Lattice solvent- and substituent-dependent spin-crossover in isomeric iron(II) complexes.

Spin-state switching in iron(II) complexes composed of ligands featuring moderate ligand-field strength-for example, 2,6-bi(1H-pyrazol-1-yl)pyridine (BPP)-is dependent on many factors. Herein, we show that spin-state switching in isomeric iron(II) complexes composed of BPP-based ligands-ethyl 2,6-bis(1H-pyrazol-1-yl)isonicotinate (BPP-COOEt, L1) and (2,6-di(1H-pyrazol-1-yl)pyridin-4-yl)methylacetate (BPP-CH2OCOMe, L2)-is dependent on the nature of the substituent at the BPP skeleton. Bi-stable spin-state switching-with a thermal hysteresis width (ΔT1/2) of 44 K and switching temperature (T1/2) = 298 K in the first cycle-is observed for complex 1·CH3CN composed of L1 and BF4- counter anions. Conversely, the solvent-free isomeric counterpart of 1·CH3CN-complex 2a, composed of L2 and BF4- counter anions-was trapped in the high-spin (HS) state. For one of the polymorphs of complex 2b·CH3CN-2b·CH3CN-Y, Y denotes yellow colour of the crystals-composed of L2 and ClO4- counter anions, a gradual and non-hysteretic SCO is observed with T1/2 = 234 K. Complexes 1·CH3CN and 2b·CH3CN-Y also underwent light-induced spin-state switching at 5 K due to the light-induced excited spin-state trapping (LIESST) effect. Structures of the low-spin (LS) and HS forms of complex 1·CH3CN revealed that spin-state switching goes hand-in-hand with pronounced distortion of the trans-N{pyridyl}-Fe-N{pyridyl} angle (ϕ), whereas such distortion is not observed for 2b·CH3CN-Y. This observation points that distortion is one of the factors making the spin-state switching of 1·CH3CN hysteretic in the solid state. The observation of bi-stable spin-state switching with T1/2 centred at room temperature for 1·CH3CN indicates that technologically relevant spin-state switching profiles based on mononuclear iron(II) complexes can be obtained.

New Pyridine Dicarbene Pincer Ligands with Ring Expanded NHCs and their Nickel and Chromium Complexes.

The pincer complexes [NiIIBr(CNC)]Br (4), [CrIIIBr3(CNC)] (5 a) and [CrIIIBr2.3Cl0.7(CNC)] (5 b), where CNC=3,3'-(pyridine-2,6-diyl)bis(1-mesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene), were obtained from the novel ligand CNC, generated in situ from the precursor (CHNCH)Br2 and [NiIIBr2(PPh3)2] or from [CrII{N(SiMe3)2}2(THF)2] and (CHNCH)Br2 by aminolysis, respectively. The tetrahedrally distorted square planar (τ4≅0.30) geometry and the singlet ground state of Ni in 4 were attributed to steric constraints of the CNC backbone. Computational methods highlighted the dependence of the coordination geometry and the singlet-triplet energy difference on the size of the N-substituent of the tetrahydropyrimidine wingtips and contrasted it to the situation in 5-membered imidazolin-2-ylidene pincer analogues. The octahedral CrIII metal center in 5 a and 5 b is presumably formed after one electron oxidation from CH2Cl2. 4/MAO and 5 a/MAO were catalysts of moderate activity for the oligomerization and polymerization of ethylene, respectively. The analogous (CH^N^CH)Br2 precursor, where (CH^N^CH)=3,3'-(pyridine-2,6-diylbis(methylene))bis(1-mesityl-3,4,5,6-tetrahydropyrimidin-1-ium), was also prepared, however its coordination chemistry was not studied due to the inherent instability of the resulting free C^N^C ligand.

Crystal structures of a copper(II) and the isotypic nickel(II) and palladium(II) complexes of the ligand (E)-1-[(2,4,6-tri-bromo-phen-yl)diazen-yl]naphthalen-2-ol.

