Some chemistry with a chiral phosphine generated from fenchone–pinacolone mixed azine: crystal structure of Z,E-Ph2PCH2C(But)N–NC10H16

Abstract

Treatment of fenchone hydrazone with tert-butyl methyl ketone gave the mixed azine MeC (Bu^t)N–NC₁₀H₁₆ which on treatment with LiBuⁿ followed by PClPh₂ gave the mixed azine monophosphine Z,E-Ph₂PCH₂C(Bu^t)N–NC₁₀H₁₆. This was converted into the corresponding phosphine oxide or phosphine sulfide. The azine monophosphine with [Mo(CO)₄(nbd)](nbd = norbornadiene) gave the chelate complex [[graphic omitted]C₁₀H₁₆}] which with L undergoes ring-opening to give [Mo(CO)₄L{PPh₂CH₂C(Bu^t)N–NC₁₀H₁₆}](L = CO, CN Bu^t or CNMe) with monodentate phosphine. Corresponding tungsten complexes [[graphic omitted]C₁₀H₁₆}] and [W(CO)₄L{PPh₂CH₂C(Bu^t)N–NC₁₀H₁₆}](L = CNBu^t or CNMe) were also prepared. Crystals of Z,E-Ph₂PCH₂C(Bu^t)N–NC₁₀H₁₆ are monoclinic, space group P2₁ with a= 11.0737(8), b= 11.0377(9), c= 11.1072(7)Å, β= 110.60(5)° and Z= 2 for 3492 observed reflections. Proton, ³¹P-{¹H}, ¹³C-{¹H} NMR, IR and mass spectral data are given.