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...