Skeletal vibrational spectra, force constants, and bond properties of transition metal ammine complexes
About: This article is published in Inorganic Chemistry.The article was published on 1975-09-01. It has received 60 citations till now. The article focuses on the topics: Metal K-edge & Metal L-edge.
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357 citations
TL;DR: In this paper, a series of Fe(SO3CF3)2 and one or two TPA ligands (TPA = tris(2-pyridylmethyl)amine) were used to demonstrate the complexities of the solid-state and solution coordination chemistry of labile iron(II) even with a multidentate ligand.
Abstract: The synthetic system of Fe(SO3CF3)2 and one or two TPA ligands (TPA = tris(2-pyridylmethyl)amine) affords a series of complexes that demonstrate the complexities of the solid-state and solution coordination chemistry of labile iron(II) even with a multidentate ligand. The low-spin [Fe(TPA)(CH3CN)2](SO3CF3)2 (1-OTf) complex forms in acetonitrile, but the high-spin complex Fe(TPA)(SO3CF3)2 (2) forms in chloroform. The methanol-bound complex [Fe(TPA)(CH3OH)2](BPh4)2 (3) forms in the presence of the noncoordinating anion, BPh4-, and six-coordinate [Fe(TPA)2](SO3CF3)2 (4-OTf) and eight-coordinate [Fe(TPA)2](BPh4)2 (4-BPh4) form in the presence of excess ligand. Their behavior in solution is explored by studying their magnetic properties and NMR spectra, which indicate the presence of spin and coordination equilibria. The crystal structures of these complexes are reported. Crystallographic parameters are as follows. 1-OTf·CH3CN: C26H27F6FeN7O6S2, monoclinic, P21/n, a = 12.418(2) A, b = 16.192(4) A, c = 15.855(...
126 citations
TL;DR: A one-step and energy-saving method was proposed to synthesize hierarchical and hollow Co(VO3)2-Co(OH)2 composite leaf arrays on carbon cloth, which expressed high capacitance and excellent cycling stability when tested as a supercapacitor electrode.
Abstract: A one-step and energy-saving method was proposed to synthesize hierarchical and hollow Co(VO3)2-Co(OH)2 composite leaf arrays on carbon cloth, which expressed high capacitance (522 mF cm–2 or 803 F g–1 at the current density of 0.5 mA cm–2), good rate capability (79.5% capacitance retention after a 30-fold increase of the current density) and excellent cycling stability (90% capacitance retention after 15 000 charge–discharge cycles) when tested as a supercapacitor electrode.
97 citations
TL;DR: In this paper, the authors used quantum path integral and classical molecular dynamics simulations and semi-empirical electronic structure calculations to investigate electron transfer mediated by a solvated polypeptide.
Abstract: Quantum rate theory, molecular dynamics simulations, and semiempirical electronic structure calculations are used to fully investigate electron transfer mediated by a solvated polypeptide for the first time. Using a stationary-phase approximation, the nonadiabatic electron-transfer rate constant is calculated from the nuclear free energies and the electronic coupling between the initial and final states. The former are obtained from quantum path integral and classical molecular dynamics simulations; the latter are calculated using semiempirical electronic structure calculations and the generalized Mulliken−Hush method. Importantly, no parameters are fit to kinetic data. The simulated system consists of a solvated four-proline polypeptide with a tris(bipyridine)ruthenium donor group and an oxypentamminecobalt acceptor group. From the simulation data entropy and energy contributions to the free energies are distinguished. Quantum suppression of the barrier, including important solvent contributions, is demo...
78 citations
78 citations
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TL;DR: In this article, the stability of complexes of bivalent metal ions follows the order of the order in which they are formed, and it is shown that the stability is not correlated with the order.
Abstract: MELLOR and Maley1,2 have recently pointed out that the stability of complexes of bivalent metal ions follows the order
1,015 citations
TL;DR: In this article, a method of setting up the vibrational secular equation for polyatomic molecules of ''Urey-Bradley field'' type is described, and 102 fundamental frequencies calculated using 28 distinct force constants are in satisfactory agreement with the observed, with a mean deviation of 1.4 percent.
Abstract: A method of setting up the vibrational secular equation for polyatomic molecules of ``Urey‐Bradley field'' type is described. By this method the vibration frequencies of CCl4, CBr4, CH4, CD4, CCl3Br, CCl2Br2, CClBr3, CCl3H, CCl2H2, CClH3, CCl3D, CCl2D2, CClD3, CH3D, CH2D2, and CHD3 molecules have been calculated. The 102 fundamental frequencies calculated using 28 distinct force constants are in satisfactory agreement with the observed, with a mean deviation of 1.4 percent.
351 citations
314 citations
TL;DR: In this paper, the rucktreibende Kraft verhalt sich bei Ein-, Zwei-and Dreifach bindungen wie 1:2:3, ist also ein Mas fur die Starke einer Bindung (Bindungsgrad).
Abstract: Es wird an Hand der Methylverbindungen eine Regel abgeleitet, die es gestattet, die es gestattet, die Kraftkonstante einer beliebigen Bindung ohne Kenntnis irgendwelcher experimenteller Grosen annahernd vorauszuberechnen („Produktregel”). Hierin treten neben einer universellen Konstanten nur die Kernladungszahlen der betreffenden Elemente sowie die Hauptquantenzahlen ihrer Valenzelektronen auf. Die haufig auftretenden Abweichungen von der Regel lassen sich stets auf konstitutionelle Beeinflussungen zuruckfuhren.
Weiter wird gezeigt, das die rucktreibende Kraft bei Verdopplung des Kernabstandes sich aus atomaren Inkrementen additiv zusammensetzen last („Summenregel”). Es kann bewiesen werden, das beide Regeln gleichwertig und universell gultig sind. Fur praktische Zwecke wird der Produktregel der Vorzug gegeben.
Die rucktreibende Kraft verhalt sich bei Ein-, Zwei- und Dreifachbindungen wie 1:2:3, ist also ein Mas fur die Starke einer Bindung (Bindungsgrad). Somit kann man aus der Kraftkonstanten auf den Bindungszustand schliesen. Diese Methode ist der von Pauling (Ermittlung des Bindungszustandes aus den Kernabstanden) haufig uberlegen.
191 citations