RESUMEN
Oxidation of carbene-stabilized diarsenic, L:As-As:L [L: = :C{N(2,6-(i)Pr(2)C(6)H(3))CH}(2)] (1), with gallium chloride in a 1:4 ratio in toluene affords the dicationic diarsene complex [L:AsâAs:L](2+)([GaCl(4)](-))(2) (2(2+)[GaCl(4)](2)), while oxidation of 1 with GaCl(3) in a 1:2 ratio in Et(2)O yields the monocationic diarsenic radical complex [L:AsAs:L](â¢+)[GaCl(4)](-) (2(â¢+)[GaCl(4)]). Strikingly, complex 2(â¢+) is the first arsenic radical to be structurally characterized in the solid state. The nature of the bonding in these complexes was probed computationally and spectroscopically.
RESUMEN
The reaction of N-heterocyclic carbene, L:, with BeCl(2) quantitatively yields L:BeCl(2)1 (L: = :C{N(2,6-Pr(i)(2)C(6)H(3))CH}(2)). The carbene-stabilized beryllium borohydride monomer L:Be(BH(4))(2)2 is prepared by the reaction of 1 with LiBH(4). Compound 3, prepared by the reaction of 2 with Na(2)[Fe(CO)(4)]·dioxane, represents an unusual "dual reduction" of the imidazole ring (i.e., hydroboration of the CâC backbone and hydrogenation of the C2 carbene center).
RESUMEN
Reaction of carbene-stabilized diphosphorus, L:P-P:L (L: = :C{N(2,6-Pr(i)(2)C(6)H(3))CH}(2), 1), with excess BH(3)·THF affords the boronium salt [L:P(µ-BH(2))P:L](+)[B(2)H(7)](-), 2, which contains a three-membered P(2)B ring. When 2 is dissolved in THF, compounds 1 and 2 exist in a dynamic solution equilibrium.
RESUMEN
Reaction of carbene-stabilized disilicon L:SiâSi:L (L: = :C{N(2,6-Pr(i)(2)C(6)H(3))CH}(2), 1) with BH(3)·THF results in facile cleavage of the silicon-silicon double bond and the formation of two quite different "push-pull" stabilized products with borane- and carbene-coordinated silylene moieties: 2, containing a parent silylene (:SiH(2)); and 3, containing a unique three-membered cyclosilylene.
RESUMEN
The first anionic N-heterocyclic dicarbene, polymeric [:C{[N(2,6-Pr(i)(2)C(6)H(3))](2)CHCLi(THF)}](n) 1, containing both normal (C2) and abnormal carbene (C4) centers in the same five-membered imidazole ring (III), has been prepared by lithiation of the imidazole monocarbene, :C{N(2,6-Pr(i)(2)C(6)H(3))CH}(2). The dicarbene nature of 1 was unambiguously demonstrated by the formation of the group 13 Lewis acid adducts (THF)(2)Li:C{[N(2,6-Pr(i)(2)C(6)H(3))](2)CHC(LA)}, where LA = AlMe(3) [2·(THF)(2)] and BEt(3) [3·(THF)(2)].