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1.
Hyunho Kim Minseop Kim Dr. Hayoung Song Prof. Eunsung Lee 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(11):3849-3854
The synthesis of ambiphilic N-heterocyclic carbene ligand, indol-2-ylidene (IdY, A ), is described. A series of indolenium precursors ( 2 a – f ) were prepared on a gram scale in good yields. Trapping experiments with elemental selenium, [RhCl(cod)]2 and CuCl provided the expected carbene adducts. Further computational and spectroscopic studies supported the ambiphilicity of IdY, which lies between cyclic (alkyl)(amino)carbenes (CAAC-5) and cyclic (amino)(aryl)carbene (CAArC). The copper complexes ( 6 ) show high percent buried volume (% Vbur = 58.1) and allow for carboboration of terminal alkynes within 30 minutes in a demonstration of synthetic utility with good yields and high regioselectivity. 相似文献
2.
Cyclic (Alkyl)(Amino)Carbene Complexes of Rhodium and Nickel and Their Steric and Electronic Parameters
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Ursula S. D. Paul Carolin Sieck Dr. Martin Haehnel Kai Hammond Prof. Dr. Todd B. Marder Prof. Dr. Udo Radius 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(31):11005-11014
N‐heterocyclic carbenes (NHCs) and cyclic (alkyl)(amino)carbenes (CAACs) are of great interest, as their electronic and steric properties provide a unique class of ligands and organocatalysts. Herein, substitution reactions involving novel carbonyl complexes of rhodium and nickel were studied to provide a deeper understanding of the fundamental electronic factors characterizing CAACmethyl, which were compared with the large array of data available for NHC and sterically more demanding CAAC ligands. 相似文献
3.
New N‐Alkyl‐substituted imidazolium salts as well as a series of their corresponding [Pd(NHC)(MA)2] complexes have been obtained by three routes in good yield. The previously reported synthesis for the analogous N‐aryl substituted [Pd(NHC)(MA)2] complexes has been improved. The N‐alkyl‐substituted [Pd(NHC)(MA)2] complexes are thermally more labile than their N‐aryl counterparts. Catalytic transfer semi‐hydrogenation of phenylpropyne resulted in good to excellent chemo‐ and stereo‐ selectivity conversion into (Z)‐phenylpropene. The size of the alkyl substituents correlates with the rate of hydrogenation in the sense that more bulky substituents give rise to faster transfer hydrogenation rates. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
4.
Boryl‐Functionalized σ‐Alkynyl and Vinylidene Rhodium Complexes: Synthesis and Electronic Properties
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Prof. Dr. Holger Braunschweig Christopher K. L. Brown Dr. Rian D. Dewhurst Dr. J. Oscar C. Jimenez‐Halla Thomas Kramer Dr. Ivo Krummenacher Dr. Bernd Pfaffinger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(5):1427-1433
The synthesis, reactivity, and properties of boryl‐functionalized σ‐alkynyl and vinylidene rhodium complexes such as trans‐[RhCl(?C?CHBMes2)(PiPr3)2] and trans‐[Rh(C?CBMes2)(IMe)(PiPr3)2] are reported. An equilibrium was found to exist between rhodium vinylidene complexes and the corresponding hydrido σ‐alkynyl complexes in solution. The complex trans‐[Rh(C?CBMes2)(IMe)(PiPr3)2] (IMe=1,3‐dimethylimidazol‐2‐ylidene) was found to exhibit solvatochromism and can be quasireversibly oxidized and reduced electrochemically. Density functional calculations were performed to determine the reaction mechanism and to help rationalize the photophysical properties of trans‐[Rh(C?CBMes2)(IMe)(PiPr3)2]. 相似文献
5.
