Top Organomet Chem (2016) 56: 155–188
DOI: 10.1007/3418_2015_139
# Springer International Publishing Switzerland 2015
Published online: 19 August 2015
New Concept of C–H and C–C Bond
Activation via Surface Organometallic
Chemistry
Manoja K. Samantaray, Raju Dey, Santosh Kavitake,
and Jean-Marie Basset
Abstract In this chapter we describe the recent applications of well-defined oxidesupported metal alkyls/alkylidenes/alkylidynes and hydrides of group IV, V, and VI
transition metals in the field of C–H and C–C bond activation. The activation of
ubiquitous C–H and C–C bonds of paraffin is a long-standing challenge because of
intrinsic low reactivity. There are many concepts derived from surface organometallic chemistry (SOMC): surface organometallic fragments are always intermediates in heterogeneous catalysis. The study of their synthesis and reactivity is a
way to rationalize mechanism of heterogeneous catalysis and to achieve structure
activity relationship. By surface organometallic chemistry one can enter any catalytic center by a reaction intermediate leading in fine to single site catalysts. With
surface organometallic chemistry one can coordinate to the metal which can play a
role in different elementary steps leading for example to C–H activation and Olefin
metathesis. Because of the development of SOMC there is a lot of space for the
improvement of homogeneous catalysis. After the 1997 discovery of alkane
metathesis using silica-supported tantalum hydride by Basset et al. at low temperature (150
o C) the focus in this area was shifted to the discovery of more and more
challenging surface complexes active in the application of C–H and C–C bond
activation. Here we describe the evolution of well-defined metathesis catalyst with
time as well as the effect of support on catalysis. We also describe here which
metal–ligand combinations are responsible for a variety of C–H and C–C bond
activation.
Keywords Alkane metathesis Á Metal-Alkylidene Á Metal-Alkylidyne Á MetalHydride Á Olefin metathesis Á Transition metals
M.K. Samantaray, R. Dey, S. Kavitake, and J.-M. Basset (*)
KAUST Catalysis Center (KCC), King Abdullah University of Science and Technology,
23955-6900 Thuwal, Saudi Arabia
e-mail: jeanmarie.basset@kaust.edu.sa
DOI: 10.1007/3418_2015_139
# Springer International Publishing Switzerland 2015
Published online: 19 August 2015
New Concept of C–H and C–C Bond
Activation via Surface Organometallic
Chemistry
Manoja K. Samantaray, Raju Dey, Santosh Kavitake,
and Jean-Marie Basset
Abstract In this chapter we describe the recent applications of well-defined oxidesupported metal alkyls/alkylidenes/alkylidynes and hydrides of group IV, V, and VI
transition metals in the field of C–H and C–C bond activation. The activation of
ubiquitous C–H and C–C bonds of paraffin is a long-standing challenge because of
intrinsic low reactivity. There are many concepts derived from surface organometallic chemistry (SOMC): surface organometallic fragments are always intermediates in heterogeneous catalysis. The study of their synthesis and reactivity is a
way to rationalize mechanism of heterogeneous catalysis and to achieve structure
activity relationship. By surface organometallic chemistry one can enter any catalytic center by a reaction intermediate leading in fine to single site catalysts. With
surface organometallic chemistry one can coordinate to the metal which can play a
role in different elementary steps leading for example to C–H activation and Olefin
metathesis. Because of the development of SOMC there is a lot of space for the
improvement of homogeneous catalysis. After the 1997 discovery of alkane
metathesis using silica-supported tantalum hydride by Basset et al. at low temperature (150
o C) the focus in this area was shifted to the discovery of more and more
challenging surface complexes active in the application of C–H and C–C bond
activation. Here we describe the evolution of well-defined metathesis catalyst with
time as well as the effect of support on catalysis. We also describe here which
metal–ligand combinations are responsible for a variety of C–H and C–C bond
activation.
Keywords Alkane metathesis Á Metal-Alkylidene Á Metal-Alkylidyne Á MetalHydride Á Olefin metathesis Á Transition metals
M.K. Samantaray, R. Dey, S. Kavitake, and J.-M. Basset (*)
KAUST Catalysis Center (KCC), King Abdullah University of Science and Technology,
23955-6900 Thuwal, Saudi Arabia
e-mail: jeanmarie.basset@kaust.edu.sa