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Artykuły w czasopismach na temat „Transition Metal Complexes - Organic Reactions”

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Data publikacji: 7 września 2023

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1

Sanz, Roberto, i Raquel Hernández-Ruiz. "Dichlorodioxomolybdenum(VI) Complexes: Useful and Readily Available Catalysts in Organic Synthesis". Synthesis 50, nr 20 (5.09.2018): 4019–36. http://dx.doi.org/10.1055/s-0037-1610236.

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Molybdenum(VI) dichloride dioxide (MoO2Cl2), and its addition complexes [MoO2Cl2(L)n; L = neutral ligand], are commercially or easily available and inexpensive transition-metal complexes based on a non-noble metal that can be applied as catalysts for various organic transformations. This short review aims to present the most significant breakthroughs in this field.1 Introduction2 Preparation and Reactivity of MoO2Cl2(L)n Complexes2.1 Synthesis and Structure2.2 Reactivity of Dichlorodioxomolybdenum(VI) Complexes3 Redox Processes Catalyzed by MoO2Cl2(L)n Complexes3.1 Deoxygenation Reactions Using Phosphorus Compounds3.2 Deoxygenation and Hydrosilylation Reactions Using Silanes3.3 Reduction Reactions Using Hydrogen3.4 Deoxygenation Reactions with Boranes and Thiols3.5 Reduction Reactions with Glycols3.6 Oxidation Reactions4 Ambiphilic Reactivity of MoO2Cl2 4.1 Amphoteric Lewis Acid–Lewis Base Catalyzed Reactions4.2 Lewis Acid Type Catalyzed Reactions5 Conclusion and Perspective

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2

Calter, Michael A. "Transition Metal-Catalyzed, Asymmetric Reactions of Diazo Compounds". Current Organic Chemistry 1, nr 1 (maj 1997): 37–70. http://dx.doi.org/10.2174/1385272801666220121184444.

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The past ten years have seen impressive advances in asymmetric synthesis. This review summarizes the recent advances in a particular set of asymmetric reactions, the reactions of diazo compounds catalyzed by transition metal complexes. Additionally, the emphasis of this summary is on reactions wherein the induction arises from a catalyst or an auxiliary, rather than some inherent asymmetry of the substrate. The covered reactions fall into two reaction types; cyclopropanations and insertions. The cyclopropanation section of this review describes how high stereoselectivities are possible using either chiral auxiliaries or various metal complexes. Both these strategies are effective for producing optically-enriched intermediates; however, the use of catalysts to control the stereochemistry of the cyclopropanation reaction is much more common than the corresponding use of auxiliaries Workers in the asymmetric cyclopropanation field have primarily used Cu(l) and Rh(ll) complexes as catalysts for these reactions, although several complexes of other metals do afford high asymmetric induction. Both inter- and intramolecular cyclopropanations afford synthetically useful selectivities. The insertion section of this review summarizes recent advances in the use of auxiliaries and catalysts for controlling the stereoselectivity of the insertion into various bonds. Insertion into C-H bonds are by far the most intensively studied, although there has been some success with asymmetric insertions into 0-H, S-H, Si-H and C-0 bonds. Complexes of Rh(ll) are almost universally employed for asymmetric insertions. As in the case of cyclopropanations, both inter- and intramolecular insertions can proceed with useful selectivities. Again, catalyst control has proven a more versatile way to control absolute stereochemistry than auxiliary control.

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3

Bruce, Michael I., Mark G. Humphrey, George A. Koutsantonis i Brian K. Nicholson. "Reactions of transition metal acetylide complexes". Journal of Organometallic Chemistry 296, nr 3 (grudzień 1985): c47—c50. http://dx.doi.org/10.1016/0022-328x(85)80383-1.

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4

Reznikov, Alexander N., i Yuri N. Klimochkin. "Recent Developments in Highly Stereoselective Michael Addition Reactions Catalyzed by Metal Complexes". Synthesis 52, nr 06 (3.01.2020): 781–95. http://dx.doi.org/10.1055/s-0039-1690044.

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Achieving high enantioselectivity and diastereoselectivity simultaneously is a rather challenging task for asymmetric catalytic synthesis. Thanks to the rapid development of asymmetric transition-metal catalysis, significant progress has been made during recent years in achieving highly enantio- and diastereoselective conjugate addition reactions with a diverse combination of Michael donors and acceptors. This short review surveys the advances in transition-metal-catalyzed asymmetric diastereoselective Michael addition including diastereodivergent catalysis developed between 2015 and 2019. The review is divided into multiple parts according to the type of nucleophiles involved in the reaction.1 Introduction2 Addition of Functionalized Ketones and Dicarbonyl Compounds3 Addition of Aldimino Esters and Their Cyclic Analogues4 Addition of Indolin-2-ones5 Vinylogous Michael Reactions6 Other Michael Donors7 Cascade Reactions Initiated by Michael Addition8 Conclusion

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5

Arisawa, Mieko, i Masahiko Yamaguchi. "Transition-metal-catalyzed synthesis of organosulfur compounds". Pure and Applied Chemistry 80, nr 5 (1.01.2008): 993–1003. http://dx.doi.org/10.1351/pac200880050993.

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Rhodium complexes are efficient catalysts for the synthesis of organosulfur compounds. They catalyze the addition reaction of organosulfur groups to unsaturated compounds, the substitution of C-H with organosulfur groups, and single-bond metathesis reactions. They cleave S-S bonds and transfer the organosulfur groups to various organic and inorganic molecules, including alkynes, allenes, disulfides, sulfur, isonitriles, imines, diphosphines, thiophosphinites, hydrogen, 1-alkylthio-1-alkynes, thioesters, and allyl sulfides.

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6

Bruce, MI, i MG Humphrey. "Reactions of Transition Metal σ-Acetylide Complexes. XIII. Alkylation and Related Reactions". Australian Journal of Chemistry 42, nr 7 (1989): 1067. http://dx.doi.org/10.1071/ch9891067.

