Ligand recoil and solid state exchange reactions in hexahalo complexes of Re(IV)

Bell, R.; Rössler, K.; Stöcklin, G.; Upadhyay, S.R.

doi:10.1016/0022-1902(72)80424-x

“…The results of BELL et al [13] who studied exchange of 82 Br and 3e Cl in K 2 ReCl e and K 2 ReBr e , demonstrate the importance of thermally stimulated ligand vacancies. The low activation energy for these exchange reactions and also for the annealing reactions after ligand recoil in these systems was convincingly interpreted by them as the activation energy for the migration of ligand vacancies through the crystals.…”

Section: Discussionmentioning

confidence: 93%

Szilard-Chalmers Reactions in the Hexahalocomplexes of Iridium

Ooij¹,

Houtman²

1974

Radiochimica Acta

0

View full text Add to dashboard Cite

Thermal and radiation annealing have been studied in several hexahalocomplexes of tri-and tetravalent iridium. Moreover, transfer annealing experiments after recrystallization of irradiated samples were carried out. In all irradiated compounds a post-irradiation thermal treatment results in an increase of the retention. Heating of recrystallized irradiated samples produces effects which are similar to the thermal annealing effects. Hydration or dehydration of irradiated complexes affects the product spectra but does not result in an increase of the retention. The results are discussed in terms of a model which assumes that the annealing of some of the fragments present in the anhydrous complexes is triggered by an oxidation reaction with radiation-induced electron holes or V-centres. In a second step the fragments recombine with free ligands or they acquire ligands from IrCl e -2 ions by ligand transfer reactions. In hydrated and in recrystallized samples the annealing may largely be interpreted as exchange reactions which proceed via a ligand vacancy diffusion mechanism.Radiochim. Acta 17, 73 (1972). 12. W. J. VAN OOIJ and P. LIEBERMAN, unpublished results.

show abstract

“…The contrast is even greater in the light of the studies of MÜLLEB [4][5][6] on mixed crystals of hexahalorhenates(IV) and -stannates(IV), which led to the opposite conclusion, namely a "disorder zone" with a radius of about 5 Â involving only a few atoms. Ligand recoil and solid state exchange studies in hexahalorhenates-(IV) recently carried out in our laboratory [7,8] also showed that the recoil halogen reacts and comes to rest in a quite undisturbed zone, containing complexes which cannot miss more than one ligand. Furthermore, chemical and physical solid state experiments gave evidence for a small "hot zone" in inorganic solids as well as in metals (for a review cf.…”

Section: Lettermentioning

confidence: 92%

"Super Hot Zones" by Nuclear Recoil in Amine-Complexes of Co, Rh and Ir?

Rössler

¹

,

Otterbach

²

1971

Radiochimica Acta

Self Cite

1

0

View full text Add to dashboard Cite

“…The contrast is even greater in the light of the studies of MÜLLEB [4][5][6] on mixed crystals of hexahalorhenates(IV) and -stannates(IV), which led to the opposite conclusion, namely a "disorder zone" with a radius of about 5 Â involving only a few atoms. Ligand recoil and solid state exchange studies in hexahalorhenates-(IV) recently carried out in our laboratory [7,8] also showed that the recoil halogen reacts and comes to rest in a quite undisturbed zone, containing complexes which cannot miss more than one ligand. Furthermore, chemical and physical solid state experiments gave evidence for a small "hot zone" in inorganic solids as well as in metals (for a review cf.…”

Section: Herstellung Der Legierungmentioning

confidence: 93%