Nucleophilic addition reactions to the allenylidene complex [Cp∗Rudouble bond; length as m-dashCdouble bond; length as m-dashCdouble bond; length as m-dashCPh2(CO)(PMeiPr2)]+: X-ray crystal structures of image, image, image and image

The allenylidene complex View the MathML source[Cp∗RuCCCPh2(CO)(PMeiPr2)][BAr4′] (1) reacts with benzophenoneimine yielding the azaallenyl derivative View the MathML source[Cp∗Ru{C(NCPh2)CHCPh2}(CO)(PMeiPr2)][BAr4′] (2). The addition of primary or secondary amines to 1 yields vinylaminocarbenes, which are better formulated as azoniabutadienyl complexes View the MathML source[Cp∗Ru{C(NRR′)CHCPh2}(CO)(PMeiPr2)][BAr4′] (R = H, R′ = CH2Ctriple bond; length of mdashCH (3), R = H, R′ = Me (4), R = R′ = iPr (5)). Tertiary phosphines add to the Cα atom of the allenylidene chain furnishing allenylphosphonio species View the MathML source[Cp∗Ru{C(PR3)CCPh2}(CO)(PMeiPr2)][BAr4′] (PR3 = PMe3 (6), PMeiPr2 (7)). The reaction of 1 with propanethiol afforded the thiocarbene View the MathML source[Cp∗Ru{C(SnPr)CHCPh2}(CO)(PMeiPr2)][BAr4′] (8), which can be treated as a η1-thiabutadienyl.