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1.
《应用有机金属化学》2017,31(8)
Treatment of Ru3(CO)12 with an equivalent of (2‐phenyl‐1H ‐inden‐3‐yl)dicyclohexylphosphine ( 1 ) and (2‐pyridyl‐1H ‐inden‐1‐yl)dicyclohexylphosphine ( 4 ) in refluxing heptane gave the novel trinuclear ruthenium clusters (μ3‐η1:η2:η5–2‐phenyl‐3‐Cy2PC9H4)Ru3(CO)8 ( 1c ) and [μ2‐η1–2‐(pyridin‐2‐yl)‐3‐Cy2PC9H6]Ru3(CO)9 ( 4a ), respectively, via C ─ H bond cleavage. (2‐Mesityl‐1H ‐inden‐3‐yl)dicyclohexylphosphine ( 2 ) reacted with Ru3(CO)12 in refluxing heptane to give the trinuclear ruthenium cluster [μ‐2‐mesityl‐(3‐Cy2PC9H5)](μ2‐CO)Ru3(CO)9 ( 2c ) via C ─ H bond cleavage and carbonyl insertion. 2‐(Anthracen‐9‐yl)‐1H –inden‐3‐yldicyclohexylphosphine ( 3 ) reacted with Ru3(CO)12 in refluxing heptane to give the dinuclear ruthenium cluster [μ2‐η3:η3–2‐(anthracen‐9‐yl)‐3‐Cy2PC9H6]Ru2(CO)5 ( 3a ). The structures of 1c , 2c , 3a and 4a were fully characterized using IR and NMR spectroscopy, elemental analysis and single‐crystal X‐ray diffraction. These results suggest that the 2‐aryl substituent on the indenyl ring has a pronounced effect on the reaction and coordination modes of Ru3(CO)12. 相似文献
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Andrew M. Poitras Sadie E. Knight Mark W. Bezpalko Bruce M. Foxman Christine M. Thomas 《Angewandte Chemie (International ed. in English)》2018,57(6):1497-1500
Addition of H2 across the cobalt–phosphorus bond of (PPP)CoPMe3 ( 3 ) is demonstrated, where PPP is a monoanionic diphosphine pincer ligand with a central N‐heterocyclic phosphido (NHP?) donor. The chlorophosphine CoII complex (PPClP)CoCl2 ( 2 ) can be generated through coordination of the chlorophosphine ligand (PPClP, 1 ) to CoCl2. Subsequent reduction of 2 with KC8 in the presence of PMe3 generates (PPP)CoPMe3 ( 3 ), in which both the phosphorus and cobalt centers have been reduced. The addition of 1 atm of H2 to complex 3 cleanly affords (PPHP)Co(H)PMe3 ( 4 ), in which H2 has ultimately been added across the metal–phosphorus bond. Complex 4 was characterized spectroscopically and using computational methods to predict its geometry. 相似文献
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V. S. Kaganovich Z. A. Kerzina M. I. Rybinskaya E. Kolehmainen 《Russian Chemical Bulletin》1995,44(6):1131-1132
The reaction of cluster Ru6C(CO)17 (1) with nickelocene is studied. Five CO ligands rather than a metal-ligand crown are substituted for two cyclopentadienyl groups to give a new complex Ru6C(5-Cp)2(CO)12 (2). The reaction of cluster1 with entamethylcyclopentadiene leads to new complex Ru6C(-15-CH2C5Me4)(CO)14 (3) containing the cr-bond CH2-Ru, along with an 5-coordinated cyclopentadienyl ring.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1171–1172, June, 1995. 相似文献
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Prechtl MH Ben-David Y Giunta D Busch S Taniguchi Y Wisniewski W Görls H Mynott RJ Theyssen N Milstein D Leitner W 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(5):1539-1546
The synthesis and characterisation of nonclassical ruthenium hydride complexes containing bidentate PP and tridentate PCP and PNP pincer-type ligands are described. The mononuclear and dinuclear ruthenium complexes presented have been synthesised in moderate to high yields by the direct hydrogenation route (one-pot synthesis) or in a two-step procedure. In both cases [Ru(cod)(metallyl)(2)] served as a readily available precursor. The influences of the coordination geometry and the ligand framework on the structure, binding, and chemical properties of the M--H(2) fragments were studied by X-ray crystal structure analysis, spectroscopic methods, and reactivity towards N(2), D(2), and deuterated solvents. 相似文献
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Dr. Yuehui Li Tao Yan Dr. Kathrin Junge Prof. Dr. Matthias Beller 《Angewandte Chemie (International ed. in English)》2014,53(39):10476-10480