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A series of 20 cationic vinylidene complexes of ruthenium and osmium [M(CCRR′)(L)(L′)(η- C5H5)]+ (R′ = Me, Ph, C6H4F-4, C6F5, (CH2)2C2H; R′ = Me, CH2Ph, CH2CH=CH2, CH2C2CH, (CH2hBr; L, L′=PPh3, CNBUT, dppm, dppe; not all combinations), [{Ru (CCRCH2-)(PPH3)2( η- C5H5)2]2+ and [CH2{ CPhCRu (PPh3)2(η-C5H5)]2]2+ have been obtained from reactions between the metal acetylide complexes and the appropriate organic halides.

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7

Arisawa, Mieko. "Transition-Metal-Catalyzed Synthesis of Organophosphorus Compounds Involving P–P Bond Cleavage". Synthesis 52, nr 19 (7.07.2020): 2795–806. http://dx.doi.org/10.1055/s-0040-1707890.

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Organophosphorus compounds are used as drugs, pesticides, detergents, food additives, flame retardants, synthetic reagents, and catalysts, and their efficient synthesis is an important task in organic synthesis. To synthesize novel functional organophosphorus compounds, transition-metal-catalyzed methods have been developed, which were previously considered difficult because of the strong bonding that occurs between transition metals and phosphorus. Addition reactions of triphenylphosphine and sulfonic acids to unsaturated compounds in the presence of a rhodium or palladium catalyst lead to phosphonium salts, in direct contrast to the conventional synthesis involving substitution reactions of organohalogen compounds. Rhodium and palladium complexes catalyze the cleavage of P–P bonds in diphosphines and polyphosphines and can transfer organophosphorus groups to various organic compounds. Subsequent substitution and addition reactions proceed effectively, without using a base, to provide various novel organophosphorus compounds.1 Introduction2 Transition-Metal-Catalyzed Synthesis of Phosphonium Salts by Addition Reactions of Triphenylphosphine and Sulfonic Acids3 Rhodium-Catalyzed P–P Bond Cleavage and Exchange Reactions4 Transition-Metal-Catalyzed Substitution Reactions Using Diphosphines4.1 Reactions Involving Substitution of a Phosphorus Group by P–P Bond Cleavage4.2 Related Substitution Reactions of Organophosphorus Compounds4.3 Substitution Reactions of Acid Fluorides Involving P–P Bond Cleavage of Diphosphines5 Rhodium-Catalyzed P–P Bond Cleavage and Addition Reactions6 Rhodium-Catalyzed P–P Bond Cleavage and Insertion Reactions Using Polyphosphines7 Conclusions

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8

Yu, Xianghua, Laurel A. Morton i Zi-Ling Xue. "Transition-Metal Silyl Complexes and Chemistry in the Reactions of Silanes with Transition-Metal Complexes". Organometallics 23, nr 10 (maj 2004): 2210–24. http://dx.doi.org/10.1021/om049862p.

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9

Bruce, Michael I., Christopher Dean, D. Neil Duffy, Mark G. Humphrey i George A. Koutsantonis. "Reactions of transition metal σ-acetylide complexes". Journal of Organometallic Chemistry 295, nr 3 (listopad 1985): c40—c44. http://dx.doi.org/10.1016/0022-328x(85)80329-6.

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10

Shridharshini Kumar, Praveen Sekar i Senthil Kumar Raju. "Microwave assisted Schiff base metal complexes as potential anticancer and antimicrobial agents: A critical review". Open Access Research Journal of Science and Technology 7, nr 2 (30.03.2023): 001–18. http://dx.doi.org/10.53022/oarjst.2023.7.2.0016.

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Schiff bases are organic compounds which contain azomethine group (-C=N-) by reacting primary amines and carbonyl compounds. The presence of an azomethine group in the Schiff base facilitates coordination with transition metal ions. The term Schiff base is normally applied to these compounds when they are being used as ligands to form coordination complexes with metal ions. Such complexes occur naturally, but the majority of Schiff bases are artificial and are used to form many important catalysts. Schiff base metal complexes prepared using microwave irradiation have gained more attention because of their excellent strategy in generating quick and stable products in higher yields by improving the speed of reaction with lesser energy and exhibits various biological activities including antifungal, antibacterial, anti-tubercular, antiviral, antimalarial, anti-diabetic, anticancer, antioxidant, antidiuretic, anti-inflammatory, antipyretic and anti-HIV agents. Apart from biological applications, they are also used as a catalyst in Aldol reactions, polymerization reactions, oxidation reactions and other chemical reactions. Imine-ligand containing transition metal complexes including copper, zinc and cadmium, have proven to be effective starting points for the synthesis of metal or metal chalcogenide nanoparticles. In this review, various metal complexes derived from Schiff bases synthesised using microwave approaches are discussed along with their antibacterial, antifungal and anticancer activities.

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11

Gridnev, Ilya D. "Birds of a Feather—Asymmetric Organocatalysis Meets Asymmetric Transition Metal Catalysis". Catalysts 12, nr 2 (11.02.2022): 214. http://dx.doi.org/10.3390/catal12020214.

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The results of recent studies on the mechanism of stereoinduction in asymmetric hydrogenation catalyzed by transition metal complexes suggest that hydrogen activation by metal atoms and the generation of enantioselectivity by organic ligands proceed independently. Hence, these reactions can be considered as variants of a cooperative organocatalytic reaction. This conclusion opens a broader view on rational catalyst design, suggesting that the structural ideas from different fields can be exploited reciprocally.

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12

Barbolla, Iratxe, Nuria Sotomayor i Esther Lete. "Transition metal-guanidine complexes as catalysts in organic reactions. Recent developments". Arkivoc 2020, nr 7 (28.07.2020): 158–79. http://dx.doi.org/10.24820/ark.5550190.p011.265.

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13

BOCHMANN, M. "ChemInform Abstract: Homogeneous Catalysis of Organic Reactions by Transition Metal Complexes". ChemInform 26, nr 1 (18.08.2010): no. http://dx.doi.org/10.1002/chin.199501280.

