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Structural Studies of Binuclear Cobalt (III) Cyano Complexes


Fronczek, Franklin Robert (1975) Structural Studies of Binuclear Cobalt (III) Cyano Complexes. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/wc2q-8t48.


The crystal structures of six closely related binuclear cobalt(III) complexes have been determined by single crystal X-ray diffraction methods, in order to study the effects of the pentacyano system upon the bonding to various bridging ligands. Studies pertinent to dioxygen bridging ligands include the bis(pentacyanocobalt(III)) structures K5{(CN)5Co2(CN)5}·H2O and the double salt K8{(CN)5Co2(CN)5} (NO3)2·4H2O, as well as the bis(pentaamminecobalt(III)) structure {(NH3) 5Co2(CN)5}(SCN)4. In all cases, the dioxygen ligands (peroxo and superoxo) are found to bridge to two cobalt atoms in the asymmetric, staggered arrangement, and both planar and nonplanar structures are noted. The structures of two molecules of the type pentacyanocobalt(III)pentaamminecobalt(III) are determined, with the bridging ligands cyanide and thiocyanate. These compounds are (CN)5CoNCCo(NH3)5·H2O and (CN)5CoSCNCo(NH3)5·H2O. The preparation and structure of the compound K6{(CN)5Co2(CN)5}·6H2O, containing the new bridging ligand thiosulfite (SSO22-) are reported. This ligand bridges the two cobalt atoms through its two sulfur atoms, and has a geometry similar to that of normal coordinated sulfites. Coordination to cobalt is trans planar.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Chemistry
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Schaefer, William P.
Thesis Committee:
  • Schaefer, William P.
Defense Date:21 November 1974
Record Number:CaltechTHESIS:03252022-181352122
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:14529
Deposited By: Benjamin Perez
Deposited On:28 Mar 2022 17:54
Last Modified:28 Mar 2022 17:55

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