Synthesis, characterization and spectral studies of bis(O,O-dialkylmonothiophosphato)cobalt(II) complexes and their adducts with nitrogen base ligands: crystal structures of [Co{O(S)P(OPri)(2)}(2)(C5H5N)(4)] and [Co{O(S)P(OPrn)(2)}(2)(C10H8N2)(2)]

Bingham, Ann L., Drake, John E., Hursthouse, Michael B., Light, Mark E., Nirwan, Manisha and Ratnani, Raju (2008) Synthesis, characterization and spectral studies of bis(O,O-dialkylmonothiophosphato)cobalt(II) complexes and their adducts with nitrogen base ligands: crystal structures of [Co{O(S)P(OPri)(2)}(2)(C5H5N)(4)] and [Co{O(S)P(OPrn)(2)}(2)(C10H8N2)(2)]. Polyhedron, 27 (6), 1673-1678. (doi:10.1016/j.poly.2008.01.037).

Abstract

Bis(O,O-dialkylmonothiophosphato)cobalt(II) complexes of the type [Co{O(S)P(OR)2}2] (where R = Prn, Pri, Bun) were prepared under anhydrous conditions by the reaction of cobalt(II) dichloride hexahydrate with the sodium salts of dialkyl monothiophosphoric acids. The reactions of these blue tetrahedral complexes with nitrogen bases such as pyridine (C5H5N or py) and 2,2-bipyridyl (C10H8N2 or bipy) resulted in the pink/orange octahedral adducts [Co{O(S)P(OPri)2}2(C5H5N)4], [Co{O(S)P(OPrn)2}2(C10H8N2)2] and [Co{O(S)P(OBun)2}2(C10H8N2)2]. These compounds were characterized by elemental analysis, IR spectroscopy, magnetic measurements and the single crystal X-ray diffraction structures of two of the adducts of the monothiophosphate complexes, [Co{O(S)P(OPri)2}2(C5H5N)4] and [Co{O(S)P(OPrn)2}2(C10H8N2)2], which are the first examples of this class of compounds. [Co{O(S)P(OPri)2}2(C5H5N)4] crystallizes as triclinic in the space group View the MathML source with the cell parameters a = 9.0515(4) Å, b = 10.1629(5) Å, c = 11.8468(5) Å, ? = 88.389(3)°, ? = 71.984(4)°, ? = 69.181(3)°, Z = 1, V = 964.57(8) Å3 and [Co{O(S)P(OPrn)2}2(C10H8N2)2] crystallizes as monoclinic in the space group C2/c with the cell parameters, a = 8.404(2) Å, b = 22.855(5) Å, c = 18.913(4) Å, ? = 97.56(3)°, Z = 4, V = 3601(1) Å3. These structures contain a unidentate bonding of the monothiophosphate ligands through oxygen, with the geometry of the CoO2N4 coordination sphere around cobalt being distorted octahedral.

Graphical abstract
Bis(O,O-dialkylmonothiophosphato)cobalt(II) complexes of the type [Co{O(S)P(OR)2}2] (where R = Prn, Pri, Bun) and their nitrogen bases adducts, [Co{O(S)P(OPri)2}2(C5H5N)4], [Co{O(S)P(OPrn)2}2(C10H8N2)2] and [Co{O(S)P(OBun)2}2(C10H8N2)2] have been prepared. These compounds were characterized by elemental analysis, IR spectroscopy, magnetic measurements and the single crystal X-ray diffraction structures of two of the adducts, [Co{O(S)P(OPri)2}2(C5H5N)4] and [Co{O(S)P(OPrn)2}2(C10H8N2)2].

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Contributors

Author: Mark E. Light

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