ChemInform Abstract: Transition-Metal Complexes with Sulfur Ligands. Part 49. Unusual Acid Base Reactions of Low Valence Ruthenium Nitrosyl Complexes with the Thiolate-amine Ligands “S2N2H”2- x (x = 1, 2) and Molybdenum Complexes with the Ligands “S2N2H”2

Abstract The addition reactions of N,N′-bis(diphenylphosphanylmethyl)-2,3-dihydro-1H-perimidine (1) with [(cod)2Ni] and [(Ph3P)AuCl] yield yellow [(1)Ni(η4-cod)] (2) and colorless [(1)(Ph3P)AuCl]·3MeOH (3), respectively. In these transition metal complexes of nickel(0) and gold(I) 1 acts as a bidentate chelating ligand. Crystal structures of [(1)Ni(η4-cod)]·3THF (2a) and of cosolvent-free [(1)Ni(η4-cod)] (2) reveal a distorted tetrahedral environment of the nickel atom. The gold(I) atom in 3 exhibits a very long Au-Cl bond of 296.2(1) pm. In contrast to the nickel complexes, compound 3 shows strong agostic interactions between gold(I) and a methylene fragment.

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Übergangsmetallkomplexe mit Schwefelliganden, XXXII: Synthese der sterisch anspruchsvollen Thiolat-amin-Liganden tbu2-ma-H = 2-Mercapto-3,5-di-tbutylanilin und tbu4-bmae-H2 = 1,2-Bis(2-mercapto-3,5-di-tbutylaniIino)ethan sowie ihrer Eisen-, Ruthenium- und Zink-Komplexe [Fe(CO)2(tbu2-ma)2], [Zn(tbu2-ma)2] und [RuL2(tbu4-bmae)], L = CO, PMe3, PPh3/ Transition Metal Complexes with Sulfur Ligands, XXXII: Synthesis of the Sterically Demanding New Thiolate-amine Ligands tbu2-ma-H = 2-Mercapto-3,5-di-tbutylanilin und tbu4-bmae-H2 = 1,2-Bis(2-mercapto-3,5-di-tbutylaniIino)ethane as well as of their Iron-, Ruthenium- and Zinc Complexes [Fe(CO)2(tbu2-ma)2], [Zn(tbu2-ma)2] and [RuL2(tbu4-bmae)], L = CO, PMe3, PPh3

Zeitschrift für Naturforschung B ◽

10.1515/znb-1987-1014 ◽

1987 ◽

Vol 42 (10) ◽

pp. 1291-1297 ◽

Cited By ~ 14

Author(s):

Dieter Sellmann ◽

Olaf Käppler

Keyword(s):

Transition Metal ◽

Metal Complexes ◽

Acid Hydrolysis ◽

Organic Solvents ◽

Transition Metal Complexes ◽

Zinc Complexes ◽

Metal Centers ◽

Sterically Demanding ◽

Amine Ligands ◽

Soluble Complexes

Abstract In order to obtain soluble complexes containing sterically protected metal centers the new bi- and tetradentate thiolate amine ligands 2-mercapto-3,5-di-tbutylaniline (= tbu2-ma-H) and 1,2-bis(2-mercapto-3,5-di-tbutylanilino)ethane (= tbu4-mae-H2) were synthesized. tbu2-ma-H reacts with FeCl2-4 H2O and CO to give [Fe(CO)2(tbu2-ma)2], with Zn(ac)2 -2 H2O [Zn(tbu2-ma)2] is obtained whose acid hydrolysis and reaction with H2S, respectively, yield pure tbu2-Ina-H. The condensation of tbu2-ma-H with glyoxal yields the respective bis-benzthiazolidine, which is reduced by LiAlH4 in the presence of Na[N(SiMe3)2] to tbu4-bmae-H2. tbu4-bmae-Li2. reacts with [Ru(CO)3(THF)Cl2], [Ru(PMe3)4Cl2] and [Ru(PPh3)2(CH3CN)2Cl2], respectively, to yield [Ru(L)2(Tm4-bmae)j (L = CO, PMe3, PPh3). The complexes are more soluble in organic solvents than the corresponding unsubstituted bmae complexes, bmae2- = 1,2-bis(2-mercaptoanilino)- ethane(2-).

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Development of Catalytic Conversion of Nitrogen Molecule into Ammonia Using Molybdenum Complexes under Ambient Reaction Conditions

Chemical Communications ◽

10.1039/d0cc07146c ◽

2021 ◽

Author(s):

Yuya Ashida ◽

Yoshiaki Nishibayashi

Keyword(s):

Nitrogen Fixation ◽

Transition Metal ◽

Metal Complexes ◽

Transition Metal Complexes ◽

Catalytic Conversion ◽

Nitrogen Molecule ◽

Reaction Conditions ◽

Molybdenum Complexes

Nitrogen fixation using homogeneous transition metal complexes under mild reaction conditions is a challenging topic in the field of chemistry. Several successful examples of the catalytic conversion of nitrogen molecule...

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