title: Terminal imido rhodium complexes.
abstract: Compounds of the late transition metals with M=X multiple bonds (X=CR2, NR, O) represent a synthetic challenge, partly overcome by preparative chemists, but with noticeable gaps in the second- and third-row elements. For example, there are no isolated examples of terminal imido rhodium complexes known to date. Described herein is the isolation, characterization, and some preliminary reactivity studies of the first rhodium complexes [Rh(PhBP3)(NR)] (PhBP3=PhB{CH2PPh2}3) with a multiple and terminal Rh=N bond. These imido compounds result from reactions of organic azides with the corresponding rhodium(I) complex having a labile ligand, and display a pseudo-tetrahedral core geometry with an almost linear Rh-N-C arrangement [177.5(2)°] and a short Rh-N bond [1.780(2) Å]. We also show that the Rh=N bond undergoes protonation at the nitrogen atom or addition of H2 , and also engages in nitrene-group transfer and cycloaddition reactions.
authors.affiliation: Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC-Universidad de Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza (Spain).
authors.forename: Ana M
authors.initials: AM
authors.lastname: Geer
authors.forename: Cristina
authors.initials: C
authors.lastname: Tejel
authors.forename: José A
authors.initials: JA
authors.lastname: López
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Ciriano
keywords: azides; cycloaddition; multiple bonds; rhodium; structure elucidation