Synchrony refers to the coordinated interplay of behavioural and physiological signals that reflect the bi-directional attunement of one partner to the other’s psychophysiological, cognitive, emotional, and behavioral state. In mother-child relationships, a synchronous pattern of interaction indicates parental sensitivity. Parenting stress has been shown to undermine mother-child behavioural synchrony. However, it has yet to be discerned whether parenting stress affects brain-to-brain synchrony during everyday joint activities. Here, we show that greater parenting stress is associated with less brain-to-brain synchrony in the medial left cluster of the prefrontal cortex when mother and child engage in a typical dyadic task of watching animation videos together. This brain region overlaps with the inferior frontal gyrus, the frontal eye field, and the dorsolateral prefrontal cortex, which are implicated in inference of mental states and social cognition. Our result demonstrates the adverse effect of parenting stress on mother-child attunement that is evident at a brain-to-brain level. Mother-child brain-to-brain asynchrony may underlie the robust association between parenting stress and poor dyadic co-regulation. We anticipate our study to form the foundation for future investigations into mechanisms by which parenting stress impairs the mother-child relationship.

The complexes trans,cis-RuCl2(PPh3)2(ampy) (1) and trans-RuCl2[Ph2P(CH2)4PPh2](ampy) (2) have been prepared in high yield by reaction of RuCl2(PPh3)3 and RuCl2(PPh3)[Ph2P(CH2)4PPh2] with 2-(aminomethyl)pyridine (ampy) at room temperature by PPh3 displacement. Heating compound 1 in refluxing toluene leads to the isomer cis,cis-RuCl2(PPh3)2(ampy) (3), which has been proven to be a good precursor for the preparation of the complexes cis-RuCl2(PP)(ampy) [PP = (S,S)-Chiraphos, 4; Ph2P(CH2)3PPh2, 5; (S,S)-Skewphos, 6; Ph2P(CH2)4PPh2, 7; (R,R)-Diop, 8] by displacement of two PPh3 with the appropriate diphosphine. The derivatives cis-RuCl2(PP)(ampy) [PP = (R,S)-Josiphos, 9; (R,S)-tBu-Josiphos, 10] have been synthesized from RuCl2(PPh3)3 and PP followed by addition of ampy. The chiral complexes 4, 6, 8, 9, and 10 are formed stereoselectively, as inferred by NMR data in solution. For the derivatives 7 and 9 the molecular structures have been determined by X-ray measurements. The monohydride complex trans,cis-RuHCl(PPh3)2(ampy) (11) has been prepared from RuHCl(PPh3)3 and ampy in heptane by PPh3 substitution. Compound 11 reacts with sodium isopropoxide in toluene, affording the dihydride derivative cis,trans-Ru(H)2(PPh3)2(ampy) (12) via the alkoxide route. The intermediate species cis,cis-Ru(H)2(PPh3)2(ampy) (A) has been also characterized by NMR in solution. All these complexes have been found to be highly efficient transfer hydrogenation catalysts. With the complexes cis-RuCl2(PP)(ampy) a large number of ketones (dialkyl, diaryl, and alkyl-aryl) can be quantitatively reduced to alcohols in 2-propanol and in the presence of NaOH (ketone/Ru/NaOH = 2000/1/40) with remarkably high TOF values (up to 400 000 h-1 at 50% conversion). The derivatives containing chiral diphosphines afforded rapid (TOF > 105 h-1) and enantioselective (ee up to 94%) reduction of methyl-aryl ketones using low loading of catalysts (0.05−0.01 mol %). In the absence of base the dihydride compound 12 catalyzes the transfer hydrogenation of acetophenone.

Fathering plays an important role in infants’ socioemotional and cognitive development. Previous studies have identified brain regions that are important for parenting behavior in human mothers. However, the neural basis of parenting in human fathers is largely unexplored. In the current longitudinal study, we investigated structural changes in fathers’ brains during the first four months postpartum using voxel-based morphometry (VBM) analysis. Biological fathers (n=16) with full-term, healthy infants were scanned at 2–4 weeks postpartum (Time 1) and at 12–16 weeks postpartum (Time 2). Fathers exhibited increases in gray matter volume in several neural regions involved in parental motivation, including the hypothalamus, amygdala and striatum and lateral prefrontal cortex. On the other hand, fathers exhibited decreases in gray matter volume in the orbitofrontal cortex, posterior cingulate cortex and insula. The findings provide evidence for neural plasticity in fathers’ brains. We also discuss the distinct patterns of associations among neural changes, postpartum mood symptoms, and parenting behaviors among fathers.

