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Jacques Weber

Publications and source records attributed to Jacques Weber.

17 recordsLinked to original sources
PubMed2006

On line clinical reasoning assessment with Script Concordance test in urology: results of a French pilot study.

BACKGROUND: The Script Concordance test (SC) test is an assessment tool that measures the capacity to solve ill-defined problems, that is, reasoning in a context of uncertainty. This study assesses the feasibility, reliability and validity of the SC test made available on the Web to French urologists. METHODS: A 97 items SC test was developed based on major educational objectives of French urology training programmes. A secure Web site was created with two sequential modules: a) The first one for the reference panel to elaborate the scoring system; b) The second for candidates with different levels of experience in urology: Board certified urologists, chief-residents, residents, medical students. All participants were recruited on a voluntary basis. Statistical analysis included descriptive statistics of the participants' scores and factorial analysis of variance (ANOVA) to study differences between groups' means. Reliability was evaluated with Cronbach's alpha coefficient. RESULTS: The on line SC test has been operational since June 2004. Twenty-six faculty members constituted the reference panel. During the following 10 months, 207 participants took the test online (124 urologists, 29 chief-residents, 38 residents, 16 students). No technical problem was encountered. Forty-five percent of the participants completed the test partially only. Differences between the means scores for the 4 groups were statistically significant (P = 0.0123). The Bonferroni post-hoc correction indicated that significant differences were present between students and chief-residents, between students and urologists. There were no differences between chief-residents and urologists. Reliability coefficient was 0.734 for the total group of participants. CONCLUSION: Feasibility of Web-based SC test was proved successful by the large number of participants who participated in a few months. This Web site has permitted to quickly confirm reliability of the SC test and develop strategy to improve construct validity of the test when applied in the field of urology. Nevertheless, optimisation of the SC test content, with a smaller number of items will be necessary. Virtual medical education initiative such as this SC test delivered on the Internet warrants consideration in the current context of national pre-residency certification examination in France.

Academic Medical Centers↗
PubMed2006

A web-based teaching resource to prepare for final undergraduate examination: a French pilot study.

Access to accurate and quality-controlled health information on the Internet for medical students is not an easy task. CISMeF is the search tool of a MeSH-indexed directory of medical Internet resources in French. Since 2004, a new French Pre-Residency Examination (PRE) is compulsory for all medical students in the 6th year of the curriculum. The goal of this study is to evaluate CISMeF as a tool to provide teaching resources available on the Internet covering PRE material. The CISMeF terminology and the PRE CISMeF module are described. To assess the CISMeF performance in covering PRE program, its precision (number of relevant resources/number of overall resources extracted by CISMeF) and coverage (number of PRE questions covered by at least one resource in the CISMeF gateway) were computed. The CISMeF module for the new French Pre-Residency Examination is efficient as it already covers 95.7% of the program with a precision of 82.2%. Our data demonstrates that CISMeF is acceptable to guide students' learning and should be a useful teaching resource for the preparation of the French Pre-Residency Examination.

Education, Medical, Undergraduate↗
PubMed2005

Online clinical reasoning assessment with the Script Concordance test: a feasibility study.

BACKGROUND: The script concordance (SC) test is an assessment tool that measures capacity to solve ill-defined problems, that is, reasoning in context of uncertainty. This tool has been used up to now mainly in medicine. The purpose of this pilot study is to assess the feasibility of the test delivered on the Web to French urologists. METHODS: The principle of SC test construction and the development of the Web site are described. A secure Web site was created with two sequential modules: (a) The first one for the reference panel (n = 26) with two sub-tasks: to validate the content of the test and to elaborate the scoring system; (b) The second for candidates with different levels of experience in Urology: Board certified urologists, residents, medical students (5 or 6th year). Minimum expected number of participants is 150 for urologists, 100 for residents and 50 for medical students. Each candidate is provided with an individual access code to this Web site. He/she may complete the Script Concordance test several times during his/her curriculum. RESULTS: The Web site has been operational since April 2004. The reference panel validated the test in June of the same year during the annual seminar of the French Society of Urology. The Web site is available for the candidates since September 2004. In six months, 80% of the target figure for the urologists, 68% of the target figure for the residents and 20% of the target figure for the student passed the test online. During these six months, no technical problem was encountered. CONCLUSION: The feasibility of the web-based SC test is successful as two-thirds of the expected number of participants was included within six months. Psychometric properties (validity, reliability) of the test will be evaluated on a large scale (N = 300). If positive, educational impact of this assessment tool will be useful to help urologists during their curriculum for the acquisition of clinical reasoning skills, which is crucial for professional competence.

