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1.
Dr. Zhenbo Mo Dr. Takanori Shima Prof. Dr. Zhaomin Hou 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(22):8713-8722
Studies on N2 activation and transformation by transition metal hydride complexes are of particular interest and importance. The synthesis and diverse transformations of a dinitrogen dititanium hydride complex bearing the rigid acridane-based acriPNP-pincer ligands {[(acriPNP)Ti]2(μ2-η1:η2-N2)(μ2-H)2} are presented. This complex enabled N2 cleavage and hydrogenation even without additional H2 or other reducing agents. Furthermore, diverse transformations of the N2 unit with a variety of organometallic compounds such as ZnMe2, MgMe2, AlMe3, B(C6F5)3, PinBH, and PhSiH3 have been well established at the rigid acriPNP-ligated dititanium framework, such as reversible bonding-mode change between the end-on and side-on/end-on fashions, diborylative N=N bond cleavage, the formal insertion of two dimethylaluminum species into the N=N bond, and the formal insertion of two silylene units into the N=N bond. This work has revealed many unprecedented aspects of dinitrogen reaction chemistry. 相似文献
2.
3.
The Unexpected Mechanism Underlying the High‐Valent Mono‐Oxo‐Rhenium(V) Hydride Catalyzed Hydrosilylation of CN Functionalities: Insights from a DFT Study
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In this study, we theoretically investigated the mechanism underlying the high‐valent mono‐oxo‐rhenium(V) hydride Re(O)HCl2(PPh3)2 ( 1 ) catalyzed hydrosilylation of C?N functionalities. Our results suggest that an ionic SN2‐Si outer‐sphere pathway involving the heterolytic cleavage of the Si?H bond competes with the hydride pathway involving the C?N bond inserted into the Re?H bond for the rhenium hydride ( 1 ) catalyzed hydrosilylation of the less steric C?N functionalities (phenylmethanimine, PhCH=NH, and N‐phenylbenzylideneimine, PhCH=NPh). The rate‐determining free‐energy barriers for the ionic outer‐sphere pathway are calculated to be ~28.1 and 27.6 kcal mol?1, respectively. These values are slightly more favorable than those obtained for the hydride pathway (by ~1–3 kcal mol?1), whereas for the large steric C?N functionality of N,1,1‐tri(phenyl)methanimine (PhCPh=NPh), the ionic outer‐sphere pathway (33.1 kcal mol?1) is more favorable than the hydride pathway by as much as 11.5 kcal mol?1. Along the ionic outer‐sphere pathway, neither the multiply bonded oxo ligand nor the inherent hydride moiety participate in the activation of the Si?H bond. 相似文献
4.
Dr. Shaoguang Zhang Dr. Haixia Li Dr. Aaron M. Appel Prof. Michael B. Hall Dr. R. Morris Bullock 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(28):9493-9497
Unusual cleavage of P?C and C?H bonds of the P2N2 ligand, in heteroleptic [Ni(P2N2)(diphosphine)]2+ complexes under mild conditions, results in the formation of an iminium formyl nickelate featuring a C,P,P‐tridentate coordination mode. The structures of both the heteroleptic [Ni(P2N2)(diphosphine)]2+ complexes and the resulting iminium formyl nickelate have been characterized by NMR spectroscopy and single‐crystal X‐ray diffraction analysis. Density functional theory (DFT) calculations were employed to investigate the mechanism of the P?C/C?H bond cleavage, which involves C?H bond cleavage, hydride rotation, Ni?C/P?H bond formation, and P?C bond cleavage. 相似文献
5.
Shoi Suzuki Yutaka Ishida Hajime Kameo Shigeyoshi Sakaki Hiroyuki Kawaguchi 《Angewandte Chemie (International ed. in English)》2020,59(32):13444-13450
We report the synthesis of anionic diniobium hydride complexes with a series of alkali metal cations (Li+, Na+, and K+) and the counterion dependence of their reactivity with N2. Exposure of these complexes to N2 initially produces the corresponding side‐on end‐on N2 complexes, the fate of which depends on the nature of countercations. The lithium derivative undergoes stepwise migratory insertion of the hydride ligands onto the aryloxide units, yielding the end‐on bridging N2 complex. For the potassium derivative, the N?N bond cleavage takes place along with H2 elimination to form the nitride complex. Treatment of the side‐on end‐on N2 complex with Me3SiCl results in silylation of the terminal N atom and subsequent N?N bond cleavage along with H2 elimination, giving the nitride‐imide‐bridged diniobium complex. 相似文献
6.
