reza Kia Paul R. Raithby 《应用有机金属化学》2018,32(4)
The present investigation introduces a new series of cycloplatinated(II) complexes, with the general formula Pt(O‐bpy)(Me)(CN‐R)] (R = benzyl, 2‐naphtyl and tert‐butyl), which are able to generate the stable trans‐Pt(IV) product in the solution after the reaction with iodomethane. In fact, the trans product is both the kinetic and thermodynamic product of the reaction; this observation was supported by DFT calculations. These Pt(II) complexes are supported by 2,2'‐bipyridine N‐oxide (O‐bpy) and one of several isocyanides as the cyclometalated and ancillary ligands, respectively. These new Pt(II) complexes undergo oxidative addition with MeI to give the corresponding trans‐Pt(IV) complexes. All the complexes were identified employing the multi‐nuclear NMR spectroscopy and single crystal X‐ray crystallography. The kinetic investigations were also performed for the oxidative addition reactions in order to measure the reaction rates; the reaction was followed by UV‐Vis spectroscopy. The rates obtained follow the trend CN‐tBu > CN‐Bz > CN‐2 Np for the CN‐R ligands in the Pt(II) complexes. The order can be related to the degree of electron‐donation of the R group (tert‐butyl > benzyl > 2‐naphtyl). 相似文献