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14

BOCHMANN, M. "ChemInform Abstract: Homogeneous Catalysis of Organic Reactions by Transition Metal Complexes". ChemInform 23, nr 15 (22.08.2010): no. http://dx.doi.org/10.1002/chin.199215337.

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15

Jeganmohan, Masilamani, i Pinki Sihag. "Recent Advances in Transition-Metal-Catalyzed C–H Functionalization Reactions Involving Aza/Oxabicyclic Alkenes". Synthesis 53, nr 18 (14.06.2021): 3249–62. http://dx.doi.org/10.1055/a-1528-1711.

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AbstractBicyclic alkenes, including oxa- and azabicyclic alkenes, readily undergo activation with facial selectivity in the presence of transition-metal complexes. This is due to the intrinsic angle strain on the carbon–carbon double bonds in such unsymmetrical bicyclic systems. During the past decades considerable progress has been made in the area of ring opening of bicyclic strained rings by employing the concept of C–H activation. This short review comprehensively compiles the various C–H bond activation assisted reactions of oxa- and azabicyclic alkenes, viz., ring-opening reactions, hydroarylation, and annulation reactions.1 Introduction2 Reactions of Heterobicyclic Ring Systems2.1 Ring-Opening Reactions of Oxa- and Azabenzonorbornadienes2.1.1 Reactions Using 7-Oxabenzonorbornadienes2.1.2 Reactions Using 7-Azabenzonorbornadienes2.2 Hydroarylation Reactions2.3 Annulation Reactions2.4 Other Reactions3 Conclusion

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16

HIROI, Kunio. "Stereochemistry of Asymmetric Reactions via Chiral .PI.-Allyl Transition Metal Complexes." Journal of Synthetic Organic Chemistry, Japan 53, nr 12 (1995): 1090–101. http://dx.doi.org/10.5059/yukigoseikyokaishi.53.1090.

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17

MURAKAMI, Masahiro, Kenichiro ITAMI, Minoru UBUKATA, Itaru TSUJI i Yoshihiko ITO. "New Cycloaddition Reactions of Conjugated Allenes Catalyzed by Transition Metal Complexes." Journal of Synthetic Organic Chemistry, Japan 56, nr 5 (1998): 406–12. http://dx.doi.org/10.5059/yukigoseikyokaishi.56.406.

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18

Ojima, Iwao. "New cyclization reactions in organic syntheses". Pure and Applied Chemistry 74, nr 1 (1.01.2002): 159–66. http://dx.doi.org/10.1351/pac200274010159.

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Recent development in the transition metal-catalyzed cyclization reactions for organic syntheses in the author's laboratories is summarized, which includes (i) novel silylcarbocyclizations (SiCaCs) and carbonylative carbotricyclizations, (ii) intramolecular silylformylations and desymmerization of siloxydiynes by sequential double silylformylation, (iii) efficient total synthesis of (+)-prosopinine, (iv) enantioselective desymmetrization of aminodienes, and (iv) new and efficient routes to 1-azabicyclo[x.y.0]alkane amino acids. All these processes are catalyzed by Rh or RhCo complexes, and useful for rapid and efficient construction of a variety of heterocyclic and carbocyclic compounds. Mechanisms of these new carbocyclization and cyclohydrocarbonylation reactions are also discussed.

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19

Wei, Yi, Quan-Quan Zhou, Fen Tan, Liang-Qiu Lu i Wen-Jing Xiao. "Visible-Light-Driven Organic Photochemical Reactions in the Absence of External Photocatalysts". Synthesis 51, nr 16 (20.05.2019): 3021–54. http://dx.doi.org/10.1055/s-0037-1611812.

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Visible-light-driven organic photochemical reactions have attracted substantial attention from the synthetic community. Typically, catalytic quantities of photosensitizers, such as transition metal complexes, organic dyes, or inorganic semiconductors, are necessary to absorb visible light and trigger subsequent organic transformations. Recently, in contrast to these photocatalytic processes, a variety of photocatalyst-free organic photochemical transformations have been exploited for the efficient formation of carbon–carbon and carbon–heteroatom bonds. In addition to not requiring additional photocatalysts, they employ low-energy visible light irradiation, have mild reaction conditions, and enable broad substrate diversity and functional group tolerance. This review will focus on a summary of representative work in this field in terms of different photoexcitation modes.1 Introduction2 Visible Light Photoexcitation of a Single Substrate3 Visible Light Photoexcitation of Reaction Intermediates4 Visible Light Photoexcitation of EDA Complexes between Substrates5 Visible Light Photoexcitation of EDA Complexes between Substrates and Reaction Intermediates6 Visible Light Photoexcitation of Products7 Conclusion and Outlook

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20

Rieger, D., S. D. Lotz, U. Kernbach, C. André, J. Bertran-Nadal i W. P. Fehlhammer. "Synthesis of organic heterocycles via multicomponent reactions with cyano transition metal complexes". Journal of Organometallic Chemistry 491, nr 1-2 (kwiecień 1995): 135–52. http://dx.doi.org/10.1016/0022-328x(94)05258-d.

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Siddiqui, Mujahuddin M., Joel T. Mague i Marvanji S. Balakrishna. "cis-Bisphenylalkynyl cyclodiphosphazane: Oxidation reactions and transition metal complexes". Journal of Organometallic Chemistry 794 (październik 2015): 81–87. http://dx.doi.org/10.1016/j.jorganchem.2015.06.033.

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Mehrotra, Raj Narain. "Review on the Chemistry of [M(NH3)n](XO4)m (M = Transition Metal, X = Mn, Tc or Re, n = 1–6, m = 1–3) Ammine Complexes". Inorganics 11, nr 7 (20.07.2023): 308. http://dx.doi.org/10.3390/inorganics11070308.