Rachad ElMail MaríaA. Garralda Ricardo Hernndez Lourdes Ibarlucea Elena Pinilla M.Rosario Torres 《Helvetica chimica acta》2002,85(5):1485-1495
The reaction of cationic diolefinic rhodium(I) complexes with 2‐(diphenylphosphino)benzaldehyde (pCHO) was studied. [Rh(cod)2]ClO4 (cod=cycloocta‐1,5‐diene) reacted with pCHO to undergo the oxidative addition of one pCHO with (1,2,3‐η)cyclooct‐2‐en‐1‐yl (η3‐C8H13) formation, and the coordination of a second pCHO molecule as (phosphino‐κP)aldehyde‐κO(σ‐coordination) chelate to give the 18e− acyl(allyl)rhodium(III) species [Rh(η3‐C8H13)(pCO)(pCHO)]ClO4 (see 1 ). Complex 1 reacted with [Rh(cod)(PR3)2]ClO4 (R=aryl) derivatives 3 – 6 to give stable pentacoordinated 16e− acyl[(1,2,3‐η)‐cyclooct‐2‐en‐1‐yl]rhodium(III) species [Rh(η3‐C8H13)(pCO)(PR3)]ClO4 7 – 10 . The (1,2,3‐η)‐cyclooct‐2‐en‐1‐yl complexes contain cis‐positioned P‐atoms and were fully characterized by NMR, and the molecular structure of 1 was determined by X‐ray crystal diffraction. The rhodium(III) complex 1 catalyzed the hydroformylation of hex‐1‐ene and produced 98% of aldehydes (n/iso=2.6). 相似文献
6.
Generalization of the Copper to Late‐Transition‐Metal Transmetallation to Carbenes beyond N‐Heterocyclic Carbenes
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Dr. Yannick D. Bidal Orlando Santoro Dr. Mohand Melaimi Dr. David B. Cordes Prof. Alexandra M. Z. Slawin Prof. Guy Bertrand Dr. Catherine S. J. Cazin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(27):9404-9409
Carbene transition‐metal complexes have become a prevalent family of catalysts enabling numerous organic transformations. Their facile synthetic access is a matter of great importance. To this end, the CuI‐NHC transfer methodology has emerged as a powerful alternative presenting attractive advantages over other methods. Herein, we report the remarkable ability of copper to transfer not only NHCs but also other types of carbenes such as abnormal NHCs (aNHCs), cyclic (alkyl)(amino)carbenes (CAACs), and mesoionic carbenes (MICs) to various transition metal precursors. 相似文献
7.
Synthesis,Characterization, and Theoretical Investigation of Two‐Coordinate Palladium(0) and Platinum(0) Complexes Utilizing π‐Accepting Carbenes
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Dr. Sudipta Roy Dr. Kartik Chandra Mondal Dipl.‐Chem. Jann Meyer Dipl.‐Chem. Benedikt Niepötter Christian Köhler Dr. Regine Herbst‐Irmer Prof. Dr. Dietmar Stalke Dr. Birger Dittrich Dr. Diego M. Andrada Prof. Dr. Gernot Frenking Prof. Dr. Herbert W. Roesky 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(26):9312-9318
An elegant general synthesis route for the preparation of two coordinate palladium(0) and platinum(0) complexes was developed by reacting commercially available tetrakis(triphenylphosphine)palladium/platinum with π‐accepting cyclic alkyl(amino) carbenes (cAACs). The complexes are characterized by NMR spectroscopy, mass spectrometry, and single‐crystal X‐ray diffraction. The palladium complexes exhibit sharp color changes (crystallochromism) from dark maroon to bright green if the C‐Pd‐C bond angle is sharpened by approximately 6°, which is chemically feasible by elimination of one lattice THF solvent molecule. The analogous dark orange‐colored platinum complexes are more rigid and thus do not show this phenomenon. Additionally, [(cAAC)2Pd/Pt] complexes can be quasi‐reversibly oxidized to their corresponding [(cAAC)2Pd/Pt]+ cations, as evidenced by cyclic voltammetry measurements. The bonding and stability are studied by theoretical calculations. 相似文献
8.
