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- W2334673521 abstract "The reaction of H2C(PCl2)2 with 4 equiv of tBuMgCl in tetrahydrofuran (THF) produces 1,4-(CH2)2(PtBu)4, 1, in about 65% yield. This six-membered ring reacts directly with elemental sulfur or selenium in toluene at low temperatures to give the mono- and dichalcogenides 1,4-(CH2)2(PtBuE)(PtBu)3 (E = S, 2a, E = Se, 2b) and 1,4-(CH2)2-2,5-(PtBuE)2(PtBu)2 (E = S, 3a, E = Se, 3b). X-ray structural determinations showed that 3a and 3b are isostructural in the solid state; the six-membered C2P4 ring exhibits a twist-boat geometry with chalcogen substituents in syn positions in each case. Density functional theory (DFT) calculations for the three possible isomers of disubstitution were performed to elucidate the factors that favor the 2,5-isomer. Thermal isomerism was observed in solutions of 3b or 3a in toluene at 60 and 95 °C, respectively, to give the corresponding 2,6-isomers. With an excess of chalcogen in toluene at reflux, the four-membered rings (H2C)(PtBuE)2E (E = S, 4a, E = Se, 4b) were obtained and identified by multinuclear NMR spectroscopy and single crystal X-ray crystallography, which showed the tBu groups in a trans orientation with respect to the CP2E ring. With a large excess of chalcogen, the five-membered rings (H2C)(PtBuE)2E2 (E = S, 5a, E = Se, 5b) were also observed; the X-ray structure of 5b revealed a half-envelope conformation for the CP2Se2 ring. The direct reaction of 4a with sulfur in boiling toluene does not produce 5a, whereas 5b is formed slowly and in low yields from 4b and selenium under similar conditions. On the basis of DFT calculations of the relative energies of likely intermediates, chalcogen insertion into the P–P bonds of 3a and 3b to give eight-membered C2P4E2 rings, followed by monomerization, is proposed as a feasible pathway for the formation of the four-membered CP2E heterocycles 4a and 4b." @default.
- W2334673521 created "2016-06-24" @default.
- W2334673521 creator A5015736816 @default.
- W2334673521 creator A5052240063 @default.
- W2334673521 date "2013-06-20" @default.
- W2334673521 modified "2023-09-24" @default.
- W2334673521 title "Chalcogenation of the 1,4-C<sub>2</sub>P<sub>4</sub> Ring: Oxidation, Isomerization, Insertion, and Ring Contraction" @default.
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- W2334673521 doi "https://doi.org/10.1021/ic401002b" @default.
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