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The preparation of ammine complexes of transition metals having oxidizing anions such as permanganate and perrhenate ions is a great challenge due to possible reactions between ammonia and oxidizing anions during the synthesis of these materials. However, it has an important role in both the development of new oxidants in organic chemistry and especially in the preparation of mixed-metal oxide catalyst precursors and metal alloys for their controlled temperature decomposition reactions. Therefore, in this paper, synthetic procedures to prepare ammonia complexes of transition metal permanganate, pertechnetate, and perrhenate (the VIIB group tetraoxometallates) salts have been comprehensively reviewed. The available data about these compounds’ structures and spectroscopic properties, including the presence of hydrogen bonds that act as redox reaction centers during thermal decomposition, are given and evaluated in detail. The nature of the thermal decomposition products has also been summarized. The available information about the role of the ammine complexes of transition metal permanganate salts in organic oxidation reactions, such as the oxidation of benzyl alcohols and regeneration of oxo-compounds from oximes and phenylhydrazones, including the kinetics of these processes, has also been collected. Their physical and chemical properties, including the thermal decomposition characteristics of known diammine (Ag(I), Cd, Zn, Cu(II), Ni(II)), triammine (Ag(I)), and simple or mixed ligand tetraammine (Cu(II), Zn, Cd, Ni(II), Co(II), Pt(II), Pd(II), Co(III)), Ru(III), pentaammine (Co(III), Cr(III), Rh(III) and Ir(III)), and hexaammine (Ni(II), Co(III), Cr(III)) complexes of transition metals with tetraoxometallate(VII) anions (M = Mn, Tc and Re), have been summarized. The preparation and properties of some special mixed ligand/anion/cation-containing complexes, such as [Ru(NH3)4(NO)(H2O)](ReO4)2, [Co(NH3)5(H2O)](ReO4)2, [Co(NH3)5X](MnO4)2 (X = Cl, Br), [Co(NH3)6]Cl2(MnO4), [Co(NH3)5ReO4]X2 (X = Cl, NO3, ClO4, ReO4), and K[Co(NH3)6]Cl2(MnO4)2, are also included.

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23

Mazzoni, Rita, Fabio Marchetti, Andrea Cingolani i Valerio Zanotti. "Bond Forming Reactions Involving Isocyanides at Diiron Complexes". Inorganics 7, nr 3 (26.02.2019): 25. http://dx.doi.org/10.3390/inorganics7030025.

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The versatility of isocyanides (CNR) in organic chemistry has been tremendously enhanced by continuous advancement in transition metal catalysis. On the other hand, the urgent need for new and more sustainable synthetic strategies based on abundant and environmental-friendly metals are shifting the focus towards iron-assisted or iron-catalyzed reactions. Diiron complexes, taking advantage of peculiar activation modes and reaction profiles associated with multisite coordination, have the potential to compensate the lower activity of Fe compared to other transition metals, in order to activate CNR ligands. A number of reactions reported in the literature shows that diiron organometallic complexes can effectively assist and promote most of the “classic” isocyanide transformations, including CNR conversion into carbyne and carbene ligands, CNR insertion, and coupling reactions with other active molecular fragments in a cascade sequence. The aim is to evidence the potential offered by diiron coordination of isocyanides for the development of new and more sustainable synthetic strategies for the construction of complex molecular architectures.

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Yu, Haizhu, Yao Fu, Qingxiang Guo i Zhenyang Lin. "DFT Studies on Reactions of Transition Metal Complexes with O2". Organometallics 28, nr 15 (10.08.2009): 4443–51. http://dx.doi.org/10.1021/om9002957.

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Bruce, Michael I. "Some Organometallic Chemistry of Tetracyanoethene: CN-displacement and Cycloaddition Reactions with Alkynyl - Transition Metal Complexes and Related Chemistry". Australian Journal of Chemistry 64, nr 1 (2011): 77. http://dx.doi.org/10.1071/ch10307.

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The highly electron-deficient cyanocarbons tetracyanoethene (tcne) and, to a lesser extent, tetracyanoquinodimethane (tcnq), display a fascinating chemistry with transition metal substrates. In particular, the [2 + 2]-cycloadditions of the cyanocarbons with alkynyl- or poly-ynyl–metal complexes have been extensively studied by the author’s group. These reactions proceed via polar adducts to give σ-cyclobutenyl complexes, which then undergo facile ring-opening (retro-electrocyclic) reactions to form the corresponding butadienyl derivatives. In some cases, further reactions can occur by displacement of weakly bound ligands from the metal centre. The subsequent chemistry of these derivatives has been only cursorily investigated, while related studies of organic analogues have produced molecules with interesting electronic and optical properties.

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Kobiki, Yohsuke, Shin-ichi Kawaguchi, Takashi Ohe i Akiya Ogawa. "Photoinduced synthesis of unsymmetrical diaryl selenides from triarylbismuthines and diaryl diselenides". Beilstein Journal of Organic Chemistry 9 (13.06.2013): 1141–47. http://dx.doi.org/10.3762/bjoc.9.127.

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A novel method of photoinduced synthesis of unsymmetrical diaryl selenides from triarylbismuthines and diaryl diselenides has been developed. Although the arylation reactions with triarylbismuthines are usually catalyzed by transition-metal complexes, the present arylation of diaryl diselenides with triarylbismuthines proceeds upon photoirradiation in the absence of transition-metal catalysts. A variety of unsymmetrical diaryl selenides can be conveniently prepared by using this arylation method.

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Shan, He, Li Ling, Jianfeng Hu i Hao Zhang. "Application in the Asymmetric Catalytic Reactions of Chiral Cyclopentadienyl-Transition-Metal Complexes". Chinese Journal of Organic Chemistry 39, nr 6 (2019): 1548. http://dx.doi.org/10.6023/cjoc201903012.

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Shi, Hang, Qi-Kai Kang, Yunzhi Lin i Yuntong Li. "Transition-Metal-Catalyzed Amination of Aryl Fluorides". Synlett 31, nr 12 (14.05.2020): 1135–39. http://dx.doi.org/10.1055/s-0040-1707118.

