Lanthanide mediated activation of C-H and C-X bonds

In dit proefschrift wordt de activering van C-H en C-X bindingen door organolanthanide complexen beschreven (X = hetero-atoom).

Organolanthanide-catalysed Oligomerisation of 2-Cycloalken-1-ones

Yttrium and lanthanum hydrides [(C5Me5)2LnH]2 are active catalysts for the oligomerisation of 2-cycloalken-1-ones; the average degree of oligomerisation increases with temperature.

A Direct Catalytic Synthesis of Sodium Diarylphosphinates and Their Corresponding Acids from Sodium Phosphinate

Widely available, hazard-free sodium phosphinate directly furnishes sodium diarylphosphinates and their corresponding acids in yields up to 86 % by using Pd-catalysis. This versatile method tolerates moieties such as keto and carboxyl, incompatible with the classical Grignard or organolithium reagents. This route also eliminates the need for PCl3 and alkyl- or ammoniumphosphinates

Reaction of (Cp*2LnH)2 (Ln = Y, La) and Cp*2Y(2-C6H4CH2NMe2) with Esters and Amides and Molecular Structure of [Cp*2Y(μ-OCMe=CHC(OEt)O)]2

The activation of esters and amides by (Cp*2LnH)2 [Ln=Y (1a), Ln=La (1b), Cp*=C5Me] and Cp*2Y(2-C6H4CH2NMe2) (2) is described. Compounds 1a and 1b react with ethyl acetate to form Cp*2YOEt (3a) and Cp*2LaOEt (3b). With 1a and ethyl benzoate a 1:1 mixture of 3a and Cp*2YOCH2Ph (4a) is produced and the corresponding 1:1 mixture of 3b and Cp*2LaOCH2Ph (4b) is observed with 1b. Ethyl acrylate is polymerized rapidly by both 1a and 1b. The reaction of 1a with N,N-dimethylacetamide leads to a mixture of the carbonyl insertion product Cp*2Y(OCH(NMe2)Me) (5) and the aldol condensation product Cp*2Y(OC(NMe2)(Me)CH2C(O)NMe2) (6). Formation of the condensation product [Cp*2Y(μ-OCMe=CHC(OEt)O)]2 (7) occurred when 2 was reacted with ethyl acetate. The molecular structure of 7 was determined by X-ray diffraction: a=10.129(1)Å, b=10.650(1)Å, c=12.093(1) Å, α=77.642(6)°, β=79.402(7), γ=86.408(9), V=1252.2(2) Å3, space group P1, Z=1. Anisotropic least-squares refinement based on 4871 reflections converged to RF=0.034 and Rw=0.041 for 428 refined parameters. The more sterically hindered ester ethyl 2-methylpropanoate reacted with 2 to produce the enolate complex Cp*2Y{OC(2-C6H4CH2NMe2)=CMe2}(Me2CHCOOEt) (8). With N,N-dimethylacetamide 2 gives a clean aldol condensation to form 6.