Construction of {Mn[Ph2P(O)NP(O)Ph2]2} units with mono- and bi-pyridines: Syntheses, molecular structures, and spectroscopic properties of manganese(II) complexes with tetraphenylimidodiphosphinates

Treatment of [Mn(CH3COO)(2)center dot 4H(2)O] with two equivalents of K[N(Ph2PO)(2)] in the presence of two equivalents of pyridine (py) or 4-Bu-t-pyridine (4-Bu-t-py) in MeOH-H2O afforded mononuclear complexes [Mn {N(Ph2PO)(2)}(2)(pY)(2)]center dot 2H(2)O (1) and [Mn[N(Ph2PO)(2))(2)(4-Bu-t-py)(2)] (2), respectively. Interaction of [Mn (CH3COO)(2)center dot 4H(2)O] with two equivalents of K[N(Ph2PO)(2)] in the presence of one equivalent of rigid dipyridyl-based ligand 4,4'-bipyridine (bpy) or trans-1,4-bis-(pyridyl)ethene (bpe) resulted in formation of one-dimensional linear polymeric chains [Mn{N(Ph2PO)(2)}(2)(mu-bPY)(n) (3) and [Mn{N(Ph2PO)(2)}(2)(mu-bpe)center dot 2CH(2)Cl(2)](n) (5), respectively. Reaction of [Mn(CH3COO)(2)center dot 4H(2)O] with each of one equivalent of K[N (Ph2PO)(2)] and K[Ph2PO2] in the presence of one equivalent of bpy afforded a polymeric complex [Mn {N(Ph2PO)(2))(2)(mu-bPY)(n)-[Mn-2(N(ph(2)PO)(2))(2)(mu-Ph2PO2)(2)(mu-bPY)(n) (4) which contains two independent one-dimensional linear polymeric chains. Self-assembly reaction of [Mn(CH3COO)(2)center dot 4H(2)O], K[N (Ph2PO)(2)], bpy and bpe in a 1:2:1:1 ratio gave a dinuclear complex [Mn(bpe){N(Ph2PO)(2)}(2)](2)(mu-bPY)center dot H2O (6). Self-assembly reaction of [Mn(CH3COO)(2)center dot 4H(2)O], K[N(Ph2PO)(2)], and a flexible dipyridyl-based ligand 4,4'-trimethylenedipyridine (tmpy) in a 1:2:1 ratio gave a tetranuclear complex [Mn{N (Ph2PO)(2)}(2)(mu-tmpy)](4)center dot 2CH(3)OH center dot 3H(2)O (7). All complexes are air-stable in the solid-state, and were well characterized by electronic, infrared and mass spectroscopies along with thermogravimetric analyses, and their molecular structures have been well established by X-ray crystallography. (C) 2018 Elsevier Ltd. All rights reserved.