In view of the isosterism of the sulfonyl group(‐SO2‐) and the phosphoryl group, two new types of compounds N‐(N‐aryl‐O‐alkyl phosphoryl)‐N′‐(4,6‐dimethoxypyrimidin‐2‐yl) ureas (2) and N‐(N‐aryl‐N‐alkylphosphoryl)‐N′‐(4,6‐dimethoxypyrimidin‐2‐yl) ureas (3) were designed and synthesized by treating N‐(arylaminochlorophosphoryl)‐N′‐(4,6‐dimethoxypy‐rimidinyl‐2‐) ureas (4) with alcohols or amines. Compounds 4 were obtained by treating dichloro‐phosphoryl isocyanate with 4,6‐dimethoxy‐2‐amino‐pyrimidine and then with aromatic amines. The enzyme tests in vitro indicated that compounds 2 and 3 were two novel classes of acetolactate synthase (ALS) inhibitors and also showed that phosphoryl groups[‐P(O)(OR)‐, R=alkyl] and [‐P(O)(NHR), R=alkyl] were likely to be good bioisosteres of the sulfonyl group (‐SO2‐) in the sulfonylureas. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10:237–241, 1999 相似文献
9.
The water‐soluble phosphine ligands, 1,3,5‐triaza‐7‐phosphatricyclo[3.3.1.13,7]decane (tpa) and 1‐alkyl‐1‐azonia‐3,5‐diaza‐7‐phosphatricyclo[3.3.1.13,7]decane iodides (Rtpa+I−), with alkyl=methyl(mtpa+I−), ethyl (etpa+I−) and n‐propyl, (ptpa+I−), and mtpa+Cl− react with [Rh2Cl2(CO)4] giving the rhodium(I) complexes [RhCl(CO)(tpa)2], [RhI(CO)(Rtpa+I−)2], [RhCl‐(CO)(mtpa+Cl−)3] and [RhI(CO)(Rtpa+I−)3]. The properties and reactivities of the complexes have been investigated using 1H and 31PNMR and IR spectroscopies. The five‐coordinate complexes in solutions show dynamic properties. The complexes are catalysts of the water‐gas shift reaction, the hydrogenation of CC and CO bonds, the hydroformylation of alkenes and the isomerization of unsaturated compounds. Copyright © 1999 John Wiley & Sons, Ltd. 相似文献
10.
Rhodium‐catalyzed transfer hydrogenation with aminophosphines and analysis of electrical characteristics of rhodium(I) complex/n‐Si heterojunctions
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Murat Aydemir Yusuf Selim Ocak Khadichakhan Rafikova Nurzhamal Kystaubayeva Cezmi Kayan Alexey Zazybin Fatih Ok Akın Baysal Hamdi Temel 《应用有机金属化学》2014,28(6):396-404
A series of novel neutral mononuclear rhodium(I) complexes of the P―NH ligands have been prepared starting from [Rh(cod)Cl]2 complex. Structural elucidation of the complexes was carried out by elemental analysis, IR and multinuclear NMR spectroscopic data. The complexes were applied to the transfer hydrogenation of acetophenone derivatives to 1‐phenylethanol derivatives in the presence of 2‐propanol as the hydrogen source. Catalytic studies showed that all complexes are also excellent catalyst precursors for transfer hydrogenation of aryl alkyl ketones in 0.1 m iso‐PrOH solution. In particular, [Rh(cod)(PPh2NH―C6H4―4‐CH(CH3)2)Cl] acts as an excellent catalyst, giving the corresponding alcohols in excellent conversion up to 99% (turnover frequency ≤ 588 h?1). Furthermore, rhodium(I) complexes have been used in the formation of organic–inorganic heterojunction by forming their thin films on n‐Si and evaporating Au on the films. It has been seen that the structures have rectifying properties. Their electrical properties have been analyzed with the help of current–voltage measurements. Finally, it has been shown that the complexes can be used in the fabrication of temperature and light sensors. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
11.