Photochemically Induced Reductive Elimination as a Route to a Zirconocene Complex with a Strongly Activated N2 Ligand
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Grant W. Margulieux Scott P. Semproni Prof. Dr. Paul J. Chirik 《Angewandte Chemie (International ed. in English)》2014,53(35):9189-9192
The zirconocene dinitrogen complex [{(η5‐C5Me4H)2Zr}2(μ2,η2,η2‐N2)] was synthesized by photochemical reductive elimination from the corresponding zirconium bis(aryl) or aryl hydride complexes, providing a high‐yielding, alkali metal‐free route to strongly activated early‐metal N2 complexes. Mechanistic studies support the intermediacy of zirconocene arene complexes that in the absence of sufficient dinitrogen promote C? H activation or undergo comproportion to formally ZrIII complexes. When N2 is in excess arene displacement gives rise to strong dinitrogen activation. 相似文献
7.
On the Electronic Structure and Photochemistry of Coordinatively Unsaturated Complexes: The Case of Nickel Bis‐dinitrogen,Ni(N2)2
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Dr. Olaf Hübner Dr. Laurent Manceron Prof. Hans‐Jörg Himmel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(51):17025-17038
The electronic ground and excited states of the coordinatively unsaturated complex Ni(η1‐N2)2, isolated in an Ar matrix, are analyzed in detail by vibrational and electronic absorption and emission spectroscopies allied with quantum chemical calculations. The bond force constants are determined from a normal coordinate analysis and compared with those of the isoelectronic carbonyl complex. The consequences for the bond properties are discussed, and the trend in the force constants is compared with the standard formation enthalpies. The linear complex Ni(η1‐N2)2 with two terminal dinitrogen ligands can be photoisomerized to two isomeric, metastable forms Ni(η1‐N2)(η2‐N2) and Ni(η2‐N2)2, with one and two side‐on coordinated dinitrogen ligands, respectively. 相似文献
8.
Dihydrogen Catalysis of the Reversible Formation and Cleavage of CH and NH Bonds of Aminopyridinate Ligands Bound to (η5‐C5Me5)IrIII
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Dr. Ana Zamorano Dr. Nuria Rendón Dr. Joaquín López‐Serrano Dr. José E. V. Valpuesta Dr. Eleuterio Álvarez Prof. Dr. Ernesto Carmona 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2576-2587
This study focuses on a series of cationic complexes of iridium that contain aminopyridinate (Ap) ligands bound to an (η5‐C5Me5)IrIII fragment. The new complexes have the chemical composition [Ir(Ap)(η5‐C5Me5)]+, exist in the form of two isomers ( 1+ and 2+ ) and were isolated as salts of the BArF? anion (BArF=B[3,5‐(CF3)2C6H3]4). Four Ap ligands that differ in the nature of their bulky aryl substituents at the amido nitrogen atom and pyridinic ring were employed. In the presence of H2, the electrophilicity of the IrIII centre of these complexes allows for a reversible prototropic rearrangement that changes the nature and coordination mode of the aminopyridinate ligand between the well‐known κ2‐N,N′‐bidentate binding in 1+ and the unprecedented κ‐N,η3‐pseudo‐allyl‐coordination mode in isomers 2+ through activation of a benzylic C?H bond and formal proton transfer to the amido nitrogen atom. Experimental and computational studies evidence that the overall rearrangement, which entails reversible formation and cleavage of H?H, C?H and N?H bonds, is catalysed by dihydrogen under homogeneous conditions. 相似文献
9.
