The reaction of 1,1,2,3,3-pentamethyltrimethylenephosphinic acid cycP(O)OH and (C6H11)2P(O)OH with monoorganotellurium trichloride RTeCl3 (R = 2-phenylazophenyl) in benzene at room temperature afforded two pentanuclear complexes, [(RTe)4(TeO)(U-O) 6(cycPO2)2]·THF(1) [cycPO2 = 1,1,2,3,3-pentamethylene phosphinate] and [(RTe)4(TeO)(U-O) 6{(C6H11)2PO2} 2]·2C6H6 (2). The reactions leading to the formation of 1 and 2 involve a Te-C bond cleavage. 1 and 2 are isostructural complexes and contain a Te4P2O6 macrocyclic framework that is part of a Te5O11P2 multi-metallacyclic framework. Both of these compounds contain a central inorganic Te=O connected to four other tellurium centers through four U-O bridges. © 2014 American Chemical Society.