Serenella Medici Marcella Gagliardo ScottB. Williams PrestonA. Chase Serafino Gladiali Martin Lutz AnthonyL. Spek GerardP.M. vanKlink Gerard vanKoten 《Helvetica chimica acta》2005,88(3):694-705
Achiral P‐donor pincer‐aryl ruthenium complexes ([RuCl(PCP)(PPh3)]) 4c , d were synthesized via transcyclometalation reactions by mixing equivalent amounts of [1,3‐phenylenebis(methylene)]bis[diisopropylphosphine] ( 2c ) or [1,3‐phenylenebis(methylene)]bis[diphenylphosphine] ( 2d ) and the N‐donor pincer‐aryl complex [RuCl{2,6‐(Me2NCH2)2C6H3}(PPh3)], ( 3 ; Scheme 2). The same synthetic procedure was successfully applied for the preparation of novel chiral P‐donor pincer‐aryl ruthenium complexes [RuCl(P*CP*)(PPh3)] 4a , b by reacting P‐stereogenic pincer‐arenes (S,S)‐[1,3‐phenylenebis(methylene)]bis[(alkyl)(phenyl)phosphines] 2a , b (alkyl=iPr or tBu, P*CHP*) and the complex [RuCl{2,6‐(Me2NCH2)2C6H3}(PPh3)], ( 3 ; Scheme 3). The crystal structures of achiral [RuCl(equation/tex2gif-sup-3.gifPCP)(PPh3)] 4c and of chiral (S,S)‐[RuCl(equation/tex2gif-sup-6.gifPCP)(PPh3)] 4a were determined by X‐ray diffraction (Fig. 3). Achiral [RuCl(PCP)(PPh3)] complexes and chiral [RuCl(P*CP*)(PPh3)] complexes were tested as catalyst in the H‐transfer reduction of acetophenone with propan‐2‐ol. With the chiral complexes, a modest enantioselectivity was obtained. 相似文献
12.
L3C3P3: Tricarbontriphosphide Tricyclic Radicals and Cations Stabilized by Cyclic (alkyl)(amino)carbenes
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Dr. Zhongshu Li Yuanfeng Hou Yaqi Li Dr. Alexander Hinz Prof. Dr. Jeffrey R. Harmer Prof. Dr. Cheng‐Yong Su Prof. Dr. Guy Bertrand Prof. Dr. Hansjörg Grützmacher 《Angewandte Chemie (International ed. in English)》2018,57(1):198-202
Alkynes usually oligomerize to give rings with a conjugated π‐electron system. In contrast, phosphaalkynes, R?C≡P, frequently give compounds with polycyclic structures, which are thermodynamically more stable than the corresponding π‐conjugated isomers. The syntheses of the first C3P3 tricyclic compounds are reported with either radical or cationic ground states stabilized by cyclic (alkyl)(amino)carbenes (CAACs). These compounds may be considered as examples of tricarbontriphosphide coordinated by carbenes and are likely formed via trimerization of the corresponding mono‐radicals CAAC‐CP.. The mechanism for the formation of these tricarbontriphosphide radicals has been rationalized by a combination of experiments and DFT calculations. 相似文献
13.
C‐Selective and Diastereoselective Alkyl Addition to β,γ‐Alkynyl‐α‐imino Esters with Zinc(II)ate Complexes
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Dr. Manabu Hatano Kenji Yamashita Mai Mizuno Orie Ito Prof. Dr. Kazuaki Ishihara 《Angewandte Chemie (International ed. in English)》2015,54(9):2707-2711
Since umpolung α‐imino esters contain three electrophilic centers, regioselective alkyl addition with traditional organometallic reagents has been a serious problem in the practical synthesis of versatile chiral α‐amino acid derivatives. An unusual C‐alkyl addition to α‐imino esters using a Grignard reagent (RMgX)‐derived zinc(II)ate was developed. Zinc(II)ate complexes consist of a Lewis acidic [MgX]+ moiety, a nucleophilic [R3Zn]? moiety, and 2 [MgX2]. Therefore, the ionically separated [R3Zn]? selectively attacks the imino carbon atom ,which is most strongly activated by chelation of [MgX]+. In particular, chiral β,γ‐alkynyl‐α‐imino esters can strongly promote highly regio‐ and diastereoselective C‐alkylation because of structural considerations, and the corresponding optically active α‐quaternary amino acid derivatives are obtained within 5 minutes in high to excellent yields. 相似文献
14.