Activation of Molecular Hydrogen by Bis(η5,η1‐pentafulvene)‐titanium Complexes – Efficient Formation of Titanium(III)hydrides
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The synthesis and crystal structures of two dinuclear titanocene hydride complexes are reported. Both complexes, namely bis(η5‐(di‐para‐tolylmethyl)cyclopentadienyl)titanium hydride dimer, [(η5‐C20H19)2Ti(μ‐H)]2 ( 2a ), and bis(η5‐2‐adamantylcyclopentadienyl)‐titanium hydride dimer, [(η5‐C15H19)2Ti(μ‐H)]2 ( 2b ), are formed via activation of molecular hydrogen by the corresponding bis(η5,η1‐pentafulvene)titanium complexes 1a and 1b at ambient temperatures and pressures in high yields. The hydride complexes 2a and 2b exhibit planar [Ti2H2] cores and, as a result of the heterolytic cleavage of molecular hydrogen, substituted Cp Ligands were formed during the reaction. 相似文献
10.
3‐Rhoda‐1,2‐diazacyclopentanes: A Series of Novel Metallacycle Complexes Derived From CN Functionalization of Ethylene
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Marcus W. Drover Daniel W. Beh Prof. Dr. Pierre Kennepohl Prof. Dr. Jennifer A. Love 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(41):13345-13355
Rh‐containing metallacycles, [(TPA)RhIII(κ2‐(C,N)‐CH2CH2(NR)2‐]Cl; TPA=N,N,N,N‐tris(2‐pyridylmethyl)amine have been accessed through treatment of the RhI ethylene complex, [(TPA)Rh(η2‐CH2CH2)]Cl ([ 1 ]Cl) with substituted diazenes. We show this methodology to be tolerant of electron‐deficient azo compounds including azo diesters (RCO2N?NCO2R; R=Et [ 3 ]Cl, R=iPr [ 4 ]Cl, R=tBu [ 5 ]Cl, and R=Bn [ 6 ]Cl) and a cyclic azo diamide: 4‐phenyl‐1,2,4‐triazole‐3,5‐dione (PTAD), [ 7 ]Cl. The latter complex features two ortho‐fused ring systems and constitutes the first 3‐rhoda‐1,2‐diazabicyclo[3.3.0]octane. Preliminary evidence suggests that these complexes result from N–N coordination followed by insertion of ethylene into a [Rh]?N bond. In terms of reactivity, [ 3 ]Cl and [ 4 ]Cl successfully undergo ring‐opening using p‐toluenesulfonic acid, affording the Rh chlorides, [(TPA)RhIII(Cl)(κ1‐(C)‐CH2CH2(NCO2R)(NHCO2R)]OTs; [ 13 ]OTs and [ 14 ]OTs. Deprotection of [ 5 ]Cl using trifluoroacetic acid was also found to give an ethyl substituted, end‐on coordinated diazene [(TPA)RhIII(κ2‐(C,N)‐CH2CH2(NH)2‐]+ [ 16 ]Cl, a hitherto unreported motif. Treatment of [ 16 ]Cl with acetyl chloride resulted in the bisacetylated adduct [(TPA)RhIII(κ2‐(C,N)‐CH2CH2(NAc)2‐]+, [ 17 ]Cl. Treatment of [ 1 ]Cl with AcN?NAc did not give the Rh?N insertion product, but instead the N,O‐chelated complex [(TPA)RhI ( κ2‐(O,N)‐CH3(CO)(NH)(N?C(CH3)(OCH?CH2))]Cl [ 23 ]Cl, presumably through insertion of ethylene into a [Rh]?O bond. 相似文献
11.
