Charakterisierung von Distorsionsisomeren der Anionen Pentacyano‐oxo‐molybdat(IV) sowie Tetracyano‐oxo‐aqua‐molybdat(IV) im festen Zustand. Kristallstrukturen von [(C6H5)4P]3[MoO(CN)5] · 7 H2O(grün), [(C6H5)4As]2 [MoO(OH2)(CN)4] · 4 H2O (blau) und [(C6H5)4P]2[MoO(OH2)(CN)4] · 4 H2O (grün)

Wieghardt, Karl; Backes-Dahmann, G.; Holzbach, Wolfgang; Swiridoff, W.; Weiß, Johannes

doi:10.1002/zaac.19834990406

Cited by 46 publications

(12 citation statements)

References 11 publications

(2 reference statements)

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“…This is also in agreement with monodentate ligand substitution [9][10][11][12][13][14] which also indicated that the aqua molecule is by far the most labile ligand bonded to the metal center which will preferably be replaced as a first step in a bidentate substitution reaction. Fig.…”

Section: Discussionsupporting

confidence: 86%

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Kinetic study of reaction of [ReN(H2O)(CN)4]2− with quinoline-2-carboxylate and pyridine-2,3-dicarboxylate anions

Mtshali

Purcell

Visser

et al. 2008

Transition Met Chem

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The kinetics of the reaction between [ReN(H 2 O)(CN) 4 ] 2-with different j 2 N,O-donor ligands (quin -and 2,3-dipic -, respectively) have been studied in the pH 4-12 range in aqueous solution. Two consecutive reaction steps with the formation of the [ReN(g 1 -quin)(CN) 4 ] 3-and [ReN(l 2 -quin) (CN) 3 ] 2-complexes, respectively, were spectrophotometrically observed and kinetically investigated. The same reaction mechanism is proposed for these two ligands. The first fast reaction (for quin -) is attributed to the aqua substitution of [ReN(H 2 O)(CN) 4 ] 2-with forward and reverse rate constants of 1.96(5) 9 10 -1 M -1 s -1 and 5.6(3) 9 10 -2 s -1 , while a rate of 2.64(3) M -1 s -1 was observed for the reaction between the conjugate base [ReN(OH)(CN) 4 ] 3-and quin -at 40.2°C. Due to small absorbance changes, it was difficult to obtain any good quality data for the fast reactions for 2,3-dipic -. The second, slower reaction is attributed to cyano substitution with rate constants (k 3 K 1 ) of 4.17(4) 9 10 -3 for quin -and 4.68(7) 9 10 -3 M -1 s -1 for 2,3-dipic -, at 80.02°C, respectively. The acid dissociation constant for the aqua complex was spectrophotometrically determined as 11.58(3) and 11.54(2) and kinetically as 11.51(8) and 11.41(1), at 80.4°C, respectively. Negative DS 6 ¼ values of -83.5(2) and -144.1(2) J K -1 mol -1 as well as the DH 6 ¼ of 71.4(3) and 47.3(3) kJ mol -1 , for the slow quin -and 2,3-dipic -reactions, respectively, point to an ordered transition state where bond formation is responsible for the major driving force of the reaction. The DH 6 ¼ ¼ 39:6ð2Þ kJ mol À1 and DS 6 ¼ ¼ À142:8ð1Þ J K À1 mol À1 for the fast forward reaction of quin -is indicative of expected associative activation in the transition state.

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Section: Discussionsupporting

confidence: 86%

“…The hydroxo complexes are mostly inert towards substitution, whereas aqua complexes are reactive species. The reaction with monodentate ligands (such as, F -, NCS -, N 3 -, CN -and py) gives the aqua substituted complex of the type [MX(CN) 4 (L)] n- [9][10][11][12][13][14].…”

Section: Introductionmentioning

confidence: 99%

Kinetic study of reaction of [ReN(H2O)(CN)4]2− with quinoline-2-carboxylate and pyridine-2,3-dicarboxylate anions

Mtshali

Purcell

Visser

et al. 2008

Transition Met Chem

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“…The protonated oxygen bond length increased from 2.077 (7) 4 ] 2-, respectively [2][3][4]. The same tendency was observed for the corresponding complexes of tungsten(IV), rhenium(V) and technetium(V) [5][6][7][8][9].…”

Section: Introductionsupporting

confidence: 76%

“…It is, however interesting to note that the Re(2)-N(10) bond resulted in a somewhat longer trans-Re Table 3). The ethylenediamine, en, only has a r-donating sp 3 nitrogen donor 4 ] 2-complex that was isolated by Mtshali et al [23] but is significantly shorter than the corresponding bond length of 2.496(7) Å in the same structure that was isolated by Purcell et al [12] (see Table 3). …”

Section: O)(cn) 3 -(L-cn)-ren(cn) 4 ] 4-anion and Five Water Moleculesmentioning

confidence: 86%

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A novel rhenium-aqua structure: the synthesis and structural characterization of (PPh4)4[ReN(H2O)(CN)3-μ-CN-ReN(CN)4] · 5H2O

Mtshali

Purcell

Visser

et al. 2008

Transition Met Chem

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A novel cyano bridged rhenium nitrido complex, [ReN(H 2 O)(CN) 4 -l-CN-ReN(CN) 4 ] 4-(I) was isolated during a kinetic study of the reaction of ReN(H 2 O)(CN) 4 ] 2-with pyridine-2,3-dicarboxylic acid. Yellow crystals of (I), suitable for X-ray structure determination were isolated and the structural data showed an unsymmetrical binuclear rhenium complex with a cyano ligand acting as a bridge between two metal atoms, Re(1) and Re(2). The nitrogen of the bridged cyano ligand coordinates trans to the nitrido ligand of Re(1). The rhenium-nitrido bond distances are 1.657(4) and 1.656(5) Å for Re(1)-N(9) and Re(2)-N(10) respectively. Re(1) and Re(2) are displaced from the planes formed by the four carbon atoms of the cyano ligands towards the nitrido ligands by 0.348(2) and 0.3403(2) Å , respectively.

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The Chemistry of 1,4,7‐Triazacyclononane and Related Tridentate Macrocyclic Compounds

Chaudhuri

Wieghardt

1987

Progress in Inorganic Chemistry

302

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Cited by 46 publications

References 11 publications

Kinetic study of reaction of [ReN(H2O)(CN)4]2− with quinoline-2-carboxylate and pyridine-2,3-dicarboxylate anions

Kinetic study of reaction of [ReN(H2O)(CN)4]2− with quinoline-2-carboxylate and pyridine-2,3-dicarboxylate anions

A novel rhenium-aqua structure: the synthesis and structural characterization of (PPh4)4[ReN(H2O)(CN)3-μ-CN-ReN(CN)4] · 5H2O

The Chemistry of 1,4,7‐Triazacyclononane and Related Tridentate Macrocyclic Compounds

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