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Arene activation via transition-metal (TM) η6-coordination has merged as a powerful method to diversify the aromatic C–F bond, which is relatively less reactive due to its high bond energy. However, this strategy in general requires to use largely excess arenes or TM η6-complexes as the substrates. Herein, we highlight our recent work on the catalytic SNAr amination of electron-rich and electron-neutral aryl fluorides that are inert in classical SNAr reactions. This protocol enabled by a Ru/hemilabile ligand catalyst covers a broad scope of substrates without wasting arenes. Mechanistic studies revealed that the nucleophilic substitution proceeded on a Ru η6-arene complex, and the hemilabile ligand significant promoted the arene dissociation.

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Ojima, Iwao, Núria Clos i Cecilia Bastos. "Recent advances in catalytic asymmetric reactions promoted by transition metal complexes". Tetrahedron 45, nr 22 (1989): 6901–39. http://dx.doi.org/10.1016/s0040-4020(01)89159-6.

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Patil, Mahendra. "Mechanism of the t-BuOM (M = K, Na, Li)/DMEDA-Mediated Direct C–H Arylation of Benzene: A Computational Study". Synthesis 52, nr 19 (22.06.2020): 2883–91. http://dx.doi.org/10.1055/s-0040-1707882.

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Over the past ten years, a combination of organic additive and t-BuOK/t-BuONa has been successfully used for the direct C–H arylation of arenes. Conceptually different from transition-metal-catalyzed cross-coupling reactions, these t-BuOK-mediated reactions have raised significant curiosity among organic chemists. Herein, a systematic computational study of each elementary step of the t-BuOM (M = K, Na, Li)/N 1,N 2-dimethylethane-1,2-diamine (DMEDA) mediated direct C–H arylation of benzene is detailed. The presented mechanistic proposal relies on the complexation and reaction of t-BuOM with DMEDA (additive), which leads to the formation of different complexes such as SED(M+)…PhI. These complexes mainly involve coordination of the metal ion (from t-BuOM) to the additive and iodobenzene via stabilizing cation–lone pair and cation–π interactions. Such complexation of a metal ion to an additive and iodobenzene not only ensures facile electron transfer to iodobenzene but also provides a lowest energy pathway for the subsequent radical addition and deprotonation step.

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Mayr, Herbert, i Armin R. Ofial. "Kinetics of electrophile-nucleophile combinations: A general approach to polar organic reactivity". Pure and Applied Chemistry 77, nr 11 (1.01.2005): 1807–21. http://dx.doi.org/10.1351/pac200577111807.

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Benzhydrylium ions (Ar2CH+) and structurally related quinone methides are employed as reference electrophiles for comparing the nucleophilicities of a large variety of compounds, e.g., alkenes, arenes, alkynes, allylsilanes, allylstannanes, enol ethers, enamines, diazo compounds, carbanions, transition-metal π-complexes, hydride donors, phosphanes, amines, alkoxides, etc., using the correlation equation log k (20 °C) = s(N + E), where s and N are nucleophile-dependent parameters and E is an electrophilicity parameter. The same equation was employed to derive the electrophilicity parameter E for different types of carbocations, cationic transition-metal π-complexes, typical Michael acceptors, and electron-deficient arenes. The E, N, and s parameters thus obtained can be used for predicting rates and selectivities of polar organic reactions.

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Salzer, A. "Nomenclature of Organometallic Compounds of the Transition Elements (IUPAC Recommendations 1999)". Pure and Applied Chemistry 71, nr 8 (30.08.1999): 1557–85. http://dx.doi.org/10.1351/pac199971081557.

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Organometallic compounds are defined as containing at least one metal-carbon bond between an organic molecule, ion, or radical and a metal. Organometallic nomenclature therefore usually combines the nomenclature of organic chemisty and that of coordination chemistry. Provisional rules outlining nomenclature for such compounds are found both in Nomenclature of Organic Chemistry, 1979 and in Nomenclature of Inorganic Chemistry, 1990This document describes the nomenclature for organometallic compounds of the transition elements, that is compounds with metal-carbon single bonds, metal-carbon multiple bonds as well as complexes with unsaturated molecules (metal-p-complexes).Organometallic compounds are considered to be produced by addition reactions and so they are named on an addition principle. The name therefore is built around the central metal atom name. Organic ligand names are derived according to the rules of organic chemistry with appropriate endings to indicate the different bonding modes. To designate the points of attachment of ligands in more complicated structures, the h, k, and m-notations are used. The final section deals with the abbreviated nomenclature for metallocenes and their derivatives.ContentsIntroduction Systems of Nomenclature2.1 Binary type nomenclature 2.2 Substitutive nomenlcature 2.3 Coordination nomenclature Coordination Nomenclature3.1 General definitions of coordination chemistry 3.2 Oxidation numbers and net charges 3.3 Formulae and names for coordination compounds Nomenclature for Organometallic Compounds of Transition Metals 4.1 Valence-electron-numbers and the 18-valence-electron-rule 4.2 Ligand names 4.2.1 Ligands coordinating by one metal-carbon single bond 4.2.2 Ligands coordinating by several metal-carbon single bonds 4.2.3 Ligands coordinating by metal-carbon multiple bonds 4.2.4 Complexes with unsaturated molecules or groups 4.3 Metallocene nomenclature

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Cenini, Sergio, Emma Gallo, Alessandro Caselli, Fabio Ragaini, Simone Fantauzzi i Cristiana Piangiolino. "Coordination chemistry of organic azides and amination reactions catalyzed by transition metal complexes". Coordination Chemistry Reviews 250, nr 11-12 (czerwiec 2006): 1234–53. http://dx.doi.org/10.1016/j.ccr.2005.10.002.