Dedicated to Professor Fausto Calderazzo on the occasion of his 75th birthdayPincer ECE (E = N, P) transition-metal complexes, in which the terdentate ligands contain two stable five-membered cyclometalated rings, have reached a high level of sophistication and appear extremely attractive for both catalytic and stoichiometric reactions.[1] The great interest in pincer ligands arises from the high level of control over the reactivity and the stereochemistry that they impose around the metal center as a result of their electronic properties and geometric restrictions. These factors afford highly selective transformations and lead to some unique species of relevance for the investigation of elementary processes.[2] In spite of the great attention afforded to ruthenium for its versatility in catalysis, [3] no examples of terdentate ruthenium CNN catalysts have been reported thus far. It is worth noting that CNN complexes are expected to have significantly different reactivity compared to the NCN analogues, mainly because of the different geometrical disposition of the s-donor carbon atom.Recently, we have shown that 2-(aminomethyl)pyridine (ampy) shows a high ligand acceleration effect in transfer hydrogenation [4] catalyzed by ruthenium(ii) complexes with phosphane ligands. Thus, complete reduction of many ketones in 2-propanol is quickly achieved with the cyclometalated complex [RuCl(CO)(CP)(ampy)] (CP = (2-CH 2 -6-MeC 6 H 3 )PPh 2 ), with turnover frequencies (TOF values) up to 6.3 10 4 h À1 , whereas the derivatives cis-[RuCl 2 (PP)-(ampy)] (PP = diphosphane) lead to TOF values up to 4.0 10 5 h À1 and ee values up to 94 % by using chiral diphosphanes.[5] Since it is well known that 2-phenylpyridine readily gives access to orthometalated CN ruthenium complexes, [6] we decided to investigate the coordination chemistry of the related 6-(4'-methylphenyl)-2-pyridylmethylamine with the aim of obtaining terdentate CNN complexes. We report herein on novel complexes of formula [RuX(CNN)(dppb)] (X = Cl, H; dppb = Ph 2 P(CH 2 ) 4 PPh 2 ), which are remarkably active catalysts for transfer hydrogenation that afford TOF values up to 2.5 10 6 h À1 with very low loading of catalysts (0.005-0.001 mol %) compared to the most active systems reported. [2f, 7] Evidence is provided that the reduction of the ketone proceeds through the formation of a Ru IIalkoxide complex by insertion of the carbonyl group of the substrate into the RuÀH bond of a ruthenium(ii) hydride formed as an intermediate from the chloride complex 1.Treatment of [RuCl 2 (PPh 3 )(dppb)] with an equimolar amount of 6-(4'-methylphenyl)-2-pyridylmethylamine in 2-propanol at reflux in the presence of NEt 3 affords the thermally stable orthometalated ruthenium(ii) complex 1 [8] in high yield [Eq. (1)].The signals for the diastereotopic NCH 2 protons in the 1 H NMR spectrum are at d = 4.12 and 3.72 ppm with 2 J(H,H) = 15.5 Hz. The doublet at d = 52.5 ppm with a 3 J(C,P) = 2.7 Hz in the 13 C NMR spectrum corresponds to the CH 2 N group which is shifted downfield relati...

The human infant face represents an essential source of communicative signals on the basis of which adults modulate their interactions with infants. Behavioral studies demonstrate that infants faces activate sensitive and attuned responses in adults through their gaze, face expression, voice, and gesture. In this study we aimed to identify brain responses that underlie adults’ general propensity to respond to infant faces. We recorded fMRI during adults’ (non-parents) processing of unfamiliar infant faces compared to carefully matched adult faces and infrahuman mammal infant and adult faces. Human infant faces activated several brain systems including the lateral premotor cortex, supplementary motor area, cingulate cortex, anterior insula and the thalamus. Activation of these brain circuits suggests adults’ preparation for communicative behavior with infants as well as attachment and caregiving. The same brain regions preferentially responded to human infant faces when compared to animal infant faces, indicating species-specific adult brain responses. Moreover, results of support vector machine based classification analysis indicated that these regions allowed above chance-level prediction of brain state during perception of human infant faces. The complex of brain responses to human infant faces appear to include biological mechanisms that underlie responsiveness and a caring inclination toward young children which appear to transcend adult’s biological relationship to the baby.

