Ligand exchange reactions and hydroamination with tris(oxazolinyl)borato yttrium compounds.

Ligand substitution reactions and catalytic hydroamination/cyclization of aminoalkenes have been studied with a new oxazolinylborato yttrium compound, tris(4,4-dimethyl-2-oxazolinyl)phenylborato bis(trimethylsilylmethyl)yttrium ([Y(kappa(3)-To(M))(CH(2)SiMe(3))(2)(THF)], 1). THF exchange in 1 is rapid at room temperature, and activation parameters obtained by simulation of (1)H NMR spectra acquired from 190 to 280 K are consistent with a dissociative mechanism (DeltaS(++) = 30 +/- 1 e.u.

A tris(alkyl)yttrium compound containing six beta-agostic Si-H interactions.

The new homoleptic rare earth compound [Y(C(SiHMe(2))(3))(3)] () is prepared in 82% yield by salt metathesis of YCl(3) and 3 equivalents of [KC(SiHMe(2))(3)] (); two beta-agostic Y(H-Si) interactions are observed for each C(SiHMe(2))(3) ligand in , giving six agostic interactions per yttrium(iii) center.

Easily prepared chiral scorpionates: tris(2-oxazolinyl)boratoiridium(i) compounds and their interactions with MeOTf.

Optically active C 3-symmetric monoanionic ligands are uncommon in organometallic chemistry. Here we describe the synthesis of readily prepared tris(4 S-isopropyl-2-oxazolinyl)phenylborate [To (P)] and fluxional, zwitterionic four- and five-coordinate iridium(I) compounds [Ir(To (P))(eta (4)-C 8H 12)] ( 4) and [Ir(To (P))(CO) 2] ( 5). The highly fluxional nature of 4 and 5 makes structural assignment difficult, and the interaction between the iridium(I) center and the [To (P)] ligand is established by solid-state and solution (15)N NMR methods that permit the direct comparison between solution and solid-state structures.

Alkyl carbon-nitrogen reductive elimination from platinum(IV)-sulfonamide complexes.

Platinum(IV) complexes containing monodentate sulfonamide ligands, fac-(dppbz)PtMe(3)(NHSO(2)R) (dppbz = o-bis(diphenylphosphino)benzene; R = p-C(6)H(4)(CH2)(3)CH(3) (1a), p-C(6)H(4)CH(3) (1b), CH(3) (1c)), have been synthesized and characterized, and their thermal reactivity has been explored. Compounds 1a-c undergo competitive C-N and C-C reductive elimination upon thermolysis to form N-methylsulfonamides and ethane, respectively. Selectivity for either C-N or C-C bond formation can be achieved by altering the reaction conditions.