The scope and limitations of the copper-catalyzed propargylic amination various esters with amines are presented, where optically active diphosphines such as Cl-MeO-BIPHEP BINAP work good chiral ligands. A variety secondary available nucleophiles for this catalytic reaction to give corresponding a high enantioselectivity. results some stoichiometric reactions indicate that proceeds via copper−allenylidene complexes formed in situ, attack electrophilic γ-carbon atom allenylidene complex is an...

Novel mixed-ligand Ir(III) complexes, [Ir(L)(NwedgeC)X]n+ (L = N/\C/\N or N/\N/\N; X Cl, Br, I, CN, CH3CN, -CCPh; n 0 1), were synthesized, where N/\CwedgeN bis(N-methylbenzimidazolyl)benzene (Mebib) and bis(N-phenylbenzimidazolyl)benzene (Phbib), N/\N/\N bis(N-methylbenzimidazolyl)pyridine (Mebip), N/\C phenylpyridine (ppy) derivatives. The X-ray crystal structures of [Ir(Phbib)(ppy)Cl] [Ir(Mebib)(mppy)Cl] [mppy 5-methyl-2-(2'-pyridyl)phenyl] indicate that the nitrogen atom ppy ligand is...

Novel neutral mixed-ligand Ir(N=C=N)(N=C)X complexes (N=C=N = 1,3-bis(3-methylpyrazolyl)benzene (bpzb), 1,5-dimethyl-2,4-bis(3-methylpyrazolyl)benzene (dmbpzb), and 1,5-difluoro-2,4-bis(3-methylpyrazolyl)benzene (dfbpzb); N=C 2-phenyl pyridine (ppy); X Cl or CN) have been synthesized characterized. An X-ray single-crystal structure of the complex Ir(dmbpzb)(ppy)Cl shows that nitrogen atom in ppy ligand occupied trans position to carbon tridentate N=C=N dmbpzb with Ir-C bond length 1.94(1) A,...

Abstract The NN bond of molecular dinitrogen bridging two molybdenum atoms in the pentamethylcyclopentadienyl complexes that bear ferrocenyldiphosphine as an auxiliary ligand is homolytically cleaved under visible light irradiation at room temperature to afford molar nitride complexes. Conversely, reformed by oxidation complex temperature. This result provides a successful example cleavage and formation induced pair different external stimuli using single system assisted bearing ambient conditions.

This paper presents recent progress in catalytic transformation of molecular dinitrogen into ammonia or its equivalents, such as silylamine, especially using transition metal-dinitrogen complexes under ambient reaction conditions. Several systems have been recently established molybdenum-, iron-, and cobalt-dinitrogen their precursors catalysts, providing new approaches to the development novel nitrogen fixation

Abstract The development of transition metal‐catalyzed enantioselective propargylic substitution reactions has gained much progress in recent years, however, no successful example with phosphorus‐centered nucleophiles yet been reported until now. Herein, we report the first ruthenium‐catalyzed alcohols diarylphosphine oxides as nucleophiles. This synthetic approach provides a new method to prepare chiral phosphorus‐containing organic compounds.

A ruthenium cyclotriphosphato (P(3)O(9)(3-)) complex with a labile MeOH ligand can affect the vinylidene rearrangement of general internal alkynes via 1,2-migration alkyl, aryl, and acyl groups. This provides first alkyne-to-vinylidene isomerization high generality. Several intermediary eta(2)-alkyne complexes could be isolated were successfully transformed into corresponding complexes. The reaction mechanism is also discussed on basis kinetic study migratory aptitude groups; present...

A series of heterobimetallic complexes, including [M1Me(μ-η5:η1-C5H4PEt2)2M2Cp*] (5a, M1 = Zr, M2 Ru; 5b, Hf, 5c, Fe) have been prepared and characterized by X-ray analyses. Dehydrogenation Me2NH·BH3 takes place in the presence a catalytic amount these complexes. Studies on reaction pathway dehydrogenation lead us to propose cycle where two metal centers cooperatively participate catalysis. Here, hydride species serve as key intermediates.

Novel optically active ruthenium−allenylidene complexes are prepared and characterized by X-ray crystallography. Intramolecular edge-to-face aromatic π−π interaction in the allenylidene is observed between two phenyl groups chiral ligands, which may play a critical role achieving high enantioselectivity enantioselective propargylic substitution reactions of alcohols with nucleophiles.

Novel mono- and dimolybdenum-dinitrogen complexes bearing an arsenic-containing ANA-type pincer ligand are prepared characterized by X-ray analyses. These afford a stoichiometric amount of ammonia treatment with sulfuric acid at room temperature.

Fix me! Molybdenum–dinitrogen complexes containing ferrocenyldiphosphine and pentamethylcyclopentadienyl moieties as auxiliary ligands have been designed, prepared, characterized (see scheme). The works a unique ligand to inhibit dissociation of dinitrogen, well make the coordinated molecular dinitrogen reactive toward electrophiles. As service our authors readers, this journal provides supporting information supplied by authors. Such materials are peer reviewed may be re-organized for...

The molybdenum dinitrogen complex trans-[Mo(N2)2(dppe)2] (2) reacted with 2−2.5 equiv of various β-ketonitriles at room temperature to afford the (nitrido)(nitrile-enolato) complexes trans-[Mo(N)(NCCR1COR2)(dppe)2] (4; R1 = H, R2 4-MeOCOC6H4, 4-ClC6H4, 4-Tol, 4-MeOC6H4, 2-C4H3O, 2-C4H3S, Pri; CN, Me, Ph; dppe Ph2PCH2CH2PPh2) via C⋮N triple bond cleavage nitriles on center. On other hand, reaction 2 pivaloylacetonitrile led isolation (alkylideneamido)(nitrile-enolato)...

Abstract Molybdenum‐catalyzed conversion of molecular dinitrogen into ammonia under ambient reaction conditions has been achieved by using a proton source generated in situ from the ruthenium‐catalyzed oxidation water combination with visible light and photosensitizer. The preset system is considered as new model for nitrogen fixation photosynthetic bacteria.

Molybdenum complexes bearing an anionic pyrrole-based PNP-type pincer ligand have been prepared and found to work as catalysts for the conversion of N₂ into NH₃ under ambient conditions.

Cooperative photoredox- and nickel-catalyzed alkylative cyclization reactions of iodoalkynes with 4-alkyl-1,4-dihydropyridines as alkylation reagents under visible light irradiation have been achieved to afford the corresponding alkylated cyclopentylidenes in good high yields. Introduction substituents at propargylic position has led stereoselective formation E-isomers. The present reaction system provides a novel synthetic method for both terminal internal alkynes cooperative photoredox...

Dual photoredox- and nickel-catalyzed hydroalkylation of terminal alkynes with 4-alkyl-1,4-dihydropyridines under visible light irradiation to afford Markovnikov- or anti-Markovnikov-type alkylated alkenes in good-to-high yields has been achieved, which the regioselectivity products was effectively controlled by coordination ligands for nickel species. Using [NiCl2 (dtbbpy)] as a catalyst led formation Markovnikov-type products, whereas using NiCl2 ⋅ 6 H2 O products.

Dinuclear and mononuclear ruthenium complexes bearing an arsenic-containing arsenic-nitrogen-arsenic (ANA)-type pincer ligand are designed, prepared, characterized by X-ray analyses. Both work as effective catalysts toward dehydrogenative transformations of alcohols.