Guido D. Frey Rian D. Dewhurst Shazia Kousar Bruno Donnadieu Guy Bertrand 《Journal of organometallic chemistry》2008,693(8-9):1674-1682
A series of mono- and dicarbene gold(I) complexes of types Au(CAAC)(Cl) [CAAC = cyclic (alkyl)(amino)carbene] (1) and [Au(CAAC)2]+[X]? (X = Cl, AuCl2) (2) have been prepared through reaction of AuCl(SMe2) with free carbenes a–e, and structurally characterized by single X-ray diffraction studies (1a, 1b, 2d, 2e). In addition two new free cyclic (alkyl)(amino)carbenes (c and e) have been synthesized. 相似文献
15.
Elmira Ghabraie Morteza Bararjanian Saeed Balalaie Frank Rominger Hamid Reza Bijanzadeh 《Helvetica chimica acta》2011,94(8):1440-1447
The Michael‐type addition of a 4‐hydroxycoumarin (=4‐hydroxy‐2H‐1‐benzopyran‐2‐one) 1 to a β‐nitrostyrene (=(2‐nitroethenyl)benzene) 2 in the presence of AcONH4 leads to substituted (3E)‐3‐[amino(aryl)methylidene]chroman‐2,4‐diones (=(3E)‐3‐[amino(aryl)methylene]‐2H‐1‐benzopyran‐2,4(3H)‐diones) 4 (Table 1). High yields, short reaction time, and easy workup are advantages of this novel one‐pot three‐component reaction. 相似文献
16.
Studies on [PtCl2]‐ or [AuCl]‐Catalyzed Cyclization of 1‐(Indol‐2‐yl)‐2,3‐Allenols: The Effects of Water/Steric Hindrance and 1,2‐Migration Selectivity
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Youai Qiu Prof. Dr. Chunling Fu Prof. Dr. Xue Zhang Prof. Dr. Shengming Ma 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(33):10314-10322
The [PtCl2]‐ or [AuCl]‐catalyzed reaction of 1‐(indol‐2‐yl)‐2,3‐allenols occurred smoothly at room temperature to afford a series of poly‐substituted carbazoles efficiently. Compared with the [PtCl2]‐catalyzed process, the [AuCl]‐catalyzed reaction represents a significant advance in terms of the scope and the selectivity. Selective 1,2‐alkyl or aryl migration of the gold carbene intermediate was observed: compared with the methyl group, the isopropyl, cyclopropyl, cyclobutyl, and cyclohexyl groups migrate exclusively; the cyclopropyl group shifts selectively over the ethyl group; the 1,2‐migration of a non‐methyl linear alkyl is faster than methyl group; the phenyl group migrates exclusively over methyl or ethyl group. DFT calculations show that water makes the elimination of H2O facile requiring a much lower energy and validates the migratory preferences of different alkyl or phenyl groups observed. 相似文献
17.
《Journal of heterocyclic chemistry》2017,54(2):1199-1209
By reaction with sodium ethoxide and as a function of their structures, 2‐[(1‐alkyl(aryl)‐4‐cyano‐6,7‐dihydro‐5H‐cyclopenta[c ]pyridin‐3‐yl)oxy]acetamides 11 gave 1‐amino‐5‐alkyl(aryl)‐7,8‐dihydro‐6H‐cyclopenta[d ]furo[2,3‐b ]pyridine‐2‐carboxamides 10 and/or 1‐alkyl(aryl)‐3‐amino‐6,7‐dihydro‐5H‐cyclopenta[c ]pyridine‐4‐carbonitriles 12 . 相似文献
18.