Formation of C? C bonds from CO2 is a much sought after reaction in organic synthesis. To date, other than C? H carboxylations using stoichiometric amounts of metals, base, or organometallic reagents, little is known about C? C bond formation. In fact, to the best of our knowledge no catalytic methylation of C? H bonds using CO2 and H2 has been reported. Described herein is the combination of CO2 and H2 for efficient methylation of carbon nucleophiles such as indoles, pyrroles, and electron‐rich arenes. Comparison experiments which employ paraformaldehyde show similar reactivity for the CO2/H2 system. 相似文献
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Sellmann D Hille A Rösler A Heinemann FW Moll M Brehm G Schneider S Reiher M Hess BA Bauer W 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(4):819-830
In the quest for low-molecular-weight metal sulfur complexes that bind nitrogenase-relevant small molecules and can serve as model complexes for nitrogenase, compounds with the [Ru(PiPr(3))('N(2)Me(2)S(2)')] fragment were found ('N(2)Me(2)S(2)'(2-)=1,2-ethanediamine-N,N'-dimethyl-N,N'-bis(2-benzenethiolate)(2-)). This fragment enabled the synthesis of a first series of chiral metal sulfur complexes, [Ru(L)(PiPr(3))('N(2)Me(2)S(2)')] with L=N(2), N(2)H(2), N(2)H(4), and NH(3), that meet the biological constraint of forming under mild conditions. The reaction of [Ru(NCCH(3))(PiPr(3))('N(2)Me(2)S(2)')] (1) with NH(3) gave the ammonia complex [Ru(NH(3))(PiPr(3))('N(2)Me(2)S(2)')] (4), which readily exchanged NH(3) for N(2) to yield the mononuclear dinitrogen complex [Ru(N(2))(PiPr(3))('N(2)Me(2)S(2)')] (2) in almost quantitative yield. Complex 2, obtained by this new efficient synthesis, was the starting material for the synthesis of dinuclear (R,R)- and (S,S)-[micro-N(2)[Ru(PiPr(3))('N(2)Me(2)S(2)')](2)] ((R,R)-/(S,S)-3). (Both 2 and 3 have been reported previously.) The as-yet inexplicable behavior of complex 3 to form also the R,S isomer in solution has been revealed by DFT calculations and (2)D NMR spectroscopy studies. The reaction of 1 or 2 with anhydrous hydrazine yielded the hydrazine complex [Ru(N(2)H(4))(PiPr(3))('N(2)Me(2)S(2)')] (6), which is a highly reactive intermediate. Disproportionation of 6 resulted in the formation of mononuclear diazene complexes, the ammonia complex 4, and finally the dinuclear diazene complex [micro-N(2)H(2)[Ru(PiPr(3))('N(2)Me(2)S(2)')](2)] (5). Dinuclear complex 5 could also be obtained directly in an independent synthesis from 1 and N(2)H(2), which was generated in situ by acidolysis of K(2)N(2)(CO(2))(2). Treatment of 6 with CH(2)Cl(2), however, formed a chloromethylated diazene species [[Ru(PiPr(3))('N(2)Me(2)S(2)')]-micro-N(2)H(2)[Ru(Cl)('N(2)Me(2)S(2)CH(2)Cl')]] (9) ('N(2)Me(2)S(2)CH(2)Cl'(2-) =1,2-ethanediamine-N,N'-dimethyl-N-(2-benzenethiolate)(1-)-N'-(2-benzenechloromethylthioether)(1-)]. The molecular structures of 4, 5, and 9 were determined by X-ray crystal structure analysis, and the labile N(2)H(4) complex 6 was characterized by NMR spectroscopy. 相似文献
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Barbaro P Di Vaira M Peruzzini M Seniori Costantini S Stoppioni P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(23):6682-6690
