Mono- and Bimetallic Alkynyl Metallocenes and Half-Sandwich Complexes: A Simple and Versatile Synthetic Approach.
A general process for the synthesis of alkynyl mono and dimetallic metallocenes and half-sandwich complexes has been developed. This approach uses the addition of lithium derivatives of sandwich or half-sandwich complexes to arylsulfonylacetylenes. The reaction occurs in two steps (lithiation and anti-Michael addition to alkynylsulfone followed by elimination of the ArSO2moiety) to form the corresponding mono- or bimetallic alkynes in clearly higher yields, simpler experimental procedures, and more environmentally benign conditions than those of the so far reported for the synthesis of this type of products. The electrochemical properties of the newly obtained complexes have also been studied.
Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Complutense, 28040, Madrid, Spain.|Centro de Innovación en Química Avanzada (ORFEO-CINQA), Spain.|Instituto de Química Orgánica General, Consejo Superior de Investigaciones Científicas (CSIC), Juan de la Cierva 3, 28006, Madrid, Spain.
Carolina
C
Valderas
Organic Chemistry Department, Universidad Autónoma de Madrid, 28049, Madrid, Spain.
Leyre
L
Marzo
Centro de Innovación en Química Avanzada (ORFEO-CINQA), Spain.|Instituto de Química Orgánica General, Consejo Superior de Investigaciones Científicas (CSIC), Juan de la Cierva 3, 28006, Madrid, Spain.
María C
MC
de la Torre
Organic Chemistry Department, Universidad Autónoma de Madrid, 28049, Madrid, Spain.
José Luis
JL
García Ruano
Organic Chemistry Department, Universidad Autónoma de Madrid, 28049, Madrid, Spain. jose.aleman@uam.es.
José
J
Alemán
Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Complutense, 28040, Madrid, Spain.|Centro de Innovación en Química Avanzada (ORFEO-CINQA), Spain.
Luis
L
Casarrubios
Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Complutense, 28040, Madrid, Spain. sierraor@ucm.es.|Centro de Innovación en Química Avanzada (ORFEO-CINQA), Spain. sierraor@ucm.es.
Miguel A
MA
Sierra
acetylene sulfones; anti-Michael addition; half-sandwich complexes; metallocenes