Association Coordination Research Articles

Computational Study of the Palladium-Catalyzed Carbonylative Synthesis of Aromatic Acid Chlorides: The Synergistic Effect of PtBu3 and CO on Reductive Elimination.

We describe herein computational studies on the unusual ability of Pd(PtBu3 )2 to catalyze formation of highly reactive acid chlorides from aryl halides and carbon monoxide. These show a synergistic role of carbon monoxide in concert with the large cone angle PtBu3 that dramatically lowers the barrier to reductive elimination. The tertiary structure of the phosphine is found to be critical in allowing CO association and the generation of a high energy, four coordinate (CO)(PR3 )Pd(COAr)Cl intermediate. The stability of this complex, and the barrier to elimination, is highly dependent upon phosphine structure, with the tertiary steric bulk of PtBu3 favoring product formation over other ligands. These data suggest that even difficult reductive eliminations can be rapid with CO association and ligand manipulation. This study also represents the first detailed exploration of all the steps involved in palladium-catalyzed carbonylation reactions with simple phosphine ligands, including the key rate-determining steps and palladium(0) catalyst resting state in carbonylations.

A Matter of Trust? A Study of Coordination of Swedish Stakeholders in Return-to-Work

Stakeholder cooperation in return-to-work has been increasingly emphasized over the last years. However, there is a lack of empirical studies on the subject. This study explores different public stakeholders' experiences of participating in Coordination Associations (CAs), a Swedish form of structured cooperation in return-to-work. The aim of the study is to determine the impact of stakeholder interests on the prerequisites for cooperation. Thirty-five representatives from two CAs in eastern Sweden were interviewed regarding the aim, structure and strategies for their common work. Stakeholders' actions are to a high degree determined by their institutional preferences and self-interest. In the CAs, the motives for cooperation differ, and although these differences supposedly could be overcome, they are in fact not. One of the stakeholders, the Public Employment Service, limit its interest to coordinating resources, while the other three wishes to engage in elaborated cooperative work forms, implying the crossing of organizational borders. This discrepancy can largely be attributed to the difficulties for representatives from state authorities in changing their priorities in order to make cooperation work. Stakeholders' interests have a high impact on the prerequisites for cooperation in return-to-work. By referring to organizational goals, stakeholders engage in non-cooperative behaviour, which threatens to spoil cooperative initiatives and to develop distrust in cooperative work forms. The results of this study expose the complexity of and threats to cooperation, and its conclusions may be used by return-to-work stakeholders in different jurisdictions to improve the possibilities for the development of cooperative structures.