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Sellmann, Dieter, Gerhard Freyberger i Matthias Moll. "Übergangsmetallkomplexe mit Schwefelliganden, XLVIa. Zn-, Cd-, Hg-, Sn-, Pb-, Sb-, Bi- und Ti-Komplexe mit den zwei- und vierzähnigen Thiolatliganden 'buS2'2- = 3,5-Di(t-butyl)benzol-1,2-dithiolat(2—), 'S4'2- = 1,2-Bis(2-mercaptophenylthio)ethan(2—) und 'buS4'2- = 1,2-Bis(3,5-di(t-butyl)-2-mercaptophenylthio)ethan(2–) / Transition Metal Complexes with Sulfur Ligands, XLVIa. Zn, Cd, Hg, Sn, Pb, Bi and Ti Complexes with the Bi- and Tetradentate Thiolato Ligands 'buS2'2- = 3,5-Di(t-butyl)benzene-1,2-dithiolate(2–), 'S4'2 = 1,2-Bis(2-mercaptophenylthio)ethane(2–) and 'buS4'2- = 1,2-Bis(3,5-di(t-butyl)-2-mercaptophenylthio)ethane(2 – )". Zeitschrift für Naturforschung B 44, nr 9 (1.09.1989): 1015–22. http://dx.doi.org/10.1515/znb-1989-0905.

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Syntheses of neutral 'buS2'-, 'S4'- and 'buS4'- and of anionic .buS2-complexes with various main group and transition metals are described. The complexes were prepared by reacting the neutral sulfur ligands or their alkali salts with the metal halide or alkoxide. The ligands coordinate to metal ions in normal as well as high oxidation states. No redox reactions occur in the latter case. The complexes are usually soluble in organic solvents and were characterized by elemental analysis and spectroscopic means.

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Chiou, Wen-Hua, Seung-Yub Lee i Iwao Ojima. "Recent advances in cyclohydrocarbonylation reactions". Canadian Journal of Chemistry 83, nr 6-7 (1.06.2005): 681–92. http://dx.doi.org/10.1139/v05-035.

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This article describes recent advances in the cyclohydrocarbonylation reactions catalyzed by transition-metal complexes and their applications in organic synthesis as a review covering the relevant literature up to the middle of 2004. The reactions are categorized into four types, i.e., intramolecular amidocarbonylation reactions, intramolecular aminocarbonylation reactions, cyclohydrocarbonylation reactions involving carbonnucleophiles, and other cyclohydrocarbonylation reactions. Cyclohydrocarbonylation reactions provide efficient routes to various monocyclic, bicyclic, and polycyclic compounds as a one-step cascade process or a one-pot process. Reaction mechanisms for these cascade processes are discussed as needed for clarification. The heterocyclic and carbocyclic compounds, thus obtained, can be further transformed to specific targets. Examples of such applications are also discussed.Key words: catalysis, cyclohydrocarbonylation, hydroformylation, amidocarbonylation, cyclization, regioselectivity, aldehydes, regioselective, cascade, heterocycles, rhodium.

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36

Huszthy, Péter, Hajnalka Szabó-Szentjóbi, István Majoros, Anna Márton, Ibolya Leveles, Beáta G. Vértessy, Miklós Dékány i Tünde Tóth. "Synthesis of New Chiral Crown Ethers Containing Phosphine or Secondary Phosphine Oxide Units". Synthesis 52, nr 19 (10.06.2020): 2870–82. http://dx.doi.org/10.1055/s-0040-1707854.

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The transition-metal complexes of phosphine and secondary phosphine oxide compounds can be used in various catalytic reactions. In this paper, the synthesis and characterization of eight new crown ethers containing trivalent phosphorus in their macroring are reported. These macrocycles are promising candidates as ligands for catalytic reactions.

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Ryabov, Alexander D. "The Exchange of Cyclometalated Ligands". Molecules 26, nr 1 (3.01.2021): 210. http://dx.doi.org/10.3390/molecules26010210.

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Reactions of cyclometalated compounds are numerous. This account is focused on one of such reactions, the exchange of cyclometalated ligands, a reaction between a cyclometalated compound and an incoming ligand that replaces a previously cyclometalated ligand to form a new metalacycle: + H-C*~Z ⇄ + H-C~Y. Originally discovered for PdII complexes with Y/Z = N, P, S, the exchange appeared to be a mechanistically challenging, simple, and convenient routine for the synthesis of cyclopalladated complexes. Over four decades it was expanded to cyclometalated derivatives of platinum, ruthenium, manganese, rhodium, and iridium. The exchange, which is also questionably referred to as transcyclometalation, offers attractive synthetic possibilities and assists in disclosing key mechanistic pathways associated with the C–H bond activation by transition metal complexes and C–M bond cleavage. Both synthetic and mechanistic aspects of the exchange are reviewed and discussed.

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Orysyk, Svitlana, Vasyl Pekhnyo, Viktor Orysyk, Yuri Zborovskii, Polina Borovyk i Vovk Mykhailo. "FUNDAMENTAL ASPECTS OF THE COORDINATION CHEMISTRY OF TRANSITION METALS WITH FUNCTIONALLY SUBSTITUTED THIOAMIDES (PART 1)". Ukrainian Chemistry Journal 88, nr 2 (25.03.2022): 85–115. http://dx.doi.org/10.33609/2708-129x.88.02.2022.85-115.