In the copper(II) complex, bis-{(E)-1-[(2,4,6-tri-bromo-phen-yl)diazen-yl]naph-thalen-2-olato}copper(II), [Cu(C16H8Br3N2O)2], (I), the metal cation is coord-inated by two N atoms and two O atoms from two bidentate (E)-1-[(2,4,6-tri-bromo-phen-yl)diazen-yl]naphthalen-2-olate ligands, forming a slightly distorted square-planar environment. In one of the ligands, the tri-bromo-benzene ring is inclined to the naphthalene ring system by 37.4 (5)°, creating a weak intra-molecular Cu⋯Br inter-action [3.134 (2) Å], while in the other ligand, the tri-bromo-benzene ring is inclined to the naphthalene ring system by 72.1 (6)°. In the isotypic nickel(II) and palladium(II) complexes, namely bis-{(E)-1-[(2,4,6-tri-bromo-phen-yl)diazen-yl]naphthalen-2-olato}nickel(II), [Ni(C16H8Br3N2O)2], (II), and bis-{(E)-1-[(2,4,6-tri-bromo-phen-yl)diazen-yl]naphthalen-2-olato}palladium(II), [Pd(C16H8Br3N2O)2], (III), respectively, the metal atoms are located on centres of inversion, hence the metal coordination spheres have perfect square-planar geometries. The tri-bromo-benzene rings are inclined to the naphthalene ring systems by 80.79 (18)° in (II) and by 80.8 (3)° in (III). In the crystal of (I), mol-ecules are linked by C-H⋯Br hydrogen bonds, forming chains along [010]. The chains are linked by C-H⋯π inter-actions, forming sheets parallel to (011). In the crystals of (II) and (III), mol-ecules are linked by C-H⋯π inter-actions, forming slabs parallel to (10-1). For the copper(II) complex (I), a region of disordered electron density was corrected for using the SQUEEZE routine in PLATON [Spek (2015 ▸). Acta Cryst. C71, 9-18]. The formula mass and unit-cell characteristics of the disordered solvent mol-ecules were not taken into account during refinement.

First stabilization of 14-electron rhodium(I) complexes by hemichelation.

Hemichelation is emerging as a new mode of coordination where non-covalent interactions crucially contribute to the cohesion of electron-unsaturated organometallic complexes. This study discloses an unprecedented demonstration of this concept to a Group 9 metal, that is, Rh(I). The syntheses of new 14-electron Rh(I) complexes were achieved by choosing the anti-[(η(6):η(6)-fluorenyl){Cr(CO)3}2] anion as the ambiphilic hemichelating ligand, which was treated with [{Rh(nbd)Cl}2] (nbd=norbornadiene) and [{Rh(CO)2Cl}2]. The new T-shaped Rh(I) hemichelates were characterized by analytical and structural methods. Investigations using the methods of the DFT and electron-density topology analysis (NCI region analysis, QTAIM theory) confirmed the closed-shell, non-covalent and attractive characters of the interaction between the Rh(I) center and the proximal Cr(CO)3 moiety. This study shows that, by appropriate tuning of the electronic properties of the ambiphilic ligand, truly coordination-unsaturated Rh(I) complexes can be synthesized in a manageable form.

Hemichelation, a way to stabilize electron-unsaturated complexes: the case of T-shaped Pd and Pt metallacycles.

A rational method of synthesis of stable neutral T-shaped 14 electron Pd and Pt complexes is proposed. It takes advantage of the ambiphilic character of the tricarbonyl(η(6)-indenyl)chromium anion, of which the main property is to behave as a hemichelating ligand, that is a nonconventional heteroditopic ligand capable of chelating a metal center by way of covalent and noncovalent bonding, thus preserving its unsaturated valence shell. The reaction of the in situ formed tricarbonyl(η(6)-2-methylindenyl)chromium anion with a series of Pd and Pt metallacycles afforded new air-stable and persistent synfacial heterobimetallic complexes in which the metallacycle binds the indenyl fragment via its metal in an η(1) fashion, leaving the fourth coordination site at the chelated metal virtually vacant. The structures of eight of these novel complexes are disclosed, and their bonding features are investigated by an array of theoretical methods based on the density functional theory (NBO, EDA, ETS-NOCV, AIM, NCI region analysis). Theory shows that the formation of these unusual structures of bimetallic synfacial η(1)-indenyl-Pd/Pt complexes is driven thermodynamically by attractive Coulombic occlusion of the fourth vacant coordination site at Pd/Pt centers by the Cr(CO)3 moiety.

Capillary permeability and extracellular volume fraction in uterine cervical cancer as patient outcome predictors: measurements by using dynamic MRI spin-lattice relaxometry.

PURPOSE: To improve the outcome prediction of uterine cervical carcinoma by measuring the vascular permeability (k(ep)) and the extracellular volume fraction (v(e)) of the tumor from Dynamic T(1)- IRM Relaxometry. MATERIALS AND METHODS: Twenty-six patients with proven cervical carcinoma were divided into good outcome and poor outcome groups. Classic tumor prognostic factors, the longest diameter L and the volume V of the tumor, were measured from morphologic MR images. The tumor parameters k(ep) and v(e) were determined from the relaxometry time-curve acquired during the contrast uptake after a bolus intravenous injection of an extracellular contrast agent. RESULTS: All "small" tumors (L<35 mm or V<11 cm(3)) were good outcome with 100% sensitivity but a rather low specificity (36% and 43% for L and V, respectively). With regard to the physiopathological parameter k(ep), "large" tumors (L >or= 35 mm) can also be classified as good outcome on the condition that k(ep) >or= 2.2 min(-1) with 100% sensitivity and 89% specificity. Regarding the extracellular volume fraction (v(e)), no significant difference was observed between the two groups. CONCLUSION: Measurement of the tumor vascular permeability might be useful to predict prognostic, to evaluate the treatment efficacy, and to adapt a proper therapy schedule.