The reaction of [CpRu(PPh(3))(2)Cl] (1) with half an equivalent of P(4) or P(4)S(3) in the presence of AgCF(3)SO(3) as chloride scavenger affords the stable dimetal complexes [{CpRu(PPh(3))(2)}(2)(micro,eta(1:1)-P(4))][CF(3)SO(3)](2).3 CH(2)Cl(2) (2) and [{CpRu(PPh(3))(2)}(2)(micro,eta(1:1)-P(apical)-P(basal)-P(4)S(3))][CF(3)SO(3)](2).0.5 C(7)H(8) (3), in which the tetrahedral P(4) and mixed-cage P(4)S(3) molecules are respectively bound to two CpRu(PPh(3))(2) fragments through two phosphorus atoms. The coordinated cage molecules, at variance with the free ligands, readily react with an excess of water in THF under mild conditions. Among the hydrolysis products, the new, remarkably stable complexes [{CpRu(PPh(3))(2)}(2)(micro,eta(1:1)-P(2)H(4))][CF(3)SO(3)](2) (4) and [CpRu(PPh(3))(2)(eta(1)-PH(2)SH)]CF(3)SO(3) (8) were isolated. In the former, diphosphane, P(2)H(4), is coordinated to two CpRu(PPh(3))(2) fragments, and in the latter thiophosphinous acid, H(2)PSH, is coordinated to the metal centre through the phosphorus atom. All compounds were characterised by elemental analyses and IR and NMR spectroscopy. The crystal structures of 2, 3, 4 and 8 were determined by X-ray diffraction. 相似文献
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Rankin MA McDonald R Ferguson MJ Stradiotto M 《Angewandte Chemie (International ed. in English)》2005,44(23):3603-3606
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H2 Oxidation Electrocatalysis Enabled by Metal‐to‐Metal Hydrogen Atom Transfer: A Homolytic Approach to a Heterolytic Reaction
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Dr. Geoffrey M. Chambers Dr. Eric S. Wiedner Dr. R. Morris Bullock 《Angewandte Chemie (International ed. in English)》2018,57(41):13523-13527
Oxidation of H2 in a fuel cell converts the chemical energy of the H?H bond into electricity. Electrocatalytic oxidation of H2 by molecular catalysts typically requires one metal to perform multiple chemical steps: bind H2, heterolytically cleave H2, and then undergo two oxidation and two deprotonation steps. The electrocatalytic oxidation of H2 by a cooperative system using Cp*Cr(CO)3H and [Fe(diphosphine)(CO)3]+ has now been invetigated. A key step of the proposed mechanism is a rarely observed metal‐to‐metal hydrogen atom transfer from the Cr?H complex to the Fe, forming an Fe?H complex that is deprotonated and then oxidized electrochemically. This “division of chemical labor” features Cr interacting with H2 to cleave the H?H bond, while Fe interfaces with the electrode. Neither metal is required to heterolytically cleave H2, so this system provides a very unusual example of a homolytic reaction being a key step in a molecular electrocatalytic process. 相似文献
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Sellmann D Hille A Heinemann FW Moll M Reiher M Hess BA Bauer W 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(17):4214-4224
The reactions of [Ru(N2)(PR3)(‘N2Me2S2’)] [‘N2Me2S2’=1,2‐ethanediamine‐N,N′‐dimethyl‐N,N′‐bis(2‐benzenethiolate)(2?)] [ 1 a (R=iPr), 1 b (R=Cy)] and [μ‐N2{Ru(N2)(PiPr3)(‘N2Me2S2’)}2] ( 1 c ) with H2, NaBH4, and NBu4BH4, intended to reduce the N2 ligands, led to substitution of N2 and formation of the new complexes [Ru(H2)(PR3)(‘N2Me2S2’)] [ 2 a (R=iPr), 2 b (R=Cy)], [Ru(BH3)(PR3)(‘N2Me2S2’)] [ 3 a (R=iPr), 3 b (R=Cy)], and [Ru(H)(PR3)(‘N2Me2S2’)]? [ 4 a (R=iPr), 4 b (R=Cy)]. The BH3 and hydride complexes 3 a , 3 b , 4 a , and 4 b were obtained subsequently by rational synthesis from 1 a or 1 b and BH3?THF or LiBEt3H. The primary step in all reactions probably is the dissociation of N2 from the N2 complexes to give coordinatively unsaturated [Ru(PR3)(‘N2Me2S2’)] fragments that add H2, BH4?, BH3, or H?. All complexes were completely characterized by elemental analysis and common spectroscopic methods. The molecular structures of [Ru(H2)(PR3)(‘N2Me2S2’)] [ 2 a (R=iPr), 2 b (R=Cy)], [Ru(BH3)(PiPr3)(‘N2Me2S2’)] ( 3 a ), [Li(THF)2][Ru(H)(PiPr3)(‘N2Me2S2’)] ([Li(THF)2]‐ 4 a ), and NBu4[Ru(H)(PCy3)(‘N2Me2S2’)] (NBu4‐ 4 b ) were determined by X‐ray crystal structure analysis. Measurements of the NMR relaxation time T1 corroborated the η2 bonding mode of the H2 ligands in 2 a (T1=35 ms) and 2 b (T1=21 ms). The H,D coupling constants of the analogous HD complexes HD‐ 2 a (1J(H,D)=26.0 Hz) and HD‐ 2 b (1J(H,D)=25.9 Hz) enabled calculation of the H? D distances, which agreed with the values found by X‐ray crystal structure analysis ( 2 a : 92 pm (X‐ray) versus 98 pm (calculated), 2 b : 99 versus 98 pm). The BH3 entities in 3 a and 3 b bind to one thiolate donor of the [Ru(PR3)(‘N2Me2S2’)] fragment and through a B‐H‐Ru bond to the Ru center. The hydride complex anions 4 a and 4 b are extremely Brønsted basic and are instantanously protonated to give the η2‐H2 complexes 2 a and 2 b . 相似文献