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The influence of competitive coordination, a tautomeric form of functionally substituted thioamides, conditions of synthesis and nature of the metal on the course of the reaction and structure of mono-, bi, and polynuclear complexes of 3d, 4d-metals is considered based on results obtained in the Department of "Chemistry of Complex Compounds" of the V.I. Vernadsky Institute of General and Inorganic Chemistry NAS of Ukraine, together with the staff of the Department of “Chemistry of Heterocyclic Compounds” of the Institute of Organic Chemistry NAS of Ukraine. The influence of ligand denticity, as well as conditions of complex formation on the structure of obtained complexes and their polymorphic modifications, was studied based on the reaction of d-metals with functionally substituted N, S- and O, N, S-containing thioamides. In addition, it is proved the influence of tautomeric forms of thioamides on the stereochemistry of coordination polyhedra: it is found that the thionic tautomeric form promotes the transposition of thioureas, while the thiol form promotes its cis-position in the square-planar of a polyhedron of 3d, 4d-metals in the structure of complexes. However, it was found that the thion tautomeric form leads to the formation of octahedral, while the thiol form to the square-planar of coordination nodes in complexes of Cu(II) and Ni(II), which are characterized by a change in coordination polyhedra (from square-planar and tetrahedron to octahedron) that depending on the strength of the ligand field. It is obvious that this effect of tautomeric forms of thioamides is associated with the formation of a conjugate system of double bonds in their molecules. In this case, the transition of thioamide to thiol form depends on the pH and the nature of the organic solvent: in a weakly alkaline medium or polar organic solvent (pyridine, chloroform) there is a shift of equilibrium towards to the dominance of thiol tautomeric form. It was found that the thionic tautomeric form of thioamides (depending on pH and substituent composition) reacts with metal salts mainly in neutral form or in the monoanionic form, forming complexes of molecular or ionic nature, while thiol form reacts in the form of dianion, forming complexes preferably anionic type. Ionic compounds are usually soluble or sparingly soluble in water in low concentrations (10-3–10-5 mol/l), while compounds of the molecular type are soluble only in DMSO and DMF. It is shown that the stereoselective synthesis of various ligand complexes is carried out mainly in three ways: 1) by the interaction of the initial components in the corresponding stoichiometry. In this case, the vacancy in the metal environment is occupied by either the anions of the starting metal salt (Hal-, SO42-, NO3-, CH3COO-, etc.) or other organic molecules (triphenylphosphine, pyridine, etc.); 2) carrying out parallel reactions (hydrolysis and oxidation of thioureas), which lead to participation in the coordination of by-products of the reaction; 3) carrying out reactions with intraligand rearrangements, which leads to the cyclization of organic ligands and coordination of the products of their transformation to the central metal ion. However, it was found that hydrolysis / oxidation or intraligand cyclization of substituted polydentate thioamides can occur both under the action of synthesis conditions and under the action of complexing metals as promoters of organic reactions. It was found that depending on the temperature and time of interaction of the starting reagents, different polymorphic modifications of complexes (triclinic or monoclinic) are formed, which differ in packing density and the nature of intermolecular interactions. As a result, such polymorphic modifications have different solubilities in water, which is important for the controlled synthesis of appropriate structures and their practical application.

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39

Yang, Zhonglie, Yutong Liu, Kun Cao, Xiaobin Zhang, Hezhong Jiang i Jiahong Li. "Synthetic reactions driven by electron-donor–acceptor (EDA) complexes". Beilstein Journal of Organic Chemistry 17 (6.04.2021): 771–99. http://dx.doi.org/10.3762/bjoc.17.67.

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The reversible, weak ground-state aggregate formed by dipole–dipole interactions between an electron donor and an electron acceptor is referred to as an electron-donor–acceptor (EDA) complex. Generally, upon light irradiation, the EDA complex turns into the excited state, causing an electron transfer to give radicals and to initiate subsequent reactions. Besides light as an external energy source, reactions involving the participation of EDA complexes are mild, obviating transition metal catalysts or photosensitizers in the majority of cases and are in line with the theme of green chemistry. This review discusses the synthetic reactions concerned with EDA complexes as well as the mechanisms that have been shown over the past five years.

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40

Gava, Riccardo, i Elena Fernández. "Organoboron synthesis via ring opening coupling reactions". Organic & Biomolecular Chemistry 17, nr 26 (2019): 6317–25. http://dx.doi.org/10.1039/c9ob00989b.

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This review covers new trends towards the selective synthesis of organoboron compounds where boron reagents and cyclic substrates participate in the generation of carbanions, in the presence of stoichiometric amounts of main-group metals or catalytic amounts of transition metal complexes, via ring opening coupling transformations.

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41

Bao, Xuefei, Xu Li, Chunfeng Jiang, Wei Xiao i Guoliang Chen. "Recent advances in catalysts for the Henry reaction". Australian Journal of Chemistry 75, nr 10 (8.11.2022): 806–19. http://dx.doi.org/10.1071/ch22136.

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The Henry reaction, the coupling of a nitro alkane and a carbonyl group, is an important C–C bond-forming reaction giving nitro alkanols, which are useful, versatile intermediates in synthetic organic chemistry and for the pharmaceutical industry. Among the catalysts employed in the Henry reaction, transition metal complex catalysts play an important role. Transition metal complexes, including small molecules and nanoparticles, catalyze the asymmetric Henry reaction efficiently and in most of the cases give chiral nitro alkanol products in good yield and enantiomeric excess. This review summarizes transition metal complex catalysts, metal-free organic catalysts and nanoparticle catalysts for the Henry reaction.

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42

Neshat, Abdollah, Piero Mastrorilli i Ali Mousavizadeh Mobarakeh. "Recent Advances in Catalysis Involving Bidentate N-Heterocyclic Carbene Ligands". Molecules 27, nr 1 (24.12.2021): 95. http://dx.doi.org/10.3390/molecules27010095.

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Since the discovery of persistent carbenes by the isolation of 1,3-di-l-adamantylimidazol-2-ylidene by Arduengo and coworkers, we witnessed a fast growth in the design and applications of this class of ligands and their metal complexes. Modular synthesis and ease of electronic and steric adjustability made this class of sigma donors highly popular among chemists. While the nature of the metal-carbon bond in transition metal complexes bearing N-heterocyclic carbenes (NHCs) is predominantly considered to be neutral sigma or dative bonds, the strength of the bond is highly dependent on the energy match between the highest occupied molecular orbital (HOMO) of the NHC ligand and that of the metal ion. Because of their versatility, the coordination chemistry of NHC ligands with was explored with almost all transition metal ions. Other than the transition metals, NHCs are also capable of establishing a chemical bond with the main group elements. The advances in the catalytic applications of the NHC ligands linked with a second tether are discussed. For clarity, more frequently targeted catalytic reactions are considered first. Carbon–carbon coupling reactions, transfer hydrogenation of alkenes and carbonyl compounds, ketone hydrosilylation, and chiral catalysis are among highly popular reactions. Areas where the efficacy of the NHC based catalytic systems were explored to a lesser extent include CO2 reduction, C-H borylation, alkyl amination, and hydroamination reactions. Furthermore, the synthesis and applications of transition metal complexes are covered.

