Polymeric and cyclic manganese phosphates and phosphinates: Synthesis, spectral characterization and solid-state structures

• The choice of metal precursor in determining the aggregation and structure of Mn(II) phosph(in)ates is demonstrated.
• The influence of perchlorate on the nuclearity of the resultant metal phosph(in)ates is established.
• Replacement of acetate from [Mn(OAc)(bpy)2](ClO4)(H2O) by a phosphate (L) leads to dimeric [Mn(L)(bpy)2]2(ClO4)2.
• Replacement of acetate by phenyl phosphinate leads to the formation of [Mn(ppi)2(L)]n polymers.

Polymeric manganese phosphinates [Mn(ppi)2(bpy)]n (1) and [Mn(ppi)2(phen)]n (2) have been obtained by treating manganese acetate with phenylphosphinic acid (ppi-H) in the presence of either 2,2′-bpy or 1,10-phen, respectively. The reaction of preformed precursor [Mn(OAc)(bpy)2](ClO4)(H2O) with phosphinic acids or phosphate diesters yield [Mn(L)(bpy)2]2(ClO4)2 (where L-H = dtbp-H = di-tert-butyl hydrogen phosphate (3), dpp-H = diphenyl hydrogen phosphate (4), dppi-H = diphenyl phosphinic acid (5), and ppi-H = phenyl phosphinic acid (6)), which are dimeric compounds. Polymers 1–2 and dinuclear cyclic compounds 3–6 have been extensively characterized by analytical and spectroscopic methods and also in each case by a single crystal X-ray diffraction study.

Polymeric manganese phosphinates [Mn(ppi)2(bpy)]n (1) and [Mn(ppi)2(phen)]n (2) have been obtained by treating manganese acetate with phenylphosphinic acid (ppi-H) in the presence of either 2,2’-bpy or 1,10-phen, respectively. The reaction of preformed precursor [Mn(OAc)(bpy)2](ClO4)(H2O) with phosphinic acids or phosphate diesters yield [Mn(L)(bpy)2]2(ClO4)2 (where L–H = dtbp-H = di-tert-butyl hydrogen phosphate (3), dpp-H = diphenyl hydrogen phosphate (4), dppi-H = diphenyl phosphinic acid (5), and ppi-H = phenyl phosphinic acid (6)), which are dimeric compounds. Polymers 1–2 and dinuclear cyclic compounds 3–6 have been extensively characterized by analytical and spectroscopic methods and also in each case by a single crystal X-ray diffraction study.Figure optionsDownload as PowerPoint slide