Syntheses and crystal structures of molybdenum(0) and palladium(II) complexes of 4-tert-butyl-2-diphenylphosphino-cyclohexanone N,N-dimethylhydrazone

Article abstract of DOI:10.1016/0020-1693(95)04618-J

Deprotonation of 4-tert-butyl-cyclohexanone N,N-dimethylhydrazone (1) with LiBu(n) at - 15°C, followed by addition of PPh2Cl gave the corresponding phosphino dimethylhydrazone Z-PPh2C10H17=NNMe2 (2), in which the PPh2 group is in the axial position. 2 reacts with [Mo(CO)4(nbd)] (nbd=norbonadiene) to give the tetracarbonyl complex [Mo(CO)4(Z-PPh2C10H17=NNMe2)] (3), containing a six-membered chelate ring and an axial PPh2 group. Treatment of 2 with Na2PdCl4 or [PdCl2(NCPh)2] gave the dichloropalladium(II) complex [PdCl2(E-PPh2C10H17=NNMe2)] (4), containing a five-membered chelate ring and an equatorial PPh2 group due to isomerisations at C(2) and around C=N. Crystals of 3 are monoclinic, space group P21/n with a=2083.4(4), b=1089.0(2), c=2521.9(5) pm, β=98.82(2)° and Z=8, R=0.0263 for 6109 observed reflections with 1>2.0 σ(I). Crystals of 4 are monoclinic, space group P21/n with a=11.271(2), b=13.205(3), c=17.849(3)?, β=104.83(1)° and Z=4, R(1)=0.0304 for3994 observed reflections.