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Issue 29, 2010
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Organo-f-element catalysts for efficient and highly selective hydroalkoxylation and hydrothiolation

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Abstract

Lanthanide and actinide catalysts have made significant contributions to many areas of homogeneous catalysis with hydroelementation of C–C unsaturation being a notable area of success. In this Perspective, we review recent advances in f-element hydroelementation for highly selective hydroalkoxylation and hydrothiolation processes. As will be discussed, f-element hydroalkoxylation and hydrothiolation catalysts exhibit selectivities unobtainable by many late transition metal complexes. First, we review lanthanide-mediated hydroalkoxylation processes with mechanistic, thermodynamic, and kinetic considerations discussed, and then compare/contrast them with analogous C–N and C–P bond-forming transformations. In addition, computational studies are discussed which provide further insight into this transformation and the observed selectivities. Next, actinide-mediated alkyne hydrothiolation is reviewed with a similar discussion of reactivity, mechanism, and thermodynamics.

Graphical abstract: Organo-f-element catalysts for efficient and highly selective hydroalkoxylation and hydrothiolation

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Article information


Submitted
15 Feb 2010
Accepted
16 Apr 2010
First published
20 May 2010

Dalton Trans., 2010,39, 6576-6588
Article type
Perspective

Organo-f-element catalysts for efficient and highly selective hydroalkoxylation and hydrothiolation

C. J. Weiss and T. J. Marks, Dalton Trans., 2010, 39, 6576
DOI: 10.1039/C003089A

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