Johan Vibenholt Magnus Magnussen Christian Anthon Jesper Bendix 《Acta Crystallographica. Section C, Structural Chemistry》2010,66(7):m177-m179
Five‐coordinate Cr(N)(salen) {salen is 2,2′‐[ethane‐1,2‐diylbis(nitrilomethylidyne)]diphenolate} reacts with [RhCl(COD)]2 (COD is 1,5‐cyclooctadiene) to yield the heterobimetallic nitride‐bridged title compound, namely chlorido‐2κCl‐[2(η4)‐1,5‐cyclooctadiene]{2,2′‐[ethane‐1,2‐diylbis(nitrilomethylidyne)]diphenolato‐1κ4O,N,N′,O′}‐μ‐nitrido‐1:2κ2N:N‐chromium(V)rhodium(I), [CrRh(C16H14N2O2)ClN(C8H12)]. The Cr—N bond of 1.5936 (14) Å is elongated by only 0.035 Å compared to the terminal Cr—N bond in the precursor. The nitride bridge is close to being linear [173.03 (9)°] and the Rh—N bond of 1.9594 (14) Å is very short for a monodentate nitrogen‐donor ligand, indicating significant π‐acceptor character of the Cr[triple‐bond]N group. 相似文献
12.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2018,130(7):1996-1999
The zirconium methylidene (PNP)Zr=CH2(OAr) ( 1 ) reacts with N3Ad to give two products (PNP)Zr=NAd(OAr) ( 2 ) and (PNP)Zr(η2‐N=NAd)(N=CH2)(OAr) ( 3 ), both resulting from a common cycloaddition intermediate (PNP)Zr(CH2N3Ad)(OAr) ( A ). Using a series of control experiments in combination with DFT calculations, it was found that 2 results from a nitrene by a carbene metathesis reaction in which N2 acts as a delivery vehicle and forms N2CH2 as a side product. In the case of 3 , N−N bond splitting of the azide at the α‐position allowed the isolation of a rare example of a parent ketimide complex of zirconium. Isotopic labeling studies and solid‐state X‐ray analysis are presented for 2 and 3 , in addition to an independent synthesis for the former. 相似文献
13.
Synthesis and Ligand Modification Chemistry of a Molybdenum Dinitrogen Complex: Redox and Chemical Activity of a Bis(imino)pyridine Ligand
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Grant W. Margulieux Zoë R. Turner Prof. Paul J. Chirik 《Angewandte Chemie (International ed. in English)》2014,53(51):14211-14215
The bis(imino)pyridine 2,6‐(2,6‐iPr2‐C6H3N?CPh)2‐C5H3N (iPrBPDI) molybdenum dinitrogen complex, [{(iPrBPDI)Mo(N2)}2(μ2,η1,η1‐N2)] has been prepared and contains both weakly (terminal) and modestly (bridging) activated N2 ligands. Addition of ammonia resulted in sequential N? H bond activations, thus forming bridging parent imido (μ‐NH) ligands with concomitant reduction of one of the imines of the supporting chelate. Using primary and secondary amines, model intermediates have been isolated that highlight the role of metal–ligand cooperativity in NH3 oxidation. 相似文献
14.
Reactivity of TpMe2‐Supported Yttrium Alkyl Complexes toward Aromatic N‐Heterocycles: Ring‐Opening or CC Bond Formation Directed by CH Activation
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Dr. Weiyin Yi Prof. Dr. Jie Zhang Shujian Huang Prof. Dr. Linhong Weng Prof. Dr. Xigeng Zhou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(3):867-876
Unusual chemical transformations such as three‐component combination and ring‐opening of N‐heterocycles or formation of a carbon–carbon double bond through multiple C–H activation were observed in the reactions of TpMe2‐supported yttrium alkyl complexes with aromatic N‐heterocycles. The scorpionate‐anchored yttrium dialkyl complex [TpMe2Y(CH2Ph)2(THF)] reacted with 1‐methylimidazole in 1:2 molar ratio to give a rare hexanuclear 24‐membered rare‐earth metallomacrocyclic compound [TpMe2Y(μ‐N,C‐Im)(η2‐N,C‐Im)]6 ( 1 ; Im=1‐methylimidazolyl) through two kinds of C–H activations at the C2‐ and C5‐positions of the imidazole ring. However, [TpMe2Y(CH2Ph)2(THF)] reacted with two equivalents of 1‐methylbenzimidazole to afford a C–C coupling/ring‐opening/C–C coupling product [TpMe2Y{η3‐(N,N,N)‐N(CH3)C6H4NHCH?C(Ph)CN(CH3)C6H4NH}] ( 2 ). Further investigations indicated that [TpMe2Y(CH2Ph)2(THF)] reacted with benzothiazole in 1:1 or 1:2 molar ratio to produce a C–C coupling/ring‐opening product {(TpMe2)Y[μ‐η2:η1‐SC6H4N(CH?CHPh)](THF)}2 ( 3 ). Moreover, the mixed TpMe2/Cp yttrium monoalkyl complex [(TpMe2)CpYCH2Ph(THF)] reacted with two equivalents of 1‐methylimidazole in THF at room temperature to afford a trinuclear yttrium complex [TpMe2CpY(μ‐N,C‐Im)]3 ( 5 ), whereas when the above reaction was carried out at 55 °C for two days, two structurally characterized metal complexes [TpMe2Y(Im‐TpMe2)] ( 7 ; Im‐TpMe2=1‐methyl‐imidazolyl‐TpMe2) and [Cp3Y(HIm)] ( 8 ; HIm=1‐methylimidazole) were obtained in 26 and 17 % isolated yields, respectively, accompanied by some unidentified materials. The formation of 7 reveals an uncommon example of construction of a C?C bond through multiple C–H activations. 相似文献
15.
