Metal-Ligand Cooperation as Key in Formation of Dearomatized NiII-H Pincer Complexes and in Their Reactivity toward CO and CO2.

The unique synthesis and reactivity of [(RPNP*)NiH] complexes (1a,b), based on metal-ligand cooperation (MLC), are presented (RPNP* = deprotonated PNP ligand, R = iPr, tBu). Unexpectedly, the dearomatized complexes 1a,b were obtained by reduction of the dicationic complexes [(RPNP)Ni(MeCN)](BF4)2 with sodium amalgam or by reaction of the free ligand with Ni0(COD)2. Complex 1b reacts with CO via MLC, to give a rare case of a distorted-octahedral PNP-based pincer complex, the Ni(0) complex 3b. Complexes 1a,b also react with CO2 via MLC to form a rare example of η1 binding of CO2 to nickel, complexes 4a,b. An unusual CO2 cleavage process by complex 4b, involving C-O and C-P cleavage and C-C bond formation, led to the Ni-CO complex 3b and to the new complex [(PiPr2NC2O2)Ni(P(O)iPr2)] (5b). All complexes have been fully characterized by NMR and X-ray crystallography.

Highly Selective, Efficient Deoxygenative Hydrogenation of Amides Catalyzed by a Manganese Pincer Complex via Metal-Ligand Cooperation.

Deoxygenative hydrogenation of amides to amines homogeneously catalyzed by a complex of an Earth-abundant metal is presented. This manganese-catalyzed reaction features high efficiency and selectivity. A plausible reaction mechanism, involving metal-ligand cooperation of the manganese pincer complex, is proposed based on NMR studies and relevant stoichiometric reactions.

Psychodynamic Parenthood Therapy: a model for therapeutic work with parents and parenthood.

The approach to therapeutic work with parents in psychotherapy has been described in the literature in various ways but is not well defined. This article will give a short review of four main types of therapeutic work with parents: 1) Meeting to update and to accompany parents (Periodic update meeting with parents complementary to the child's psychotherapy), 2) Parental counseling (guidance), 3) Parent-child therapy (Relationship or dyadic therapy), 4) Family therapy. The claim is made that those approaches, important and effective as they are, do not deal with the parent as a main issue, and do not place enough attention on parenthood. This article offers a model referred to here as Psychodynamic Parenthood Therapy (PPT). PPT is a dynamic therapeutic intervention with parents based upon a contract focusing mainly on working on their parenthood. In general, a parent's negative feelings towards his parenthood or towards his child are some of the basic issues that can be helped by this approach. After clarifying the guidelines for choosing PPT, both the contract and the process itself will be explained. The process deals with parenthood: internalizations, unconscious feelings, intergenerational transmissions and parental identity. In comparison with other methods which do not deal specifically with parenthood, PPT will often lead to a meaningful and effective therapeutic result.