Thermal reactions of Mes*-substituted triphospha[3]radialene (Mes*: 2,4,6-tri-t-butylphenyl) with [M(CO)5·(thf)] (M = Cr, W) resulted in the formation of the corresponding group 6 metal–pentacarbonyl complexes bearing the triphospha[3]radialene ligand, where one of the P=C bond moiety of the triphospha[3]radialene was σ-coordinating to the metal moiety in η1-fashion. The noncoordinating P=C bonds in the obtained complexes were found to undergo photochemical (E)–(Z) isomerization.
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