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

Abstract

Treatment of [Mn(CH3COO)2·4H2O] with two equivalents of K[N(Ph2PO)2] in the presence of two equivalents of pyridine (py) or 4-tBu-pyridine (4-tBu-py) in MeOH–H2O afforded mononuclear complexes [Mn{N(Ph2PO)2}2(py)2]·2H2O (1) and [Mn{N(Ph2PO)2}2(4-tBu-py)2] (2), respectively. Interaction of [Mn(CH3COO)2·4H2O] 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(μ-bpy)]n (3) and [Mn{N(Ph2PO)2}2(μ-bpe)·2CH2Cl2]n (5), respectively. Reaction of [Mn(CH3COO)2·4H2O] 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(μ-bpy)]n-[Mn2{N(Ph2PO)2}2(μ-Ph2PO2)2(μ-bpy)]n (4) which contains two independent one-dimensional linear polymeric chains. Self-assembly reaction of [Mn(CH3COO)2·4H2O], 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(μ-bpy)·H2O (6). Self-assembly reaction of [Mn(CH3COO)2·4H2O], 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(μ-tmpy)]4·2CH3OH·3H2O (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.