Clinical Competence↗
PubMed2005

Vibrational and electronic circular dichroism of delta-TRISPHAT [tris(tetrachlorobenzenediolato)phosphate(V)] anion.

Herein is reported an experimental and theoretical study of the circular dichroism properties of TRISPHAT (1) anion. ECD analysis of the [tetramethylammonium][delta-1] salt confirms the absolute configuration assignment obtained through X-ray crystallographic analysis of the parent cinchonidium salt. The structure, infrared, and vibrational circular dichroism (VCD) spectra derived from density functional theory (DFT) calculations are compared with experimental data.

Journal Article↗
PubMed2004

[CpRu((R)-Binop-F)(H2O)][SbF6], a new fluxional chiral Lewis acid catalyst: synthesis, dynamic nmr, asymmetric catalysis, and theoretical studies.

The C(2)-symmetric electron-poor ligand (R)-BINOP-F (4) was prepared by reaction of (R)-BINOL with bis(pentafluorophenyl)-phosphorus bromide in the presence of triethylamine. The iodo complex [CpRu((R)-BINOP-F)(I)] ((R)-6) was obtained by substitution of two carbonyl ligands by (R)-4 in the in situ-prepared [CpRu(CO)(2)H] complex followed by reaction with iodoform. Complex 6 was reacted with [Ag(SbF(6))] in acetone to yield [CpRu((R)-BINOP-F)(acetone)][SbF(6)] ((R)-7). X-ray structures were obtained for both (R)-6 and (R)-7. The chiral one-point binding Lewis acid [CpRu((R)-BINOP-F)][SbF(6)] derived from either (R)-7 or the corresponding aquo complex (R)-8 activates methacrolein and catalyzes the Diels-Alder reaction with cyclopentadiene to give the [4 + 2] cycloadduct with an exo/endo ratio of 99:1 and an ee of 92% of the exo product. Addition occurs predominantly to the methacrolein C(alpha)-Re face. In solution, water in (R)-8 exchanges readily. Moreover, a second exchange process renders the diastereotopic BINOP-F phosphorus atoms equivalent. These processes were studied by the application of variable-temperature (1)H, (31)P, and (17)O NMR spectroscopy, variable-pressure (31)P and(17)O NMR spectroscopy, and, using a simpler model complex, density functional theory (DFT) calculations. The results point to a dissociative mechanism of the aquo ligand and a pendular motion of the BINOP-F ligand. NMR experiments show an energy barrier of 50.7 kJ mol(-1) (12.2 kcal mol(-1)) for the inversion of the pseudo-chirality at the ruthenium center.

Journal Article↗
PubMed2004

Calculated volume and energy profiles for water exchange on t2g6 rhodium(III) and iridium(III) hexaaquaions: conclusive evidence for an Ia mechanism.

An I(a) mechanism was assigned for water exchange on the hexaaquaions Rh(OH(2))(6)(3+) and Ir(OH(2))(6)(3+) on the basis of negative Delta V(++) experimental values (-4.2 and -5.7 cm(3) mol(-1), respectively). The use of Delta V(++) as a mechanistic criterion was open to debate primarily because Delta V(++) could be affected by extension or compression of the nonparticipating ligand bond lengths on going to the transition state of an exchange process. In this paper, volume and energy profiles for two distinct water exchange mechanisms (D and I(a)) have been computed using quantum chemical calculations which include hydration effects. The activation energy for Ir(OH(2))(6)(3+) is 32.2 kJ mol(-1) in favor of the I(a) mechanism (127.9 kJ mol(-1)), as opposed to a D pathway; the value for the I(a) mechanism being close to Delta H(++) and Delta G(++) experimental values (130.5 kJ mol(-1) and 129.9 kJ mol(-1) at 298 K, respectively). Volumes of activation, computed using Connolly surfaces and for the I(a) pathway (DeltaV(++)(calc) = -3.9 and -3.5 cm(3) mol(-1), respectively, for Rh(3+) and Ir(3+)), are in agreement with the experimental values. Further, it is demonstrated for both mechanisms that the contribution to the volume of activation due to the changes in bond lengths between Ir(III) and the spectator water molecules is negligible: -1.8 for the D, and -0.9 cm(3) mol(-1) for I(a) mechanism. This finding clarifies the debate about the interpretation of Delta V(++) and unequivocally confirms the occurrence of an I(a) mechanism with retention of configuration and a small a character for both Rh(III) and Ir(III) hexaaquaions.

