1 Introduction
Since French chemist Louis Claude Cadet de Gassicourt synthesized the first
organometallic compound tetramethyldiarsine in 1706 [1], organometallic chemistry
has tremendously grown and become an integral part of many areas of chemistry and
beyond [2–12]. A number of researchers have been awarded the Nobel Prize in
Chemistry for their work in the area of organometallic chemistry:
1912 – Victor Grignard, discovery of the Grignard Reagent, and Paul Sabatier,
hydrogenation of organic species in the presence of metals
1963 – Karl Ziegler and Giulio Natta, Ziegler–Natta catalyst
1973 – Geoffrey Wilkinson and Ernst Otto Fischer, sandwich compounds
2001 – William Standish Knowles, Ryoji Noyori, and Karl Barry Sharpless, asymmetric hydrogenation
2005 – Yves Chauvin, Robert Grubbs, and Richard Schrock, metal-catalyzed alkene
metathesis
2010 – Richard F. Heck, Ei-ichi Negishi, and Akira Suzuki, palladium-catalyzed
cross-coupling reactions [13]
Organometallics are strictly defined as chemical compounds, which contain at
least one bonding interaction between a metal and a carbon atom belonging to an
organic molecule. However, aside from bonds to organyl fragments or molecules,
bonds to “inorganic” carbon, like carbon monoxide (metal carbonyls), cyanide, or
carbide, are generally considered as organometallic compounds as well. Likewise, in
addition to the traditional main group metals [4–16] and transition metals [2],
lanthanides and actinides [17, 18], as well as semimetals, i.e., elements such as
boron, silicon, arsenic, and selenium [19, 20], are also considered to form organometallic compounds, e.g., organoboranes [21], broadening the range of organometallic compounds substantially.
One of the major advantages of organometallic compounds is their high reactivity, which finds wide use in synthesis, where organometallic compounds are utilized
as homogeneous/heterogeneous catalysts or as stoichiometric reagents [22–
28]. Major industrial processes using organometallic catalysts include hydrogenation, hydrosilylation, hydrocyanation, olefin metathesis, alkene polymerization,
alkene oligomerization, hydrocarboxylation, methanol carbonylation, and
hydroformylation, to name just a few [9, 29–31]. Organometallic complexes are
also frequently used in cross-coupling reactions [32, 33], and they have attracted a
lot of attention in the field of organometallic-mediated radical polymerization [34–
38]. The production of fine chemicals relies on soluble organometallic complexes or
involves organometallic intermediates, which often guarantee stereospecific products [7]. A recently evolving field is organometallic electrochemistry, which is
devoted to finding solutions for the production of reliable, affordable, and environmentally friendly energy, fuels, and chemicals such as methanol or ammonia
[39, 40]. Organometallic compounds have recently been discussed as an excellent
alternative to the organic active layers used for solar cells or other light-emitting
devices, due to their better properties such as thermal and chemical stability [41], and
Characterizing the Metal–Ligand Bond Strength via Vibrational Spectroscopy:. . .
229
Since French chemist Louis Claude Cadet de Gassicourt synthesized the first
organometallic compound tetramethyldiarsine in 1706 [1], organometallic chemistry
has tremendously grown and become an integral part of many areas of chemistry and
beyond [2–12]. A number of researchers have been awarded the Nobel Prize in
Chemistry for their work in the area of organometallic chemistry:
1912 – Victor Grignard, discovery of the Grignard Reagent, and Paul Sabatier,
hydrogenation of organic species in the presence of metals
1963 – Karl Ziegler and Giulio Natta, Ziegler–Natta catalyst
1973 – Geoffrey Wilkinson and Ernst Otto Fischer, sandwich compounds
2001 – William Standish Knowles, Ryoji Noyori, and Karl Barry Sharpless, asymmetric hydrogenation
2005 – Yves Chauvin, Robert Grubbs, and Richard Schrock, metal-catalyzed alkene
metathesis
2010 – Richard F. Heck, Ei-ichi Negishi, and Akira Suzuki, palladium-catalyzed
cross-coupling reactions [13]
Organometallics are strictly defined as chemical compounds, which contain at
least one bonding interaction between a metal and a carbon atom belonging to an
organic molecule. However, aside from bonds to organyl fragments or molecules,
bonds to “inorganic” carbon, like carbon monoxide (metal carbonyls), cyanide, or
carbide, are generally considered as organometallic compounds as well. Likewise, in
addition to the traditional main group metals [4–16] and transition metals [2],
lanthanides and actinides [17, 18], as well as semimetals, i.e., elements such as
boron, silicon, arsenic, and selenium [19, 20], are also considered to form organometallic compounds, e.g., organoboranes [21], broadening the range of organometallic compounds substantially.
One of the major advantages of organometallic compounds is their high reactivity, which finds wide use in synthesis, where organometallic compounds are utilized
as homogeneous/heterogeneous catalysts or as stoichiometric reagents [22–
28]. Major industrial processes using organometallic catalysts include hydrogenation, hydrosilylation, hydrocyanation, olefin metathesis, alkene polymerization,
alkene oligomerization, hydrocarboxylation, methanol carbonylation, and
hydroformylation, to name just a few [9, 29–31]. Organometallic complexes are
also frequently used in cross-coupling reactions [32, 33], and they have attracted a
lot of attention in the field of organometallic-mediated radical polymerization [34–
38]. The production of fine chemicals relies on soluble organometallic complexes or
involves organometallic intermediates, which often guarantee stereospecific products [7]. A recently evolving field is organometallic electrochemistry, which is
devoted to finding solutions for the production of reliable, affordable, and environmentally friendly energy, fuels, and chemicals such as methanol or ammonia
[39, 40]. Organometallic compounds have recently been discussed as an excellent
alternative to the organic active layers used for solar cells or other light-emitting
devices, due to their better properties such as thermal and chemical stability [41], and
Characterizing the Metal–Ligand Bond Strength via Vibrational Spectroscopy:. . .
229