Addition of KN(R)Ph to írans-CPMeskPdCR')! (R = H, Me; R' = Ph, Me) results in the formation of the monomeric anilide complexes ircms-CPMeghPdCRONCRiPh in good yield. A single-crystal X-ray diffraction study of #rans-(PMe3)2Pd(Ph)N(H)Ph (1) reveals that it crystallizes in the space group PI with a = 8.423(3) Á, h = 10.768(4) Á, c = 12.565 Á, a = 68.81(3)°, ß -71.90(3)°, y = 87.65(3)°, V -1006.7(7) Á3, and Z = 2. There is no evidence for significant interaction between the N lone pair and the metal center, though a shortened N-C distance (1.32(2) Á) may indicate interaction between the N lone pair and the phenyl ring. Thermolysis of 1 at 90 °C in the solid state results in loss of PMes and formation of the dimeric complex [(PMe3)Pd(Ph)(w-NHPh)]2 (9), which was also characterized with a singlecrystal X-ray structure study. Compound 9 crystallizes in the space group PI with a = 6.805(1) Á, b = 12.186(2) Á, c = 18.943(3) Á, a -89.56(1)°, ß = 85.17(1)°, y = 87.67(1)°, V -1564.0(4) Á3, and Z = 2. The PMes groups are anti with respect to the Pd-Pd vector, while the phenyl groups of the anilides are anti with respect to the Pd2N2P2C2 coordination plane. In solution at 25 °C, 9 undergoes an isomerization equilibrium to form two new isomers. Spectroscopic data suggest that these two new isomers are consistent with syn PMes groups and syn anilide groups. Prolonged heating (110 °C, 12 h) of 9 results in reductive elimination of diphenylamine. 1991, 10, 2969.
From the corresponding TpMo(CO) 2 (π-allyl) complexes, four symmetrically substituted TpMo(CO)(NO)(π-allyl) + complexes (π-allyl ) propenyl, 2-methylpropenyl, cyclohexenyl, and cyclooctenyl) were prepared and characterized by IR, by 1 H and 13 C NMR spectroscopy, and in one case by X-ray crystallography. The BF 4 -salts of the cationic nitrosyl complexes were unstable in solution; however, using the noncoordinating counterion [(3,5-(CF 3 ) 2 C 6 H 3 ) 4 B] -
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.