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Octahedral molecular geometry
About: Octahedral molecular geometry is a research topic. Over the lifetime, 5986 publications have been published within this topic receiving 103241 citations.
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TL;DR: Five new metal-organic frameworks based on 2,4,6-tris(4-pyridyl)-1,3,5-triazine (tpt) ligand have been hydrothermally synthesized and Luminescence study shows that 1, 3, 4, and 5 have blue fluorescence, which can be assigned to be ligand-centered emissions.
Abstract: Five new metal-organic frameworks based on 2,4,6-tris(4-pyridyl)-1,3,5-triazine (tpt) ligand have been hydrothermally synthesized. Reaction of tpt and AgNO 3 in an acidic solution at 180 degrees C yields {[Ag(Htpt)(NO3)]NO(3).4H2O}n (1).Ag(I) is trigonally coordinated by two pyridyl nitrogen and one nitrato oxygen to form a 1D zigzag chain. Reaction of tpt with CuSO4 affords {[Cu2(tpt)2(SO4)2(H2O)2].4H2O}n (2). Copper(II) is bonded to two pyridyl nitrogen, two sulfato oxygen, and two water oxygen atoms to form an elongated octahedral geometry. Each H2O ligand bridges two copper(II), whereas sulfate bridges copper(II) via micro-1,3 and micro-1,1 fashions. The copper(II)-sulfate-H2O2D layers are linked by bidentate tpt to form a 3D polymeric structure. Reaction of Cu(SO4)2, tpt, and 1,2,4,5-benzenetetracarboxylic acid (H4btec) in the presence of piperidine gives [Cu(tpt)(H2btec)1/2]n (3). Copper(I) is located in a trigonal-pyramidal coordination environment and coordinated by three pyridyl nitrogen of tpt in a plane, whereas a carboxylate oxygen is coordinated to the copper(I) axially. The tpt-Cu forms a layer, and the layers are linked through H 2btec2- to form a 2D double-layered coordination polymer. Replacing CuSO4 with ZnI2 in the synthesis gives {[Zn(tpt)(btec)1/2].H2O}n (4). Zinc(II) is in a distorted tetrahedral geometry and linked through bidentate tpt and exotetradentate btec4- to form a 2D coordination grid. Reaction of tpt with CuCN leads to the assembly of a 3D metal-organic framework [Cu3(CN)3(tpt)]n (5). Copper(I) is trigonally coordinated by one pyridyl nitrogen and two cyanides to form an intriguing honeycomb architecture. Luminescence study shows that 1, 3, 4, and 5 have blue fluorescence, which can be assigned to be ligand-centered emissions. Thermal analysis shows that all of these complexes are quite stable, and especially for 4, the framework is stable up to 430 degrees C.
156 citations
TL;DR: The study revealed the formation of a Mn(III,IV) dinuclear cluster in direct correlation with expoxide formation and offers insight into the mechanism of catalyst degradation and formation of unwanted byproducts.
Abstract: Dual-mode electron paramagnetic resonance (EPR), in which an oscillating magnetic field is alternately applied parallel or perpendicular to the static magnetic field, is a valuable technique for studying both half-integer and integer electron spin systems and is particularly useful for studying transition metals involved in redox chemistry. We have applied this technique to the characterization of the Mn(III) salen (salen = N,N'-ethylene bis(salicylideneaminato)) complex [(R,R)-(-)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminomanganese(III)], with an S = 2 integer electron spin system. Furthermore, we have used dual-mode EPR to study the Mn salen complex during the Mn(III) salen-catalyzed epoxidation of cis-beta-methylstyrene. Our study shows that the additives N-methylmorpholine N-oxide (NMO) and 4-phenylpyridine-N-oxide (4-PPNO), which are used to improve epoxidation yields and enantioselection, bind to the Mn(III) center prior to the epoxidation reaction, as evidenced by the alteration of the Mn(III) parallel mode EPR signal. With these additives as ligands, the axial zero-field splitting values and (55)Mn hyperfine splitting of the parallel mode signal are indicative of an axially elongated octahedral geometry about the Mn(III) center. Since the dual-mode EPR technique allows the observation of both integer and half-integer electron spin systems, Mn oxidation states of II, III, IV, and potentially V can be observed in the same sample as well as any radical intermediates or Mn(III,IV) dinuclear clusters formed during the Mn(III) salen-catalyzed epoxidation reaction. Indeed, our study revealed the formation of a Mn(III,IV) dinuclear cluster in direct correlation with expoxide formation. In addition to showing the possible reaction intermediates, dual-mode EPR offers insight into the mechanism of catalyst degradation and formation of unwanted byproducts. The dual-mode technique may therefore prove valuable for elucidating the mechanism of Mn(III) salen catalyzed reactions and ultimately for designing optimum catalytic conditions (solvents, oxidants, and additives such as NMO or 4-PPNO).
