Activation of non-polar bonds by an electron-rich gallagermylene.

The electron-rich germylene LGa(µ-Cl)GeArMes (1) (L = CH[C(Me)N(Dipp)]2, Dipp = 2,6-iPr2C6H3, ArMes = 2,6-Mes2C6H3, Mes = 2,4,6-Me3C6H2) shows promising potential in the σ-bond activation of unpolar molecules as is shown in oxidative addition reactions with H2 and P4, yielding L(Cl)GaGe(H)2ArMes (2) and L(Cl)Ga(P4)GeArMes (3). Compounds 2 and 3 were characterised spectroscopically (1H, 13C{1H}, (31P{1H}), IR) and by single-crystal X-ray diffraction (sc-XRD).

Multiple ethylene activation by heteroleptic L(Cl)Ga-substituted germylenes.

Ethylene insertion into the Ga-Ge bond of the L(Cl)Ga-substituted germylene LGa(µ-Cl)GeDMP 1 (L = HC(C(Me)NAr)2, Ar = 2,6-iPr2C6H3; DMP = 2,6-Mes2C6H3, Mes = 2,4,6-Me3C6H2) at ambient temperature is followed by dimerization of the as-formed germylene to give the digermene 3, which further reacted with ethylene in a [2 + 2] cycloaddition to give the 1,2-digermacyclobutane 4. In marked contrast, the amino-substituted germylene L(Cl)GaGeN(SiMe3)Ar 2 reacted directly to the 1,2-digermacyclobutane 5. Quantum chemical calculations confirmed the assumed reaction mechanism, hence demonstrating the crucial role of the substituent on the reaction mechanism.

Structurally characterised intermediate of the oxidative addition of a heteroleptic germylene to gallanediyle.

Bond activation reactions using main group metal complexes are gaining increasing interest. We report on reactions of LGa (L = HC[C(Me)N(Ar)]2, Ar = Dipp = 2,6-i-Pr2C6H3,) with heteroleptic tetrylenes L'ECl (E = Ge, Sn; L' = N(SiMe3)Ar), yielding the donor-acceptor complex LGa-Sn(Cl)L' (1) or the oxidative addition product L(Cl)GaGeL' (3). The reaction with DMPGeCl (DMP = 2,6-Mes2C6H3, Mes = 2,4,6-Me3C6H2) yielded LGa(µ-Cl)GeDMP (2), which represents an intermediate of the oxidative addition reaction. 1-3 were characterized by NMR and IR spectroscopy as well as by single crystal X-ray diffraction (sc-XRD), while their electronic nature was analyzed by quantum chemical calculations.

Reducing intrusive memories of trauma using a visuospatial interference intervention with inpatients with posttraumatic stress disorder (PTSD).

OBJECTIVE: The core clinical feature of posttraumatic stress disorder (PTSD) is recurrent intrusive memories of trauma. This study aimed to test a novel and simple intervention, inspired by the concepts of concurrent task interference and memory reconsolidation, to reduce the occurrence of intrusive memories among inpatients with complex PTSD. METHOD: In this open-label single case series 20 patients with longstanding complex PTSD in inpatient treatment monitored the occurrence of intrusive trauma memories (intrusions) over the course of their admission (5 to 10 weeks). Patients received study-specific intervention sessions (including a memory reminder for a specific intrusion then 25 min Tetris gameplay) on a weekly basis. A within-subjects multiple baseline AB design was used, in that the length of baseline ("A," preintervention, monitoring only) and postintervention ("B") phases varied within-subjects across individual intrusions. Further, some intrusions were never targeted by the intervention. The study was registered prior to analysis, ISRCTN34320836. RESULTS: Frequency of targeted intrusions reduced by on average 64% from baseline to the postintervention phase. Conversely, never-targeted intrusions reduced in frequency by on average 11% over a comparable time-period. Of the 20 patients, 16 met our criteria for showing "response" to the intervention. CONCLUSIONS: Results provide initial evidence that this brief behavioral procedure might reduce the occurrence of intrusive traumatic memories in longstanding and complex PTSD, here delivered in an inpatient setting. The potential of this simple, focused intervention opens up new possibilities for tackling a core clinical symptom of PTSD, warranting further research. (PsycINFO Database Record (c) 2018 APA, all rights reserved).