Diphosphate−Zinc Complexes with Chelating Coligands

While the structural elucidation and coordination chemistry of organo‐monophosphates have been well investigated, research on the simplest member of organo‐oligophosphates, viz. diorganopyrophosphates, is relatively rare due to the inherent hydrolytic instability of the ligand. Water elimination from the 2,6‐diisopropyl phenyl phosphate (dippH2) by the action of dicyclohexylcarbodiimide (DCC) results in the isolation of a diorganopyrophosphates ligand formulated as [O{P(OAr)(OH)(O)}2] (1 or pyrodippH2) (Ar = 2,6‐diisopropylphenyl). Due to the instability of 1, it has been transformed into its sodium salt [O{P(OAr)(ONa)(O)}2] (2), which has been used for further reactions to prepare cobalt pyrophosphate complexes 3–7. Reaction of 2 with anhydrous cobalt(II) chloride in the presence of N‐heterocyclic ligands results in the formation of [Co(pyrodipp)(imz)3] (3), [Co(pyrodipp)(bpy)2](CH3OH) (4) and [Co(pyrodipp)(phen)2] (5) (imz = imidazole; bpy = 2,2'‐bipyridine; phen = 1,10‐phenanthroline). Use of multidentate ancillary ligand such as 4‐pyridyl‐2,2':6',2''‐terpyridine (pyterpy) under similar reaction conditions leads to the formation of a one‐dimensional zig‐zag cobalt pyrophosphate coordination polymer [Co(pyrodipp)(pyterpy)(CH3OH)]n (6). In the absence of any ancillary ligand, the reaction between cobalt(II) chloride and 2 in acetonitrile results in the isolation of an interesting inorganic polymer [Co(pyrodipp)(CH3CN)2]n (7), whose backbone consists of a chain of spirocycles of CoP2O3 rings, joined at the cobalt centers. The newly synthesized cobalt pyrophosphates 3–7 have been characterized by both analytical and spectroscopic techniques, magnetic studies apart from single‐crystal X‐ray diffraction studies in each case. A striking and persistent structural feature in 3–7 is the presence of the cobalt pyrophosphate six‐membered metallacycle Co(OPOPO). While cobalt metal exists in trigonal bipyramidal geometry in complex 3, distorted octahedral coordination geometry is observed for cobalt centers in complexes 4–7.

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Discrete and Polymeric Cobalt Pyrophosphates Derived from Pyrophosphoric Acid Diester Ar₂H₂P₂O₇

Sharma

Gupta

Murugavel

2020

Eur J Inorg Chem

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Synthesis, Characterization, and Crystal Structures of a New Coordination Polymer of Manganese(II) Containing Dimethyl Phosphate

Rafizadeh

Amani

Farajian

2007

Zeitschrift anorg allge chemie

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Coordination complexes incorporating pyrophosphate: Structural overview and exploration of their diverse magnetic, catalytic and biological properties

Ikotun¹,

Marino²,

Kruger³

et al. 2010

Coordination Chemistry Reviews

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Diphosphate−Zinc Complexes with Chelating Coligands

Cited by 13 publications

References 27 publications

Discrete and Polymeric Cobalt Pyrophosphates Derived from Pyrophosphoric Acid Diester Ar₂H₂P₂O₇

Discrete and Polymeric Cobalt Pyrophosphates Derived from Pyrophosphoric Acid Diester Ar₂H₂P₂O₇

Synthesis, Characterization, and Crystal Structures of a New Coordination Polymer of Manganese(II) Containing Dimethyl Phosphate

Coordination complexes incorporating pyrophosphate: Structural overview and exploration of their diverse magnetic, catalytic and biological properties

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Diphosphate−Zinc Complexes with Chelating Coligands

Cited by 13 publications

References 27 publications

Discrete and Polymeric Cobalt Pyrophosphates Derived from Pyrophosphoric Acid Diester Ar2H2P2O7

Discrete and Polymeric Cobalt Pyrophosphates Derived from Pyrophosphoric Acid Diester Ar2H2P2O7

Synthesis, Characterization, and Crystal Structures of a New Coordination Polymer of Manganese(II) Containing Dimethyl Phosphate

Coordination complexes incorporating pyrophosphate: Structural overview and exploration of their diverse magnetic, catalytic and biological properties

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Product

Resources

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Discrete and Polymeric Cobalt Pyrophosphates Derived from Pyrophosphoric Acid Diester Ar₂H₂P₂O₇

Discrete and Polymeric Cobalt Pyrophosphates Derived from Pyrophosphoric Acid Diester Ar₂H₂P₂O₇