Defect Engineering Metal‐Free Polymeric Carbon Nitride Electrocatalyst for Effective Nitrogen Fixation under Ambient Conditions
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Chade Lv Yumin Qian Chunshuang Yan Yu Ding Prof. Yuanyue Liu Prof. Gang Chen Prof. Guihua Yu 《Angewandte Chemie (International ed. in English)》2018,57(32):10246-10250
Electrocatalytic nitrogen reduction reaction (NRR) under ambient conditions provides an intriguing picture for the conversion of N2 into NH3. However, electrocatalytic NRR mainly relies on metal‐based catalysts, and it remains a grand challenge in enabling effective N2 activation on metal‐free catalysts. Here we report a defect engineering strategy to realize effective NRR performance (NH3 yield: 8.09 μg h?1 mg?1cat., Faradaic efficiency: 11.59 %) on metal‐free polymeric carbon nitride (PCN) catalyst. Illustrated by density functional theory calculations, dinitrogen molecule can be chemisorbed on as‐engineered nitrogen vacancies of PCN through constructing a dinuclear end‐on bound structure for spatial electron transfer. Furthermore, the N?N bond length of adsorbed N2 increases dramatically, which corresponds to “strong activation” system to reduce N2 into NH3. This work also highlights the significance of defect engineering for improving electrocatalysts with weak N2 adsorption and activation ability. 相似文献
16.
Guohai Deng Dr. Sudip Pan Xuelin Dong Prof. Dr. Guanjun Wang Prof. Dr. Lili Zhao Prof. Dr. Mingfei Zhou Prof. Gernot Frenking 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(6):2131-2137
The boron atoms react with carbon monoxide and dinitrogen forming the end-on bonded NNBCO complex in solid neon or in nitrogen matrices. The NNBCO complex rearranges to the (η2-N2)BCO isomer with a more activated side-on bonded dinitrogen ligand upon visible light excitation. (η2-N2)BCO and its weakly CO-coordinated complexes further isomerize to the NBNCO and B(NCO)2 molecules with N−N bond being completely cleaved under UV light irradiation. The geometries, energies and vibrational spectra of the molecules are calculated with quantum chemical methods and the electronic structures are analyzed with charge- and energy-partitioning methods. 相似文献
17.
Uwe Schmidt Luis Werner Merle Arrowsmith Andrea Deissenberger Alexander Hermann Alexander Hofmann Stefan Ullrich James D. Mattock Alfredo Vargas Holger Braunschweig 《Angewandte Chemie (International ed. in English)》2020,59(1):325-329
The reaction of aryl‐ and amino(dihydro)boranes with dibora[2]ferrocenophane 1 leads to the formation 1,3‐trans‐dihydrotriboranes by formal hydrogenation and insertion of a borylene unit into the B=B bond. The aryltriborane derivatives undergo reversible photoisomerization to the cis‐1,2‐μ‐H‐3‐hydrotriboranes, while hydride abstraction affords cationic triboranes, which represent the first doubly base‐stabilized B3H4+ analogues. 相似文献
18.
