title: Metallacyclic yttrium alkyl and hydrido complexes: synthesis, structures and catalytic activity in intermolecular olefin hydrophosphination and hydroamination.
abstract: Metallacyclic neutral and ionic yttrium alkyl complexes coordinated by a dianionic ene-diamido ligand ([2,6-iPr2C6H3NC(Me)=C(Me)NC6H3iPr2-2,6] = L(1)) [L(1)]Y(CH2SiMe3)(THF)2 (2), {[L(1)]Y(CH2SiMe3)2}(-){Li(THF)4}(+) (3), [L(1)]Y(OEt2)(μ-Me)2Li(TMEDA) (4) were synthesized using a salt-metathesis approach starting from the related chloro complex [L(1)]Y(THF)2(μ-Cl)2Li(THF)2 (1) in 70, 85 and 72% yields respectively. The reactions of 2 with H2 or PhSiH3 afford the dimeric hydride {[L(1)]Y(THF)(μ-H)}2(μ-THF) (5) containing two μ-bridging hydrido and one μ-bridging THF ligands (91 and 85% yields). The X-ray studies of complexes 2, 3 and 5 revealed η(2)-coordination of the C=C fragment of an ene-diamido ligand to a Y cation. DFT calculations were carried out to give an insight into the metal-ligand bonding and especially the interaction between the metal and the ene-diamido ligand. The observed bonding of the ene-diamido fragment is found to reflect the acidity of the metal center in the complex that is partially overcome by a better donation from the double bond (better overlap with an empty d orbital at the yttrium center). The treatment of complex 4 with DME resulted in the C-O bond cleavage of DME and afforded a three nuclear methoxide oxide complex [{[L(1)]Y}3(μ(2)-OMe)3(μ(3)-O)](2-)[Li(DME)3](+)2 (6). Complexes 2, 3, 5 and 7 proved to be efficient precatalysts for the intermolecular hydrophosphination of styrene, 4-vinylpyridine, and 1-nonene with PhPH2 and Ph2PH as well as hydroamination of styrene and pyrrolidine.
authors.affiliation: G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Tropinina str. 49, 603950 Nizhny Novgorod, GSP-445, Russia. trif@iomc.ras.ru.
authors.forename: Alexander A
authors.initials: AA
authors.lastname: Kissel
authors.forename: Tatyana V
authors.initials: TV
authors.lastname: Mahrova
authors.forename: Dmitry M
authors.initials: DM
authors.lastname: Lyubov
authors.forename: Anton V
authors.initials: AV
authors.lastname: Cherkasov
authors.forename: Georgy K
authors.initials: GK
authors.lastname: Fukin
authors.forename: Alexander A
authors.initials: AA
authors.lastname: Trifonov
authors.forename: Iker
authors.initials: I
authors.lastname: Del Rosal
authors.forename: Laurent
authors.initials: L
authors.lastname: Maron