Dialkylboron guanidinates: syntheses, structures and carbodiimide de-insertion reactions.
The synthesis of novel dialkylboron guanidinates is reported: the symmetrical compounds, (Me2N)C(NR)2BR'2[R =iPr, R' = Nrb (1); R = Cy, R' = Nrb (2); R =iPr, R' = Cy (3); R = R' = Cy (4); R = 2,6-iPr2-C6H3; R' = Cy (5); Nrb = exo-2-norbornyl] and the asymmetrically coordinated {iPr(H)N}C(NiPr)(NAr)BCy2[Ar = Ph (6), 4-Me-C6H4(7), 4-tBu-C6H4(8)] were prepared by the salt metathesis method from the appropriate lithium guanidinates and chloroboranes. Moreover, the bis(dicyclohexylboron)guanidinate(-2) {iPr(Cy2B)N}C(NiPr){N(4-tBu-C6H4)}BCy2(9) was also prepared from the corresponding dilithium guanidinate Li2[{N(4-tBu-C6H4)}C(NiPr)2] and ClBCy2. The structures of compounds 1, 3, 6 and 9 were confirmed by X-ray diffraction and all displayed a chelate coordination of the guanidinate ligand to the BR'2fragment, the latter displaying an additional BCy2attached to the exocyclic N atom. Solutions of compounds 1-4 reached an equilibrium with the aminoboranes Me2NBR'2[R' = Nrb (10), Cy (11)] and the corresponding carbodiimides, which was slow at 25 °C. The thermodynamic parameters for these equilibria are also reported. The activation parameters for the equilibrium for compound 1 have been calculated after a kinetic study. Compounds 5-8, with one or two N-aryl fragments bound to a B centre, are more robust and need higher temperatures (80 °C) and prolonged times to give similar carbodiimide de-insertion reactions.
Centro de Innovación en Química Avanzada (ORFEO-CINQA), Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Ciencias y Tecnologías Químicas, Universidad de Castilla-La Mancha, Campus Universitario, E-13071 Ciudad Real, Spain. Antonio.Antinolo@uclm.es.
Antonio
A
Antiñolo
Fernando
F
Carrillo-Hermosilla
Rafael
R
Fernández-Galán
María Pilar
MP
Montero-Rama
Alberto
A
Ramos
Elena
E
Villaseñor
Rene S
RS
Rojas
Antonio
A
Rodríguez-Diéguez