Complexes of N-Phosphorylated Thioureas RNHC(S)NHP(O)(OiPr)₂ (R = 2-MeC₆H₄, 2,6-Me₂C₆H₃, 2,4,6-Me₃C₆H₂) With Nickel(II)

Abstract

The reaction of O,O′-diisopropylphosphoric acid isothiocyanate (iPrO)₂P(O)NCS with 2-methylaniline 2-MeC₆H₄NH₂, 2,6-dimethylaniline 2,6-Me₂C₆H₃NH₂, or 2,4,6-trimethylaniline 2,4,6-Me₃C₆H₂NH₂ leads to the N-phosphorylated thioureas RNHC(S)NHP(O)(OiPr)₂ (R = 2-MeC₆H₄‒, HL^I ; 2,6-Me₂C₆H₃‒, HL^II ; 2,4,6-Me₃C₆H₂‒, HL^III ). Reaction of the potassium salts of HL^{I –III} with Ni(II) in aqueous EtOH leads to [Ni(L^I–III-N,S)₂] ([NiL^I–III ₂ ]) chelate complexes. The compounds obtained were investigated by ¹H, ³¹P{¹H} NMR spectroscopy and microanalysis. The molecular structure of the thiourea HL^III was elucidated by single crystal X-ray diffraction analysis. Single crystal X-ray diffraction studies showed that HL^III forms both intra- and intermolecular hydrogen bonds, which in turn leads to the formation of polymeric chains. One of the intermolecular hydrogen bonds is of the type N‒H…S. Moreover, the formation of intermolecular C‒H…η⁶-phenyl interactions was established.

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Keywords:

• Crystal structure
• hydrogen bond
• nickel(II)
• phosphorylthiourea

Acknowledgments

This work was supported by the Russian Science Support Foundation. D.A.S. and M.G.B. thank DAAD for the scholarships (Forschungsstipendien 2008/2009).