A neutron diffraction study of the complex RuCl(2)[PPh(2)(2,6-Me(2)C(6)H(3))](2) (1) defines the precise nature of the delta agostic interactions between the unsaturated metal center and two o-methyl groups of the xylyl substituents. The CH(3) carbon atoms lie in the RuP(2) equatorial plane with Ru...C distances of 2.637(7) and 2.668(6) A, whereas four short Ru.H distances (from 2.113(11) to 2.507(11) A) indicate that each methyl group interacts with two C-H bonds. A survey of the X-ray structures with beta, gamma, delta, and epsilon M...H(3)C-C moieties (no neutron data have been previously reported) shows a linear correlation between the angle M.C-C and the torsion of the methyl group about the C-C bond. Thus, the agostic interactions span the range between the classical (M...eta(2)-HC) and the nonclassical (M...eta(3)-H(2)C) types. A solution study of 1 shows intramolecular rearrangement of each xylyl substituent that equilibrates the environments of its two ortho CH(3) groups. Activation parameters, evaluated from the analysis of (1)H NMR line shape as a function of temperature, are Delta H(++) = 9.6 +/- 0.2 kcal mol(-1) with Delta S(++) = -15.4 +/- 0.7 eu (CDCl(3)). The related 14-electron complexes RuX(2)[PPh(2)(2,6-Me(2)C(6)H(3))](2) (X = I, 2; NCO, 3), prepared from 1 and NaX, show a similar dynamic process in solution, with the iodo derivative displaying the most hindered rotation of the xylyl group. A DFT optimization of the complex RuCl(2)[PH(2)(2,6-Me(2)C(6)H(3))](2) (1a) reproduces well the nonclassical Ru...eta(3)-H(2)C agostic mode, whereas the classical Ru...eta(2)-HC one corresponds to a transition state 1b, destabilized by 3.4 kcal mol(-1). A similar barrier (ca. 3.8 kcal mol(-1)) is calculated for the xylyl rotation in the further simplified model RuCl(2)[PH(2)(2,6-Me(2)C(6)H(3))][PH(2)CH[double bond]CHCH(3)] (1c), the absence of bulky phenyl substituents being largely responsible for the difference with respect to the experimental value. Finally, the MO analysis addresses the intrinsic stability of the 14-electron complex RuCl(2)(PH(3))(2) and, in agostic complexes, accounts for the different interactions between the methyl group and the metal atom in relation to the length of their interconnecting chain.

This report coordinates assessments of five types of behavioral responses in new mothers to their own infants' cries with neurobiological responses in new mothers to their own infants' cries and in experienced mothers and inexperienced nonmothers to infant cries and other emotional and control sounds. We found that 684 new primipara mothers in 11 countries (Argentina, Belgium, Brazil, Cameroon, France, Kenya, Israel, Italy, Japan, South Korea, and the United States) preferentially responded to their infants' vocalizing distress by picking up and holding and by talking to their infants, as opposed to displaying affection, distracting, or nurturing. Complementary functional magnetic resonance imaging (fMRI) analyses of brain responses to their own infants' cries in 43 new primipara US mothers revealed enhanced activity in concordant brain territories linked to the intention to move and to speak, to process auditory stimulation, and to caregive [supplementary motor area (SMA), inferior frontal regions, superior temporal regions, midbrain, and striatum]. Further, fMRI brain responses to infant cries in 50 Chinese and Italian mothers replicated, extended, and, through parcellation, refined the results. Brains of inexperienced nonmothers activated differently. Culturally common responses to own infant cry coupled with corresponding fMRI findings to own infant and to generic infant cries identified specific, common, and automatic caregiving reactions in mothers to infant vocal expressions of distress and point to their putative neurobiological bases. Candidate behaviors embedded in the nervous systems of human caregivers lie at the intersection of evolutionary biology and developmental cultural psychology.

Terdentate ruthenium(II) complexes of general formula RuX(CNN)(dppb) (X ) chloride, hydride, alkoxide; dppb ) Ph 2 P(CH 2 ) 4 PPh 2 ), where CNN is a deprotonated 2-aminomethyl-6-arylpyridine ligand, have been prepared. The orthometalated derivative RuCl(b)(dppb) (1) has been obtained by reaction of RuCl 2 (PPh 3 )(dppb) with N, N-dimethyl-2-aminomethyl-6-(4-methylphenyl)pyridine (Hb) in 2-propanol and in the presence of triethylamine by elimination of PPh 3 and HCl. Similarly, RuCl(a)(dppb) (2) and the chiral analogue RuCl(c)(dppb) (3), containing primary amine ligands, have been isolated starting from 2-aminomethyl-6-(4-methylphenyl)pyridine (Ha) and (R)-2,2-dimethyl-1-(6-phenylpyridin-2-yl)propylamine (Hc), respectively. The synthesis of the functionalized pyridines Ha-Hc is here described, whereas the crystal structure of 3 has been determined through an X-ray diffraction experiment. Treatment of 1-3 with sodium or potassium isopropoxide gives the corresponding hydrides RuH(b)(dppb) (4), RuH(a)(dppb) (5), and RuH(c)(dppb) (6) from the ruthenium isopropoxide complexes, via a β-H elimination process. Studies in solution show that the isopropoxides bearing a NH donor group are in equilibrium with the corresponding hydrides (5 and 6). Reaction of 5 with benzophenone leads to the alkoxide Ru(OCHPh 2 )(a)(dppb) (7), which has been proven to interact with benzhydrol in C 6 D 6 , leading to the adduct 7‚(HOCHPh 2 ), the alkoxide ligand, and the alcohol being in rapid exchange. Complexes 2 and 3 display a remarkable high catalytic activity for the transfer hydrogenation of ketones to alcohol in 2-propanol using a very small amount of catalyst. With the chiral complex 3 (0.005 mol %) methyl-aryl ketones can be quickly reduced (TOF ranging from 5.4 × 10 5 to 1.4 × 10 6 h -1 ) with an enatiomeric excess up to 88%.