The
reaction of [AnCl(NR2)3] (An = U or Th;
R = SiMe3) with NaCCH and tetramethylethylenediamine (TMEDA)
results in the formation of [An(CCH)(NR2)3] (1, An = U; 2, An = Th), which can be
isolated in good yields after workup. Similarly, the reaction of 3
equiv of NaCCH and TMEDA with [AnCl(NR2)3] results
in the formation of [Na(TMEDA)][An(CCH)2(NR2)3] (4, An = U; 5, An
= Th), which can be isolated in fair yields after workup. The reaction
of 1 with 2 equiv of KC8 and 1 equiv of 2.2.2-cryptand
in tetrahydrofuran results in formation of the uranium(III) acetylide
complex [K(2.2.2-cryptand)][U(CCH)(NR2)3] (3). Thermolysis of 1 or 2 results in formation of the bimetallic dicarbide complexes [{An(NR2)3}2(μ,η1:η1-C2)] (6, An = U; 7,
An = Th), whereas the reaction of 1 with [Th{N(R)(SiMe2
CH2)}(NR2)2] results in the formation of [U(NR2)3(μ,η1:η1-C2)Th(NR2)3] (8). The 13C NMR chemical shifts of the α-acetylide carbon atoms
in 2, 5, and 7 exhibit a characteristic
spin–orbit-induced downfield shift, due to participation of
the 5f orbitals in the Th–C bonds. Magnetism measurements demonstrate
that 6 displays weak ferromagnetic coupling between the
uranium(IV) centers (J = 1.78 cm–1).
1-(Trimethylsilyl)propyne 2a reacts with halogenoboranes XB(C6F5)2 (X: Cl, Br) in a 2 : 1 molar ratio under mild conditions by consecutive 1,1-carboboration reactions to give the highly substituted boryldienes 4.
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