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Hydrocarbyl derivatives of [UCl2HB(pz)32]: Synthesis, characterization and reactivity studies towards protic substrates and ketones by M. Paula C. Campello; Maria José Calhorda; Ângela Domingos; Adelino Galvão; João Paulo Leal; A. Pires de Matos; Isabel Santos is a Chemistry article available to read on EtoBox.

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The reaction of [UC12{HB(Pz)3} 2] (1) with lithium alkyls LiR (R = Me, CH2SiMe 3, C6H4-o-CH2NMe 2) in the 1:1 or 1:2 molar ratio affords the compounds [UC1R{HB(pz)3}2] (pz = CsH3N 2, R = Me (2), CH2SiMe 3 (3), C6H4-o-CHzNMe 2 (4)) and [URz{HB(pz)s}2] (R = Me (5), CHzSiM % ( 6)) respectively in 60-80% yield. Complex 2 can also be obtained (60% yield) by redistribution at room temperature between the complexes 1 and 5. Compounds 2, 3 and 4 react with pzH providing [UCl(pz){HB(pz)3} z] (7) in almost quantitative yield and 5 and 6 react also with pzH leading to [U(pz)2{HB(pz)3} 2 ] (8). The aikoxide [U(OC6H4-o-OMe)z{HB(pz)3} 1] (9) was synthesized by reacting 5 or 6 with guaiacol. By reacting the chlorohydrocarbyls 2, 3 or 4 with excess of acetone the aldolate [UCI(OCMezCH2(C=O)Me){HB(pz)3}2] (11) was obtained, due to the activation of et-CH bond of acetone; however, for 3 the reaction is not clean and a mixture of 11 and [UCI(OCMe2CH2SiMe3){HB(pz)3}2] ( 12) is always obtained. Stoichiometric amounts of acetone insert into the metal-carbon bonds of 2 and 5 yielding [UCI(OtBu){HB(pz)3}2] and [U(OtBu)2{HB(Pz)3}2] respectively, while the insertion product [U(OCMe2CH2SiMe3)z{HB(pz)3}2] (10

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Author

M. Paula C. Campello; Maria José Calhorda; Ângela Domingos; Adelino Galvão; João Paulo Leal; A. Pires de Matos; Isabel Santos

Publisher

Elsevier Science; Elsevier ; Elsevier BV (ISSN 0022-328X)

Published

1997

Language

EN

Field

Chemistry (Physical Sciences)