title: Vinyl oxidative coupling as a synthetic route to catalytically active monovalent chromium.
abstract: Reaction of the deprotonated form of cis-{(t-Bu)N(H)P[μ-N(t-Bu)](2)PN(H)(t-Bu)} with CrCl(3)(THF)(3) afforded the trivalent cis-{(t-Bu)NP[μ-N(t-Bu)](2)PN(t-Bu)}[Li (THF)])CrCl(2) (1). Subsequent reaction with 2 equiv of vinyl Grignard (CH(2)=CH)Mg Cl gave the butadiene derivative (cis-{(t-Bu)NP[μ-N(t-Bu)](2)PN(t-Bu)}[Li(THF)])Cr(cis-η(4)-butadiene) (3) formally containing the metal in its monovalent state. The presence of the monovalent state was thereafter confirmed by DFT calculations. The coordination of the butadiene unit appears to be rather robust since reaction with Me(3)P afforded cleavage of the dimeric ligand core but not its displacement. The reaction formed the new butadiene complex [(t-Bu)N-P-N(t-Bu)]Cr(cis-η(4)-butadiene)PMe(3) (4) containing a regular NPN monoanion. In agreement with the presence of monovalent chromium, complexes 3 and 4 act as single-component self-activating catalysts for selective ethylene trimerization and dimerization, respectively.
authors.affiliation: Department of Chemistry, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Khalid
authors.initials: K
authors.lastname: Albahily
authors.forename: Yacoob
authors.initials: Y
authors.lastname: Shaikh
authors.forename: Elena
authors.initials: E
authors.lastname: Sebastiao
authors.forename: Sandro
authors.initials: S
authors.lastname: Gambarotta
authors.forename: Ilia
authors.initials: I
authors.lastname: Korobkov
authors.forename: Serge I
authors.initials: SI
authors.lastname: Gorelsky