Magnetic resonance imaging contrast-enhanced relaxometry of breast tumors: an MRI multicenter investigation concerning 100 patients.

Dynamic contrast-enhanced magnetic resonance imaging (DCE-MRI) using extracellular contrast agents has proved to be useful for the characterization of breast tumors. DCE-MRI has demonstrated a high sensitivity (around 95%) but a rather poor and controversial specificity, varying, according to the different studies, from 45% to 90%. In order to increase (a) the specificity and (b) the robustness of this quantitative approach in multicenter evaluation (five MRI units), a quantitative approach called dynamic relaxometry has been developed. According to the proposed method, the time-dependent longitudinal relaxation rate measured on region of interest of the lesion was calculated during the contrast uptake, after intravenous bolus injection of contrast agent. A specifically developed method was used for fast R(1) measurements. Relaxometry time curves are fitted to the Tofts model allowing the measurement of the parameters describing the enhancement curve (maximum relation rate enhancement, initial, 30-s and 60-s slopes) and the tissue parameters [transfer constant (K(trans) min(-1)) and extracellular extravascular space fraction (v(e))]. Correspondence factorial analysis followed by hierarchical ascendant classification are then performed on the different parameters. Higher K(trans) values were observed in infiltrative ductal carcinomas than in infiltrative lobular carcinomas, in agreement with data published by other groups. Specificity of DCE-MRI has been increased up to 85%, with a sensitivity of 95% with K(trans)/v(e) and enhancement index I (ratio of initial slope by maximum relaxation rate enhancement). A multiparametric data analysis of the calculated parameters opens the way to include quantitative image-based information in new nosologic approaches to breast tumors.

[Standards, Options and Recommendations 2000: non metastatic endometrial cancer]. / Standards, Options et Recommendations 2000: cancer de l'endomètre, stades non métastatiques (rapport abrégé).

CONTEXT: The "Standards, Options and Recommendations" (SOR) project, started in 1993, is a collaboration between the Federation of French Cancer Centers (FNCLCC), the 20 French Cancer Centers, and specialists from French Public Universities, General Hospitals and Private Clinics, and some specialists learned societies. The main objective is the development of clinical practice guidelines to improve the quality of health care and the outcome of cancer patients. The SORs are developed using a methodology based on a literature review and critical appraisal by a multidisciplinary group of experts, with feedback from specialists in cancer care delivery. OBJECTIVES: To develop clinical practice guidelines for the management of patients with carcinoma of the endometrium according to the definitions of the Standards, Options and Recommendations project. METHODS: Data were identified by searching Medline , web sites, and using the personal reference lists of members of the expert groups. Once the guidelines were defined, the document was submitted for review to 63 independent reviewers. RESULTS: The main recommendations for the management of carcinoma of the endometrium are: 1) The diagnosis of carcinoma of the endometrium is based on biopsy and histological examination. However, as first intention, the first elements for diagnosis can be obtain from a hysterography, or particularly, a endovaginal ultrasound examination. Ultrasound allows locoregional metastases to be detected, the CT scan allows the lymph node involvement to be assessed and magnetic resonance imaging allows the myometrium invasion to be evaluated. 2) For the majority of patients, surgery is the initial treatment, both for localised and advanced-stage carcinomas. The excised sample can be used for pathological analysis and tumour staging, using the FIGO (Fédération internationale de gynécologie obstétrique) classification. Surgery for patients with stage I and II carcinomas involves total extrafascial hysterectomy with bilateral salpingo-oophorectomy., In patients with stage III and IV carcinomas radical surgery should be performed, when possible. If this is not possible, then surgery should be as complete as possible and be associated with a complementary treatment. In patients with the most advanced carcinomas, tumour reduction by surgery should be performed. 3) Complementary treatment includes external-beam radiotherapy and brachytherapy. The decision concerning the extent and type of irradiation should be taken taking into consideration the stage and the prognostic factors present. For patients with stage I and II carcinoma, complementary treatment with brachytherapy can be performed, if the myometrium invasion is not deep, or if the carcinoma is grade 2 or 3. Patients with stage III carcinomas can be treated with pelvic or abdominal-pelvic complementary irradiation. In patients that cannot undergo surgery, exclusive radiotherapy can be performed. 4) In the absence of any symptoms, surveillance should include a general clinical and gynaecological examination. All patients with symptoms should undergo an additional work-up.