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43

Morris, Robert H. "1995 Alcan Award Lecture New intermediates in the homolytic and heterolytic splitting of dihydrogen". Canadian Journal of Chemistry 74, nr 11 (1.11.1996): 1907–15. http://dx.doi.org/10.1139/v96-215.

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Some of the research of the author and his research group into the structure and reactions of dihydrogen complexes of transition metals is reviewed. The characterization of osmium complexes that can be regarded as having intermediate structures on the way to the homolytic splitting and to the heterolytic splitting of dihydrogen is described. The properties of an iridium complex with novel short proton–hydride contacts is also reviewed. Key words: transition metal, dihydrogen, hydride, complexes, NMR, neutron diffraction, osmium, iridium.

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44

Schenk, Wolfdieter A., Jürgen Bezler, Nicolai Burzlaff, Eberhard Dombrowski, Jürgen Frisch, Nikolai Kuhnert i Irene Reuther. "Stereo- and Enantioselective Reactions of Organosulfur Compounds Mediated by Transition Metal Complexes". Phosphorus, Sulfur, and Silicon and the Related Elements 95, nr 1-4 (październik 1994): 367–70. http://dx.doi.org/10.1080/10426509408034239.

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Mattigod, S. V., P. F. Pratt i E. B. Schalscha. "Trace Metal Speciation in a Soil Profile Irrigated with Waste Waters". Water Science and Technology 17, nr 9 (1.09.1985): 133–42. http://dx.doi.org/10.2166/wst.1985.0087.

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A chemical equilibrium computer model: GEOCHEM, was used to predict the trace metal behavior in a soil profile if subjected to a long-term irrigation with waste waters. Various categories of interactions such as acid-base equilibria, soluble complex formation of metals with organic and inorganic ligands, dissolution-precipitation reactions and ion-exchange reactions were included in simulation. The metal-soluble organic interactions were accounted for by a mixture model. The computations included a 10 metal - 15 ligand system with 262 soluble complex species and 21 possible solid phases. The results predicted that a major fraction of alkali elements in solution tend to be in free ionic forms, whereas, major fractions of the alkaline earths were predicted to be present in adsorbed and/or precipitated forms. In marked contrast, significant soluble fractions of transition series metals were predicted to be in adsorbed and/or complexed forms. The degree of attenuation of these transition series elements moving through the soil profile seems to be governed mainly by the degree of adsorption on soil surfaces and the tendency of these elements to form soluble organic complexes. The predicted mobilities of these elements in this soil profile was Cu > Ni > Zn > Cd. Application of this equilibrium model appears to provide a first approximation approach to simulate the trace element behavior in soil profiles.

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46

Ahmed, Ayman H. "Transition Metal Complexes On Insoluble Support And Their Applications In Transformations Of Organic Reactions". International Journal of ChemTech Research 11, nr 10 (2018): 260–73. http://dx.doi.org/10.20902/ijctr.2018.111032.

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Mocanu, Anca, i Corina Cernatescu. "Metal complexes of 3-chloro-4-hydrazino-carbonyl-methoxy-benzenesulfondibuthylamide". Chemical Industry and Chemical Engineering Quarterly 14, nr 1 (2008): 1–4. http://dx.doi.org/10.2298/ciceq0801001m.

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By taking the biological activity of 3-chloro-4-hydrazinocarbonyl-methoxy-benzenesulphondibuthylamide and of some transitional metals (Cu, Co, Cr, Fe, Mn, Ni, Sn) into account we considered it useful to capitalize the already obtained hydrazide by complexion reactions with various metallic salts. The reaction was carried out in the organic solvent medium, by heating under stirring. The obtained products were purified by recrystallization from organic solvents (especially ethanol) and characterized by means of melting points, elemental analysis and spectral measurements.

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López, Óscar, i José M. Padrón. "Iridium- and Palladium-Based Catalysts in the Pharmaceutical Industry". Catalysts 12, nr 2 (28.01.2022): 164. http://dx.doi.org/10.3390/catal12020164.

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Transition metal catalysts play a vital role in a wide range of industrial organic processes. The large-scale production of chemicals relying on catalyzed organic reactions represents a sustainable approach to supply society with end products for many daily life applications. Homogeneous (mainly for academic uses) and heterogeneous (crucial in industrial processes) metal-based catalysts have been developed for a plethora of organic reactions. The search for more sustainable strategies has led to the development of a countless number of metal-supported catalysts, nanosystems, and electrochemical and photochemical catalysts. In this work, although a vast number of transition metals can be used in this context, special attention is devoted to Ir- and Pd-based catalysts in the industrial manufacture of pharmaceutical drugs. Pd is by far the most widely used and versatile catalyst not only in academia but also in industry. Moreover, Ir-based complexes have emerged as attractive catalysts, particularly in asymmetric hydrogenation reactions. Ir- and Pd-based asymmetric reductions, aminations, cross-coupling reactions, and C–H activation are covered herein in the production of biologically active compounds or precursors; adaptation to bulk conditions is particularly highlighted.

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Cenini, Sergio, Francesca Porta i Maddalena Pizzotti. "Reactions of amines and related species with transition metal peroxo complexes". Journal of Organometallic Chemistry 296, nr 1-2 (listopad 1985): 291–300. http://dx.doi.org/10.1016/0022-328x(85)80356-9.

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Kongshaug, Phillip A., i Roy G. Miller. "Lewis acid assisted reactions of N-acylimidazoles with transition-metal nucleophiles. A route to formyl transition-metal complexes". Organometallics 6, nr 2 (luty 1987): 372–78. http://dx.doi.org/10.1021/om00145a022.

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