The new N‐heterocyclic carbene (NHC) precursors 4, ‐dicyano‐1, ‐dimesityl‐ ( 9 ) and 4, 5‐dicyano‐1, 3‐dineopentyl‐2‐(pentafluorophenyl)imidazoline ( 14 ) were synthesized. The structure of 9 could be determined by X‐ray crystallography. With the 2‐pentafluorophenyl‐substituted imidazolines 9 and 14 , the [AgCl(NHC)], [RhCl(COD)(NHC)], and [RhCl(CO)2(NHC)] complexes [NHC = 4, 5‐dicyano‐1, 3‐dimesitylimidazol‐2‐ylidene ( 3 ) and 4, 5‐dicyano‐1, 3‐dineopentylimidazol‐2‐ylidene ( 4 )] were obtained. Crystal structures of [AgCl( 3 )] ( 15 ), [RhCl(COD)( 3 )] ( 17 ), [RhCl(COD)( 4 )] ( 18 ), and [RhCl(CO)2( 3 )] ( 19 ) were solved and with the crystal data of 19 , the percent buried volume ( %Vbur) of 31.8(±0.1) % was determined for NHC 3 . Infrared spectra of the imidazolines 9 and 14 and of the complexes 15 – 20 were recorded and the CO stretching frequencies of complexes 19 and 20 were used to determine the Tolman electronic parameters of the newly obtained NHCs 3 (TEP: 2060 cm–1) and 4 (TEP: 2061 cm–1), thus proving that 1, 3‐substitution of maleonitrile‐NHCs does not have a significant effect for the high π‐acceptor strength of these carbenes. 相似文献
19.
Correlations and Contrasts in Homo‐ and Heteroleptic Cyclic (Alkyl)(amino)carbene‐Containing Pt0 Complexes
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Nicole Arnold Prof. Dr. Holger Braunschweig Dr. Peter B. Brenner Dr. Mehmet Ali Celik Dr. Rian D. Dewhurst Dr. Martin Haehnel Dr. Thomas Kramer Dr. Ivo Krummenacher Prof. Dr. Todd B. Marder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(35):12357-12362
An improved synthetic route to homoleptic complex [Pt(CAACMe)2] (CAAC=cyclic (alkyl)(amino)carbenes) and convenient routes to new heteroleptic complexes of the form [Pt(CAACMe)(PR3)] are presented. Although the homoleptic complex was found to be inert to many reagents, oxidative addition and metal‐only Lewis pair (MOLP) formation was observed from one of the heteroleptic complexes. The spectroscopic, structural, and electrochemical properties of the zero‐valent complexes were explored in concert with density functional theory (DFT) and time‐dependent density functional theory (TD‐DFT) calculations. The homoleptic [Pt(CAAC)2] and heteroleptic [Pt(CAAC)(PR3)] complexes were found to be similar in their spectroscopic and structural properties, but their electrochemical behavior and reactivity differ greatly. The unusually strong color of the CAAC‐containing Pt0 complexes was investigated by TD‐DFT calculations and attributed to excitations into the LUMOs of the complexes, which are predominantly composed of bonding π interactions between Pt and the CAAC carbon atoms. 相似文献
20.
Cristina Tejel Dr. M. Pilar del Río Dr. Miguel A. Ciriano Prof. Dr. Eduard J. Reijerse Dr. František Hartl Prof. Stanislav Záliš Dr. Dennis G. H. Hetterscheid Dr. Nearchos Tsichlis i Spithas Bas de Bruin Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(44):11878-11889
Treatment of [Ir(bpa)(cod)]+ complex [ 1 ]+ with a strong base (e.g., tBuO?) led to unexpected double deprotonation to form the anionic [Ir(bpa?2H)(cod)]? species [ 3 ]?, via the mono‐deprotonated neutral amido complex [Ir(bpa?H)(cod)] as an isolable intermediate. A certain degree of aromaticity of the obtained metal–chelate ring may explain the favourable double deprotonation. The rhodium analogue [ 4 ]? was prepared in situ. The new species [M(bpa?2H)(cod)]? (M=Rh, Ir) are best described as two‐electron reduced analogues of the cationic imine complexes [MI(cod)(Py‐CH2‐N?CH‐Py)]+. One‐electron oxidation of [ 3 ]? and [ 4 ]? produced the ligand radical complexes [ 3 ]. and [ 4 ].. Oxygenation of [ 3 ]? with O2 gave the neutral carboxamido complex [Ir(cod)(py‐CH2‐N‐CO‐py)] via the ligand radical complex [ 3 ]. as a detectable intermediate. 相似文献