Reduction of the tetravalent complex [{2,5-[(C4H3N)CPh2]2[C4H2N(Me)]}ThCl2 (THF)]·THF (2) of the tripyrrolide dianion 2,5-[(C4H3N)CPh2]2C4H2N(Me) afforded different products depending on the reaction conditions. In every case, the reaction proceeded via the initial formation of a reduced species, as indicated by the very rapid formation of a dark red color followed by slow and complete discoloration. In the case of the reduction in toluene, the complexes ({2,5-[(C4H3N)CPh2]2[C4H2N]}2Th[K(toluene)]2)·1.5(toluene) (3a) and {2,5-[(C4H3N)CPh2]2[C4H2N]}2Th[K(DME)]2 (3b) were obtained, depending on the crystallization solvent (toluene versus DME). In both cases, the products arose from a loss of the methyl group attached to the central pyrrole ring N atom. When the reduction was carried out in DME as a solvent, the complex {[{2,5-[(C4H3N)CPh2]2[C4H2N(Me)]}Th(OMe)]2(m-OC2H4OMe)2}· 0.75(hexane) (5) was isolated. This species is derived from two different pathways of C−O cleavage of the DME solvent. Reduction of {2,5-[(C4H3N)CPh2]2[C4H2N(Me)]}ThCl{(C4H3N)CPh2[C4H3N(Me)]} (6), containing both the monoalkylated tripyrrolide and dipyrrolide ligands, afforded instead pyrrolide ring opening and formation of [({2,5-[(C4H3N)CPh2]2[C4H2N(Me)]}Th[(C4H3N)CPh2(CCHCHCHNMe)])2(m-K)][K(DME)4]·2(hexane) (7).

A multi-pyrazolyl cyclotriphosphazene containing polymerizable group N(3)P(3)(3,5-Me(2)Pz)(5)(O-C(6)H(4)-p-C(6)H(4)-p-CH=CH(2)) (2) has been prepared from the corresponding chloro derivative N(3)P(3)Cl(5)(O-C(6)H(4)-p-C(6)H(4)-p-CH=CH(2)) (1). The X-ray structures of 1 and 2 have been determined. Compound 2 undergoes ready metalation with CuCl(2) to afford N(3)P(3)(3,5-Me(2)Pz)(5)(O-C(6)H(4)-p-C(6)H(4)-p-CH=CH(2)).CuCl(2) (3). Model compound N(3)P(3)(3,5-Me(2)Pz)(5)(O-C(6)H(4)-p-CHO).CuCl(2) (6) has been prepared and characterized by spectroscopy and X-ray crystallography. In this compound, the coordination around copper is distorted trigonal bipyramidal, and the cyclotriphosphazene coordinates in a non-gem N(3) mode. Compound 2 has been copolymerized with divinylbenzene to afford cross-linked multisite coordinating polymer CPPL which is readily metalated with CuCl(2) to afford copper-containing polymer CPPL-Cu. The coordination environment around copper in CPPL-Cu has been evaluated by obtaining its EPR, optical, and IR spectra and comparing them with those of model compounds 3 and 6. The utility of CPPL-Cu as a heterogeneous catalyst has been demonstrated in the phosphate ester hydrolysis involving three model phosphate esters: p-nitrophenyl phosphate (pNPP), bis(p-nitrophenyl) phosphate (bNPP), and 2-(hydroxypropyl)-p-nitrophenyl phosphate (hNPP). In all of these reactions, a significant rate enhancement of ester hydrolysis is observed. Detailed kinetic analyses to evaluate Michaelis-Menten parameters have also been carried out along with experiments to elucidate the effect of pH, solvent, and temperature on the rate of hydrolysis. Recycling experiments on the hydrolysis of pNPP with CPPL-Cu shows that it can be recycled several times over without affecting the rates.

Two unusual trinorsesquiterpenoids, urechitols A (1) and B (2), were isolated from the root extract of Pentalinon andrieuxii, a plant used commonly in Yucatecan traditional medicine to treat leishmaniasis. The structures of 1 and 2 were identified by interpretation of their spectroscopic data and chemical correlation reactions. The relative stereochemistry of 1 was confirmed through an X-ray crystallographic study.