Journal Article↗
PubMed2004

Tuning facial-meridional isomerisation in monometallic nine-co-ordinate lanthanide complexes with unsymmetrical tridentate ligands.

The unsymmetrical tridentate benzimidazole-pyridine-carboxamide units in ligands L1-L4 react with trivalent lanthanides, Ln(III), to give the nine-co-ordinate triple-helical complexes [Ln(Li)3]3+ (i = 1-4) existing as mixtures of C3-symmetrical facial and C1-symmetrical meridional isomers. Although the beta13 formation constants are 3-4 orders of magnitude smaller for these complexes than those found for the D3-symmetrical analogues [Ln(Li)3]3+ (i = 5-6) with symmetrical ligands, their formation at the millimolar scale is quantitative and the emission quantum yield of [Eu(L2)3]3+ is significantly larger. The fac-[Ln(Li)3]3+ <--> mer-[Ln(Li)3]3+ (i = 1-4) isomerisation process in acetonitrile is slow enough for Ln = Lu(III) to be quantified by 1H NMR below room temperature. The separation of enthalpic and entropic contributions shows that the distribution of the facial and meridional isomers can be tuned by the judicious peripheral substitution of the ligands affecting the interstrand interactions. Molecular mechanics (MM) calculations suggest that one supplementary interstrand pi-stacking interaction stabilises the meridional isomers, while the facial isomers benefit from more favourable electrostatic contributions. As a result of the mixture of facial and meridional isomers in solution, we were unable to obtain single crystals of 1:3 complexes, but the X-ray crystal structures of their nine-co-ordinate precursors [Eu(L1)2(CF3SO3)2(H2O)](CF3SO3)(C3H5N)2(H2O) (6, C45H54EuF9N10O13S3, monoclinic, P2(1)/c, Z = 4) and [Eu(L4)2(CF3SO3)2(H2O)](CF3SO3)(C4H4O)(1.5) (7, C51H66EuF9N8O(15.5)S3, triclinic, P1, Z = 2) provide crucial structural information on the binding mode of the unsymmetrical tridentate ligands.

Journal Article↗
PubMed2004

Foot orthotics decrease pain but do not improve gait in rheumatoid arthritis patients.

OBJECTIVES: Prescribing foot orthotics in rheumatoid arthritis patients with symptomatic forefoot involvement is a standard practice. However, limited research has been reported regarding gait and pain improvement with the use of foot orthotics. PATIENTS AND METHODS: Sixteen patients (13 F, 3 M; mean age: 52 +/- 12 years) with metatarsalgia due to rheumatoid arthritis were included in this prospective, randomized with crossover study, and received foot orthotics. At 1 month follow-up, space and time gait variables with and without foot orthotics were assessed by Bessou's locometer; pain was assessed by visual analogue scale (VAS). RESULTS: Pain levels significantly decreased (P = 0.008) by wearing foot orthotics. Despite a significant step length increase (P = 0.05) with orthotics, there was no significant improvement of stride length, cadence, or walking speed which was the main assessment criterion. CONCLUSIONS: Wearing foot orthotics improves pain, but not sufficiently to improve gait in rheumatoid arthritis patients with metatarsalgia. Foot orthotics improved comfort levels because of a decrease in pain, but was not sufficient to correct gait.

Adult↗
PubMed2003

Connecting terminal carboxylate groups in nine-coordinate lanthanide podates: consequences on the thermodynamic, structural, electronic, and photophysical properties.

