The possibility that MX 3 − anions can interact with one another is assessed via ab initio calculations in gas phase as well as in aqueous and ethanol solution. A pair of such anions can engage in two different dimer types. In the bridged configuration, two X atoms engage with two M atoms in a rhomboid structure with four equal M–X bond lengths. The two monomers retain their identity in the stacked geometry which contains a pair of noncovalent M⋯X interactions. The relative stabilities of these two structures depend on the nature of the central M atom, the halogen substituent, and the presence of solvent. The interaction and binding energies are fairly small, generally no more than 10 kcal mol −1 . The large electrostatic repulsion is balanced by a strong attractive polarization energy.
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{M I (CO)X(CNAr DArF2 ) 4 } (DArF = 3,5-(CF 3 ) 2 C 6 H 3 ; M = Re and Tc; X = Br and Cl) Complexes: Convenient Platforms for the Synthesis of Low-Valent Rhenium and Technetium Compounds
- Award ID(s):
- 1802646
- NSF-PAR ID:
- 10283164
- Date Published:
- Journal Name:
- Organometallics
- Volume:
- 40
- Issue:
- 9
- ISSN:
- 0276-7333
- Page Range / eLocation ID:
- 1336 to 1343
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation