Analysis of the mediating effect of mentalization on the relationship between attachment styles and emotion dysregulation.

The current study aims to explore the relationship between attachment styles, mentalization and emotion dysregulation. Moreover, the mediation effect of mentalization in the relationship between attachment and emotion dysregulation is analyzed. A sample composed of 607 participants taken from the Spanish general population completed the measures in a cross-sectional designed study. The results show that secure attachment is negatively related to emotion dysregulation dimensions, whereas insecure attachment styles show a positive correlation. Furthermore, the mentalization variables are in general significantly related to emotion dysregulation. The mediation model shows a large mediational effect size (f2  = 2.64). The results suggest that mentalization significantly mediates the relationship between emotion dysregulation and preoccupation, self-sufficiency, and childhood trauma. These results have important implications, as they indicate that clinical interventions on mentalization should reduce emotion dysregulation even in those people with a predominant insecure attachment style.

Stressful life events and hopelessness in adults: the mediating role of mentalization and emotional dysregulation.

OBJECTIVE: Hopelessness is considered a risk factor for several mental and behavioral disorders. Research has shown that a stressful life event can be a significant predictor of hopelessness. The aim of the current research study was to explore the relationship between stressful life events and hopelessness, as well as to analyses the mediation effect of both mentalization and emotional dysregulation on this relationship. METHODS: In a cross-sectional design, 607 participants recruited from the Spanish general population completed a series of measures. RESULTS: Hopelessness was significantly related to stressful life events (r = 0.24, p < 0.001), emotion dysregulation variables (r = 0.18/0.38), and most measures of mentalization (r = 0.02/0.34). A good-fitting structural equation modeling-based mediation model (χ2/df = 2.04; root mean squared error of approximation = 0.042 [90%CI 0.033-0.050]; comparative fit index = 0.97; non-normed fit index = 0.97) showed that mentalization significantly mediated the relationship between stressful life events and hopelessness, while emotion dysregulation had no significant mediating effect. CONCLUSIONS: These results could have important clinical implications, such as the development of mentalization-based interventions for people living under a large number of stressors.

Distortional isomerism with copper(I) complexes of 3,7-diazabicyclo[3.3.1]nonane derivatives.

Two structural forms of the tetradentate bispidine ligand (3,7-diazabicyclo[3.3.1]nonane, pyridine-substituted at C2 and C4), coordinated to CuI, are known: a pentacoordinate square pyramidal structure with an acetonitrile completing the coordination sphere, and a tetracoordinate distorted tetrahedral structure, where one of the pyridine groups is dissociated. Similar structures are observed in crystals of the CuI complexes of another tetradentate and two pentadentate bispidine ligands. The structural dynamics in the CuI coordination sphere of the four ligands are probed by 1H-NMR spectroscopy, supported by approximate density functional theory (DFT) calculations. DFT and NMR spectroscopy indicate that there is an additional isomeric form, and experimental as well as computational data lead to the conclusion that the potential energy surfaces are very flat with various shallow minima.

Electronic structure of bispidine iron(IV) oxo complexes.

The electronic structure, based on DFT calculations, of a range of FeIV=O complexes with two tetra- (L1 and L2) and two isomeric pentadentate bispidine ligands (L3 and L4) is discussed with special emphasis on the relative stability of the two possible spin states (S = 1, triplet, intermediate-spin, and S = 2, quintet, high-spin; bispidines are very rigid diazaadamantane-derived 3,7-diazabicyclo[3.3.1]nonane ligands with two tertiary amine and two or three pyridine donors, leading to cis-octahedral [(X)(L)FeIV=O]2+ complexes, where X = NCCH3, OH2, OH-, and pyridine, and where X = pyridine is tethered to the bispidine backbone in L3, L4). The two main structural effects are a strong trans influence, exerted by the oxo group in both the triplet and the quintet spin states, and a Jahn-Teller-type distortion in the plane perpendicular to the oxo group in the quintet state. Due to the ligand architecture the two sites for substrate coordination in complexes with the tetradentate ligands L1 and L2 are electronically very different, and with the pentadentate ligands L3 and L4, a single isomer is enforced in each case. Because of the rigidity of the bispidine ligands and the orientation of the "Jahn-Teller axis", which is controlled by the sixth donor X, the Jahn-Teller-type distortion in the high-spin state of the two isomers is quite different. It is shown how this can be used as a design principle to tune the relative stability of the two spin states.

A density functional theory study of the reaction of the biomimetic iron(II) complex of a tetradentate bispidine ligand with H2O2.

Three pathways for the reaction of bispidine-iron(II) complexes (where bispidine is a rigid tetradentate amine/pyridine ligand) with H2O2 have been studied by DFT calculations. For all oxidation states the high-spin and low-spin (intermediate-spin) forms have been optimized, and the computed data have been compared with the readily available experimental results. It is concluded that there is a direct conversion of the bispidine-iron(II)-hydrogen peroxide complex to the corresponding iron(IV)-dihydroxo compound, which is a novel possible oxidant for the dihydroxylation of olefins.

DFT models for copper(II) bispidine complexes: structures, stabilities, isomerism, spin distribution, and spectroscopy.

Various DFT and ab initio methods, including B3LYP, HF, SORCI, and LF-density functional theory (DFT), are used to compute the structures, relative stabilities, spin density distributions, and spectroscopic properties (electronic and EPR) of the two possible isomers of the copper(II) complexes with derivatives of a rigid tetradentate bispidine ligand with two pyridine and two tertiary amine donors, and a chloride ion. The description of the bonding (covalency of the copper-ligand interactions) and the distribution of the unpaired electron strongly depend on the DFT functional used, specifically on the nonlocal DF correlation and the HF exchange. Various methods may be used to optimize the DFT method. Unfortunately, it appears that there is no general method for the accurate computation of copper(II) complexes, and the choice of method depends on the type of ligands and the structural type of the chromophore. Also, it appears that the choice of method strongly depends on the problem to be solved. LF-DFT and spectroscopically oriented CI methods (SORCI), provided a large enough reference space is chosen, yield accurate spectroscopic parameters; EDA may lead to a good understanding of relative stabilities; accurate spin density distributions are obtained by modification of the nuclear charge on copper; solvation models are needed for the accurate prediction of isomer distributions.

Deviation from tetrahedral geometry in Me(2)GeCl(2): crystal structure of a model compound and insight from ab initio calculations.

The molecular structure of Me(2)GeCl(2), and the value of the C-Ge-C angle in particular, was studied by ab initio quantum calculations to examine the deviation of this molecule from ideal geometry in the gas phase and in the crystalline state. The results show that, in the crystal, intermolecular interactions do have a large influence on the geometry of the molecule. An experimental value of 121.2 +/- 0.2 degrees is found for the C-Ge-C angle in the crystal structure of dichlorodi(2-phenethyl)germane, and it provides the first crystallographic evidence for the deviation from tetrahedral geometry. This molecule crystallizes in the monoclinic space group P2(1)/c, with a = 9.2079(2) A, b = 19.5396(4) A, c = 9.7845(2) A, beta = 114.217(1) degrees, and Z = 4. Calculations show that the conformation of the organic substituents has a sizable effect on the local geometry of the Ge-atom. Analysis of the distribution of the electron density suggests that the larger value of C-Ge-C in Me(2)GeCl(2) compared to the equivalent but smaller angle in Me(2)CCl(2) is indirectly the result of the higher ionic character of the bonds in the former molecule.