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• W2068257760 abstract "Irradiation of [bis(diisopropylamino)phosphino](trimethylsilyl)diazomethane at 254 nm in the presence of tert-butylphosphaalkyne leads to 1σ4,2σ2-diphosphete 1 in 90% yield. Derivative 1 reacts with Fe2(CO)9 and W(CO)5(THF) giving rise to the corresponding η1-complexes 2 (48% yield) and 3 (75% yield), respectively. When 1 equiv of methyl trifluoromethanesulfonate and elemental selenium is added to derivative 1, the cationic and neutral 1σ4,2σ3-diphosphetes 4 and 5 are isolated in 95 and 66% yields, respectively. Addition of 2 equiv of elemental selenium and bis(trimethylsilyl)peroxide to diphosphete 1 gave rise to 1σ4,2σ4-diphosphetes 6 (43% yield) and 7 (84% yield), respectively. η1-(1σ4,2σ2-Diphosphete)tungsten complex 3 reacted with bis(trimethylsilyl)peroxide affording heterocyclic complex 8 (68% yield). Addition of 1 equiv of tetrachloro-o-benzoquinone (TCBQ) to the cationic 1σ4,2σ3-diphosphete 4 and of 2 equiv to the 1σ4,2σ2-diphosphete 1 affords the 1σ4,2σ5- and 1σ4,2σ6-diphosphetes 9 (86% yield) and 10 (92% yield), respectively. Addition of TCBQ to the η1-(1σ4,2σ2-diphosphete)tungsten complex 3 affords the η1-(1σ4,2σ4-diphosphete)complex 11 (88% yield), which reacts with 2 equiv of trimethylphosphine leading to the zwitterionic 1σ4,2σ3-diphosphete 12 (46% yield). Cleavage of the Si−C bond of complex 3 with 1 equiv of tetrabutylammonium fluoride hydrate gives η1-(1σ4,2σ2-diphosphete)complex 13 (61% yield), which reacts with TCBQ leading to the cis-1,2-diphosphino alkene complex 14 (77% yield). These results demonstrate that the unsaturated four-membered ring skeleton is a remarkable template for inducing unusual P−P interactions. However, the presence of two very bulky substituents on the ethylenic moiety is necessary for the persistence of the cyclic structure, when the two phosphorus atoms feature a high coordination state. Single crystal X-ray diffraction studies of derivatives 7 and 11−14 have been carried out." @default.
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• W2068257760 date "1997-10-01" @default.
• W2068257760 modified "2023-09-29" @default.
• W2068257760 title "1σ⁴,2σ<i>^x</i>-Diphosphetes (<i>x</i> = 2−6): On the Persistence of the P−P Bond" @default.
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• W2068257760 doi "https://doi.org/10.1021/ja971821f" @default.
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