The hydrolysis of terminal (t)butyl-ester groups provides the novel nonadentate podand tris[2-[N-methylcarbamoyl-(6-carboxypyridine-2)-ethyl]amine] (L13) which exists as a mixture of slowly interconverting conformers in solution. At pH = 8.0 in water, its deprotonated form [L13 - 3H](3-) reacts with Ln(ClO(4))(3) to give the poorly soluble and stable podates [Ln(L13 - 3H)] (log(beta(110)) = 6.7-7.0, Ln = La-Lu). The isolated complexes [Ln(L13 - 3H)](H(2)O)(7) (Ln = Eu, 8; Tb, 9; Lu, 10) are isostructural, and their crystal structures show Ln(III) to be nine-coordinate in a pseudotricapped trigonal prismatic site defined by the donor atoms of the three helically wrapped tridentate binding units of L13. The Ln-O(carboxamide) bonds are only marginally longer than the Ln-O(carboxylate) bonds in [Ln(L13 - 3H)], thus producing a regular triple helix around Ln(III) which reverses its screw direction within the covalent Me-TREN tripod. High-resolution emission spectroscopy demonstrates that (i) the replacement of terminal carboxamides with carboxylates induces only minor electronic changes for the metallic site, (ii) the solid-state structure is maintained in water, and (iii) the metal in the podate is efficiently protected from interactions with solvent molecules. The absolute quantum yields obtained for [Eu(L13 - 3H)] (Phi(Eu)(tot)= 1.8 x 10(-3)) and [Tb(L13 - 3H)] (Phi(Eu)(tot)= 8.9 x 10(-3)) in water remain modest and strongly contrast with that obtained for the lanthanide luminescence step (Phi(Eu) = 0.28). Detailed photophysical studies assign this discrepancy to the small energy gap between the ligand-centered singlet ((1)pi pi*) and triplet ((3)pi pi*) states which limits the efficiency of the intersystem crossing process. Theoretical TDDFT calculations suggest that the connection of a carboxylate group to the central pyridine ring prevents the sizable stabilization of the triplet state required for an efficient sensitization process. The thermodynamic and electronic origins of the advantages (stability, lanthanide quantum yield) and drawbacks (solubility, sensitization) brought by the "carboxylate effect" in lanthanide complexes are evaluated for programming predetermined properties in functional devices.

Journal Article↗
PubMed2003

The change of aromaticity along a Diels-Alder reaction path.

[reaction: see text] Quinodimethanes are highly reactive toward dienophiles since Diels-Alder cycloaddition results in an aromatic product. Density functional-based (13)C, (1)H NMR, NICS, and MO-NICS calculations indicate that the increase of aromatic character of the developing benzenoid ring along the reaction path is especially pronounced after the transition state is reached, even though the number of pi orbitals decreases. The forming aliphatic ring exhibits large ring current effects during the reaction.

Journal Article↗
PubMed2002

Analysis of paramagnetic NMR spectra of triple-helical lanthanide complexes with 2,6-dipicolinic acid revisited: a new assignment of structural changes and crystal-field effects 25 years later.

Variable-temperature (1)H and (13)C NMR measurements of the D(3)-symmetrical triple-helical complexes [Ln(L1-2H)(3)](3)(-) (L1 = pyridine-2,6-dicarboxylic acid; Ln = La-Lu) show evidence of dynamic intermolecular ligand-exchange processes whose activation energies depend on the size of the metal ion. At 298 K, the use of diastereotopic probes in [Ln(L3-2H)(3)](3)(-) (L3 = 4-ethyl-pyridine-2,6-dicarboxylic acid) shows that fast intramolecular P <==> M interconversion between the helical enantiomers occurs on the NMR time scale. Detailed analyses of the paramagnetic NMR hyperfine shifts according to crystal-field independent techniques demonstrate the existence of two different helical structures, one for large lanthanides (Ln = La-Eu) and one for small lanthanides (Ln = Tb-Lu), in complete contrast with the isostructurality proposed 25 years ago. A careful reconsideration of the original crystal-field-dependent analysis shows that an abrupt variation of the axial crystal-field parameter A(0)2 parallels the structural change leading to some accidental compensation effects that prevent the detection of structural variations according to the classical one-nucleus method. Crystal structures in the solid state and density functional theory calculations in the gas phase provide structural models that rationalize the paramagnetic NMR data. A regular triple-helical structure is found for small lanthanides (Ln = Tb-Lu) in which the terdentate chelating ligands are rigidly tricoordinated to the metals. A flexible and distorted structure is evidenced for Ln = La-Eu in which the central pyridine rings interact poorly with the metal ion. The origin of the simultaneous variation of structural parameters and crystal-field and hyperfine constants near the middle of the lanthanide series is discussed together with the use of crystal-field-independent techniques for the interpretation of paramagnetic NMR spectra in axial lanthanide complexes.

Journal Article↗
PubMed2002

Communication between consultants and referring physicians: a qualitative study to define learning and assessment objectives in a specialty residency program.