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CH Bond Activation during and after the Reactions of a Metallacyclic Amide with Silanes: Formation of a μ‐Alkylidene Hydride Complex,Its H–D Exchange,and β‐H Abstraction by a Hydride Ligand
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Li Wang Seth C. Hunter Zhimin Song Dr. Carlos A. Steren Tianniu Chen Prof. Dr. Zhenhong Wei Prof. Dr. Hu Cai Prof. Dr. Zi‐Ling Xue 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(20):6033-6039
Metallacyclic complex [(Me2N)3Ta(η2‐CH2SiMe2NSiMe3)] ( 3 ) undergoes C?H activation in its reaction with H3SiPh to afford a Ta/μ‐alkylidene/hydride complex, [(Me2N)2{(Me3Si)2N}Ta(μ‐H)2(μ‐C‐η2‐CHSiMe2NSiMe3)Ta(NMe2)2] ( 4 ). Deuterium‐labeling studies with [D3]SiPh show H–D exchange between the Ta?D ?Ta unit and all methyl groups in [(Me2N)2{(Me3Si)2N}Ta(μ‐D)2(μ‐C‐η2‐CHSiMe2NSiMe3)Ta(NMe2)2] ([D2]‐ 4 ) to give the partially deuterated complex [Dn]‐ 4 . In addition, 4 undergoes β‐H abstraction between a hydride and an NMe2 ligand and forms a new complex [(Me2N){(Me3Si)2N}Ta(μ‐H)(μ‐N‐η2‐C,N‐CH2NMe)(μ‐C‐η2‐C,N‐CHSiMe2NSiMe3)Ta(NMe2)2] ( 5 ) with a cyclometalated, η2‐imine ligand. These results indicate that there are two simultaneous processes in [Dn]‐ 4 : 1) H–D exchange through σ‐bond metathesis, and 2) H?D elimination through β‐H abstraction (to give [Dn]‐ 5 ). Both 4 and 5 have been characterized by single‐crystal X‐ray diffraction studies. 相似文献
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Silvia Schnitzler Dr. Thomas P. Spaniol Prof. Dr. Laurent Maron Prof. Dr. Jun Okuda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(32):11330-11334
A complex featuring a terminal magnesium hydride bond supported by an NNNN macrocyclic ligand, [Mg{Me3TACD ? Al(iBu)3}H] ( 3 ), was formed from its labile Al(iBu)3 adduct. Use of Al(iBu)3 to block the amido nitrogen of the NNNN macrocyclic ligand was essential to prevent aggregation. The structurally characterized compound 3 reacted with BH3 to give the BH4 derivative, whereas Me3SiC?CH and PhSiH3 led to the corresponding acetylide and silyl derivative under H2 elimination. Pyridine is inserted into the Mg?H bond to give selectively the 1,4‐dihydropyridinate. 相似文献
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Sara Kopf Dr. Fei Ye Dr. Helfried Neumann Prof. Dr. Matthias Beller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(38):9768-9773
A novel ruthenium-catalyzed C−H activation methodology for hydrogen isotope exchange of aromatic carbonyl compounds is presented. In the presence of catalytic amounts of specific amine additives, a transient directing group is formed in situ, which directs selective deuteration. A high degree of deuteration is achieved for α-carbonyl and aromatic ortho-positions. In addition, appropriate choice of conditions allows for exclusive labeling of the α-carbonyl position while a procedure for the preparation of merely ortho-deuterated compounds is also reported. This methodology proceeds with good functional group tolerance and can be also applied for deuteration of pharmaceutical drugs. Mechanistic studies reveal a kinetic isotope effect of 2.2, showing that the C−H activation is likely the rate-determining step of the catalytic cycle. Using deuterium oxide as a cheap and convenient source of deuterium, the methodology presents a cost-efficient alternative to state-of-the-art iridium-catalyzed procedures. 相似文献