156 citations
TL;DR: The high-spin dichloro Mn2+ and Fe2+ complexes of 4,11-dimethyl-1,4,8, 11-tetraazabicyclo[6.2]hexadecane (1) and 4,10-dimethylamine-1.4,7,10,10 -tetrasabicycleclo [5.5]tetradecANE (2) provide durable new compounds of these elements for important fundamental studies and applications as discussed by the authors.
Abstract: The high-spin dichloro Mn2+ and Fe2+ complexes of 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane (1) and 4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane (2) provide durable new compounds of these elements for important fundamental studies and applications. The compounds are especially noteable for their exceptional kinetic stabilities and redox activity. The X-ray crystal structures of all four complexes demonstrate that the ligands enforce a distorted octahedral geometry on the metals with two cis sites occupied by labile chloride ligands. Magnetic measurements reveal that all are high spin with typical magnetic moments. Cyclic voltammetry of the complexes shows reversible redox processes at +0.110 and +0.038 V (versus SHE) for the Fe3+/Fe2+ couples of Fe(1)Cl2 and Fe(2)Cl2, respectively, while the Mn3+/Mn2+ and Mn4+/Mn3+ couples were observed at +0.585 and +1.343 V, and +0.466 and +1.232 V for the complexes Mn(1)Cl2 and Mn(2)Cl2, respectively. Mn2+(1) was found to react with H2O2 and o...
156 citations
TL;DR: The thiosemicarbazone derivative of 9,10-phenanthrenequinone, 1, and its metal complexes were synthesized and the X-ray crystal structure confirms the presence of the E tautomeric arrangement in this compound.
155 citations
TL;DR: The chiral lithium (−)-trimethylsilylmyrtanyl amide reacts with benzonitrile yielding the chiral benzamidinate lithium ligand as mentioned in this paper, which has an octahedral structure with the oxygen atom and one chlorine atom at the apical positions.
Abstract: The chiral lithium (−)-trimethylsilylmyrtanyl amide reacts with benzonitrile yielding the chiral benzamidinate lithium ligand ([N-trimethylsilyl][N‘-myrtanyl]benzamidinate Li·TMEDA (TMEDA = tetramethylethylenediamine), [N(R*)−C−N]Li. An X-ray study shows that the ligand has a distorted tetrahedral environment in which the lithium atom is arranged symmetrically between the two benzamidinate and the two TMEDA nitrogen atoms. Equimolar addition of [N(R*)−C−N]Li to TiCl4 in THF yields [N(R*)−C−N]TiCl3·THF (1). An X-ray study of 1 shows that it has an octahedral structure with the oxygen atom and one chlorine atom at the apical positions. [N(R*)−C−N]3ZrCl·toluene (2) can be prepared in a manner related to that employed to synthesize 1. An X-ray study of 2 shows that it has a capped octahedral geometry with the three trimethylsilyl groups in a cis position with respect to the chlorine atom and the other three myrtanyl groups arranged on the opposite side of the chlorine. Addition of MeLi·LiBr to complex 2 yield...
154 citations