BACKGROUND: Outpatient consultation constitutes a major part of medical practice. However, little is known about the skills which should be taught to residents in order for them to improve their consultant-referring physician relationships. PURPOSES: To specify the consultant skills which are required to ensure an effective communication between specialists and referring physicians. METHODS: A qualitative study based on (a) a literature search and (b) focus group interviews. RESULTS: Skills thus identified and described are classified in two groups: observable skills and principles/attitudes. CONCLUSIONS: The consensual specification of these abilities permits a greater efficacy in the teaching of consultant skills.

Ambulatory Care↗
PubMed2002

[Patient-doctor relationship in the irritable bowel syndrome. Results of a French prospective study on the influence of the functional origin of the complaints].

UNLABELLED: The attention given by the physician and the quality of the patient-physician relationship mainly determine the outcome of a consultation. Care seeking is a main characteristic of patients with functional bowel disorders, including irritable bowel syndrome (IBS), while patients with suspected organic disease (Org) would rather expect a precise answer about their condition. The aim of this study was thus to evaluate the outcome of the consultation with a gastroenterologist in IBS patients, as compared to a group of patients with suspected organic disease. PATIENTS AND METHODS: A prospective multicenter cross-sectional study "one given week" included 158 patients consulting for the first time 18 gastroenterologists. Patients were consulting for abdominal pain and were classified as IBS or Org on the basis of the physician's clinical impression. Questionnaires including 27 common questions were distributed to the patients and the physicians at the end of the consultation and filled separately. RESULTS: The diagnosis of IBS was done in 110 patients and that of Org in 48. Groups were comparable for the characteristics, the intensity and the frequency of attacks of abdominal pain. The index of satisfaction of the patients was not different between groups (IBS: 8.7 +/- 1.4; Org: 9.1 +/- 1.4; P=0.16). The intensity of abdominal pain was reported in the same range by the patient (IBS: 5.1 +/- 2.9; Org: 4.5 +/- 2.8) and the physician (IBS: 4.6 +/- 2.3; Org: 4.8 +/- 2.6) in both groups. Digestive and extra-digestive symptoms were quoted equally by physicians, whatever the group the patient belonged to. Information given by the physician on diagnosis and therapy were equally well perceived by patients of both groups. However, the physician tended to evaluate the efficacy of the prescribed therapy to be lower in IBS (7.1 +/- 2.0) than in Org patients (8.0 +/- 1.7; P<0.01). CONCLUSION: In this study, the consultation with a gastroenterologist is equally well perceived by IBS and Org patients and it seems to meet the expectancy of the patient in most cases. However, the physician appeared less confident in the efficacy of the therapy proposed to IBS patients.

Adult↗
PubMed2001

Introducing the objective structured clinical examination to a general practice residency programme: results of a French pilot study.

OSCE for evaluating clinical competence still remains limited in France. This study presents the results of the first experimental use of an OSCE as a formative assessment of French general practice trainees. Fifty trainees rotated through a circuit of 15 standardized patient-based OSCE cases. Differences in scores were determined by analysis of variance. Reliability was calculated with the coefficient alpha. Pearson correlations were used to determine the relationship between station scores and overall OSCE score. Written questionnaires based on Likert-type scales were used to measure OSCE feasibility. No difference was found between total session scores. Significant item-total score correlations were found for 12 of the 15 clinical problems. The reliability of the examination was 0.58. Most participants agreed that the clinical situations were realistic, simulated patients were believable and sampling of cases was representative of general practice. These data confirm the feasibility of OSCE in assessing performance of general practice trainees. Optimal training of observers should improve examination reliability. This study warrants further development to confirm its usefulness as a summative assessment tool.

Journal Article↗
PubMed1998

Structure and Reactivity of [Mo(3)-&mgr;(3)S-(&mgr;S(2))(3)](4+) Complexes. Quantum Chemical Calculations, X-ray Structural Characterization, and Raman Spectroscopic Measurements.