Ansa‐Complexes of [Mn(η5‐C5H5)(η6‐C6H6)]: Preparation,Characterization, and Reactivity of [n]Manganoarenophanes (n=1, 2, 3)
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Prof. Dr. Holger Braunschweig Dr. Alexander Damme Dr. Klaus Dück Dr. Marco Fuß Dr. Christian Hörl Dr. Thomas Kramer Dr. Ivo Krummenacher Dr. Thomas Kupfer Valerie Paprocki Christoph Schneider 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(42):14797-14803
We report the synthesis of [n]manganoarenophanes (n=1, 2) featuring boron, silicon, germanium, and tin as ansa‐bridging elements. Their preparation was achieved by salt‐elimination reactions of the dilithiated precursor [Mn(η5‐C5H4Li)(η6‐C6H5Li)]?pmdta (pmdta=N,N,N′,N′,N′′‐pentamethyldiethylenetriamine) with corresponding element dichlorides. Besides characterization by multinuclear NMR spectroscopy and elemental analysis, the identity of two single‐atom‐bridged derivatives, [Mn(η5‐C5H4)(η6‐C6H5)SntBu2] and [Mn(η5‐C5H4)(η6‐C6H5)SiPh2], could also be determined by X‐ray structural analysis. We investigated for the first time the reactivity of these ansa‐cyclopentadienyl–benzene manganese compounds. The reaction of the distannyl‐bridged complex [Mn(η5‐C5H4)(η6‐C6H5)Sn2tBu4] with elemental sulfur was shown to proceed through the expected oxidative addition of the Sn?Sn bond to give a triatomic ansa‐bridge. The investigation of the ring‐opening polymerization (ROP) capability of [Mn(η5‐C5H4)(η6‐C6H5)SntBu2] with [Pt(PEt3)3] showed that an unexpected, unselective insertion into the Cipso?Sn bonds of [Mn(η5‐C5H4)(η6‐C6H5)SntBu2] had occurred. 相似文献
19.
The η2‐thio‐indium complexes [In(η2‐thio)3] (thio = S2CNC5H10, 2 ; SNC4H4, (pyridine‐2‐thionate, pyS, 3 ) and [In(η2‐pyS)2(η2‐acac)], 4 , (acac: acetylacetonate) are prepared by reacting the tris(η2‐acac)indium complex [In(η2‐acac)3], 1 with HS2CNC5H10, pySH, and pySH with ratios of 1:3, 1:3, and 1:2 in dichloromethane at room temperature, respectively. All of these complexes are identified by spectroscopic methods and complexes 2 and 3 are determined by single‐crystal X‐ray diffraction. Crystal data for 2 : space group, C2/c with a = 13.5489(8) Å, b = 12.1821(7) Å, c = 16.0893(10) Å, β = 101.654(1)°, V = 2600.9(3) Å3, and Z = 4. The structure was refined to R = 0.033 and Rw = 0.086; Crystal data for 3 : space group, P21 with a = 8.8064 (6) Å, b = 11.7047 (8) Å, c = 9.4046 (7) Å, β = 114.78 (1)°, V = 880.13(11) Å3, and Z = 2. The structure was refined to R = 0.030 and Rw = 0.061. The geometry around the metal atom of the two complexes is a trigonal prismatic coordination. The piperidinyldithiocarbamate and pyridine‐2‐thionate ligands, respectively, coordinate to the indium metal center through the two sulfur atoms and one sulfur and one nitrogen atoms, respectively. The short C‐N bond length in the range of 1.322(4)–1.381(6) Å in 2 and C‐S bond length in the range of 1.715(2)–1.753(6) Å in 2 and 3 , respectively, indicate considerable partial double bond character. 相似文献
20.
Robin Guthardt Jan Oetzel Julia I. Schweizer Clemens Bruhn Robert Langer Martin Maurer Jan Vícha Pavletta Shestakova Max C. Holthausen Ulrich Siemeling 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(5):1401-1405
The N‐heterocyclic plumbylene [Fe{(η5‐C5H4)NSiMe3}2Pb:] is in equilibrium with an unprecedented dimer in solution, whose formation involves the cleavage of a strong C?H bond and concomitant formation of a Pb?C and an N?H bond. According to a mechanistic DFT assessment, dimer formation does not involve direct PbII insertion into a cyclopentadienyl C?H bond, but is best described as an electrophilic substitution. The bulkier plumbylene [Fe{(η5‐C5H4)NSitBuMe2}2Pb:] shows no dimerization, but compensates its electrophilicity by the formation of an intramolecular Fe?Pb bond. 相似文献