Pentafluoroaryl transfer from tris(pentafluorophenyl)boron hydrate to nickel. Synthesis and X-ray crystal structure of (PPh2CH2C(O)Ph)Ni(C6F5)(2)

• Published in: Organometallics Vol. 19; no. 19; pp. 3983 - 3990
• Main Authors: Kalamarides, HA, Iyer, S, Lipian, J, Rhodes, LF, Day, C
• Format: Journal Article
• Language: English
• Published: WASHINGTON Amer Chemical Soc 18.09.2000
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Physical Sciences; Science & Technology; LIGANDS; HOMOGENEOUS OLEFIN POLYMERIZATION; MOLECULAR-STRUCTURE; LEWIS-ACID; ORGANOMETALLIC COMPLEXES; CATALYTIC ACTIVITY; METALLOCENE-LIKE INITIATOR; (ETA-CME)TIME(MU-ME)B(C6F5); ETHYLENE POLYMERIZATION; NONCOORDINATING ANIONS
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/om000606w

The reaction of tris(pentafluorophenyl)boron trihydrate, B(C6F5)(3).3H(2)O (1), with the nickel dimer [(PPh2CH=C(O)Ph)Ni(Ph)](2) (3) (synthesized by phosphine abstraction from (PPh2CH=C(O)Ph)Ni(Ph)(PPh3) (2)) yields (PPh2CH2C(O)Ph)Ni(C6F5)(2) (4). In this reaction a number of processes occur: fragmentation of the dimer 3, transfer of two protons from 1, and transfer of two C6F5 groups from boron to nickel. In solution, 4 loses one C6F5 ligand as pentafluorobenzene due to proton transfer from the chelating ligand, forming the dimer [(PPh2CH=C(O)Ph)Ni(C6F5)](2) (5) Compounds 4 and 5 were characterized by NMR and MS techniques. Compound 4 was independently synthesized by the reaction of PPh2CH2C(O)Ph and (eta(6)-toluene)Ni(C6F5)(2). The crystal structure of 4 was determined using single-crystal X-ray diffraction methods. Details concerning the synthesis and characterization of 1-3 are also given.