A series of compounds containing the [Mo(3)-&mgr;(3)S-(&mgr;S(2))(3)-(dtc)(3)](+) complex (dtc = diethyldithiocarbamate) with the anions I(-) (1), I(-) and Br(-) (2), S(2)(-) (3), ClO(4)(-) (4), NO(3)(-) (5), and SO(4)(2)(-) (6) was prepared and characterized by elemental analysis, NMR, IR, and Raman spectroscopy, and FAB mass spectrometry. The previously reported crystal structure of 1 was reinvestigated. The X-ray analysis revealed the incorporation of CH(2)Cl(2) in the crystal having the composition [Mo(3)S(7)(dtc)(3)]I.0.5CH(2)Cl(2) (1a), which was in contradiction to the previous protocol. The corresponding ClO(4)(-) compound (4a) is isotypic. Crystal data: C(15.5)H(31)Cl(2)Mo(3)N(3)O(4)S(13), orthorhombic space group Aba2, a = 25.816(5) Å, b = 17.761(4) Å, c = 16.250(3) Å, Z = 8. For 1a, 4a, 6, and the previously analyzed 2 and 3 the crystal structures revealed characteristic interactions between the anions X and the three axial (out-of-plane) sulfur atoms S(ax) of the disulfido bridges. The Raman data showed a significant decrease of the S(eq)-S(ax) stretch resonance frequency in the order 4, 5, 6 > 1 > 3. This decrease is paralleled with a slight increase of the S(eq)-S(ax) bond length and with a significant shortening of the X.S(ax) distances when compared to the sum of the corresponding van der Waals radii. A comprehensive quantum chemical study, using both density functional theory and semiempirical calculations, revealed that for hard counterions such as NO(3)(-) and ClO(4)(-) the S(ax).X interactions can be understood in terms of an almost entirely electrostatic interaction, whereas for soft nucleophiles such as I(-) and S(2)(-) significant covalency is observed. In addition, the general reaction of [Mo(3)S(7)](4+) complexes with a nucleophile was modeled. With regard to the side-on bonding of the &mgr;-S(2) groups to Mo, the calculations indicated a significantly higher bond energy for the axial (out-of-plane) sulfur atoms, explaining the much higher lability of the sulfur atoms in the equatorial (in-plane) position. Analogous differences for the ligating atoms of the peripheral ligands, having a cis and trans position with respect to &mgr;(3)-S, are less pronounced.

Journal Article↗
PubMed1997

Trans- and Cis-Water Reactivities in d(6) Octahedral Ruthenium(II) Pentaaqua Complexes: Experimental and Density Functional Theory Studies(1)(,)(2).

The hexaaqua complex of ruthenium(II) represents an ideal starting material for the synthesis of isostructural compounds with a [Ru(H(2)O-ax)(H(2)O-eq)(4)L](2+) general formula. We have studied a series of complexes, where L = H(2)O, MeCN, Me(2)SO, H(2)C=CH(2), CO, and F(2)C=CH(2). We have evaluated the effect of L on the cyclic voltammetric response, on the rate and mechanism of exchange reaction of the water molecules, and on the structures calculated with the density functional theory (DFT). As expected, the formal redox potential, E degrees '(+2/+3), increases with the pi-accepting capabilities of the ligands. For L = N(2), the oxidation to Ru(III) is followed by a fast substitution of dinitrogen by a solvent molecule, revealing the poor stability of the Ru(III)-N(2) bond. The water exchange reactions have been followed by (17)O NMR spectroscopy. The variable-pressure and variable-temperature kinetic studies made on selected examples are all in accordance with a dissociative activation mode for exchange. The positive activation volumes obtained for the axial and equatorial water exchange reactions on [Ru(H(2)O)(5)(H(2)C=CH(2))](2+) (DeltaV(ax)() and DeltaV(eq)() = +6.5 +/- 0.5 and +6.1 +/- 0.2 cm(3) mol(-)(1)) are the strongest evidence of this conclusion. The increasing cis-effect series was established according to the lability of the equatorial water molecules and is as follows: F(2)C=CH(2) congruent with CO < Me(2)SO < N(2) < H(2)C=CH(2) < MeCN < H(2)O. The increase of the lability is accompanied by a decrease of the E degrees ' values, but no change was found in the calculated Ru-H(2)O(eq) bond lengths. The increasing trans-effect series, established from the lability of the axial water molecule, is the following: N(2) << MeCN < H(2)O < CO < Me(2)SO < H(2)C=CH(2) < F(2)C=CH(2). A variation of the Ru-H(2)O(ax) bond lengths is observed in the calculated structures. However, the best correlation is found between the lability and the calculated Ru-H(2)O(ax) bond energies. It appears, also, that a decrease of the electronic density along the Ru-O(ax) bond and the increase of the lability can be related to an increase of the pi-accepting capability of the ligand. For L = N(2), the calculations have shown that the Ru(II)-N(2) bond is weak. Consequently, the water exchange reaction proceeds through a different mechanism, where first the N(2) ligand is substituted by one water molecule to produce the hexaaqua complex of Ru(II). The water exchange takes place on this compound before re-formation of the [Ru(H(2)O)(5)N(2)](2+) complex.

Journal Article↗