Using base-free Ln[N(SiHMe 2 ) 2 ] 3 complexes as highly effectiVe protodeamination reagents, the binuclear lanthanide complexes p-bis{η 5 -(2,3,4,5-tetramethylcyclopentadienyl)Ln[N(SiHMe 2 ) 2 ] 2 }phenylene [p-Ln 2 ] (Ln ) Y, La, Lu) and m-bis{η 5 -(2,3,4,5-tetramethylcyclopentadienyl)La-[N(SiHMe 2 ) 2 ] 2 }phenylene [m-La 2 ] were synthesized from the corresponding phenylene-linked tetramethylcyclopentadienes. The resulting products serVe as new types of multicenter homogeneous 4f catalysts. ReactiVity studies reVeal that these binuclear organolanthanide complexes efficiently catalyze the intramolecular hydroamination/cyclization of aminoalkenes, aminoalkynes, and aminodienes, with turnoVer frequencies as high as 10 h -1 at 60 °C.

The phenylene-bridged bimetallic organolanthanide complexes p-bis{Cp′′Ln[N(SiHMe 2 ) 2 ] 2 }phenylene (p-Ln 2 ; Ln ) Y, La, Cp′′ ) tetramethylcyclopentadienyl) and m-bis{Cp′′La[N(SiHMe 2 ) 2 ] 2 }phenylene (m-La 2 ) are investigated for possible Ln • • • Ln cooperative effects in hydroamination processes. These binuclear organolanthanide complexes efficiently catalyze the intramolecular hydroamination/cyclization of aminoalkenes, aminoalkynes, aminoallenes, and conjugated aminodienes with turnover frequencies as high as 10 h -1 at 60 °C, as well as intermolecular hydroaminations with turnover frequencies as high as 0.4 h -1 at 90 °C. Substrates include those having both compressed and extended junctures between the C-C unsaturation and the -NH 2 group, as well as those with multiple -NH 2 groups or places of C-C unsaturation. Reactivity trends appear to be dominated by nonbonded repulsive interactions, resulting in catalytic activities following the general trend m-Ln 2 < p-Ln 2 . Organolanthanide amide complexes are also shown to catalyze the prototropic isomerization of alkynes.

Deprotonation of the phosphine complexes Au(PHR2)Cl with aqueous ammonia gave the gold(I) phosphido complexes [Au(PR2)] n (PR2 = PMes2 (1), PCy2 (2), P(t-Bu)2 (3), PIs2 (4), PPhMes (5), PHMes* (6); Mes = 2,4,6-Me3C6H2, Is = 2,4,6-(i-Pr)3C6H2, Mes* = 2,4,6-(t-Bu)3C6H2, Cy = cyclo-C6H11). 31P NMR spectroscopy showed that these complexes exist in solution as mixtures, presumably oligomeric rings of different sizes. X-ray crystallographic structure determinations on single oligomers of 1−4 revealed rings of varying size (n = 4, 6, 6, and 3, respectively) and conformation. Reactions of 1−3 and 5 with PPN[AuCl2] gave PPN[(AuCl)2(μ-PR2)] (9−12, PPN = (PPh3)2N+). Treatment of 3 with the reagents HI, I2, ArSH, LiP(t-Bu)2, and [PH2(t-Bu)2]BF4 gave respectively Au(PH(t-Bu)2)(I) (14), Au(PI(t-Bu)2)(I) (15), Au(PH(t-Bu)2)(SAr) (16, Ar = p-t-BuC6H4), Li[Au(P(t-Bu)2)2] (17), and [Au(PH(t-Bu)2)2]BF4 (19).

Gold(I) Phosphanyl Complexes, such as [Au(PR2)]n, have been known for more than 25 years. However, the solid‐state structure of such complexes, as well as their nature in solution, has remained somewhat of a mystery. The figure displays the cyclic and polymeric forms that are possible (L=endgroup). The structures of the complexes, and the occurrence of Au⋅⋅⋅Au interactions are discussed.