Fausto Calderazzo

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Fausto Calderazzo
Calderazzo-Fausto-2004.jpg
Calderazzo in 2004
Born(1930-03-08)March 8, 1930
DiedJune 1, 2014(2014-06-01) (aged 84)
NationalityItalian
Education
Awards
  • A. Miolati award (1988)
  • L. Sacconi Medal (1998)
Scientific career
Fields
Institutions

Fausto Calderazzo was an Italian inorganic chemist. He gained renown from numerous contributions in inorganic chemistry and organometallic chemistry. [1] [2] Hr was born in Parma, on March 8, 1930, where his father served in the Royal Italian army. He died in Pisa on June 1, 2014, at the age of 84. [3]

Contents

Life and education

Fausto Calderazzoe entered the University of Florence, in November 1947. He worked in the laboratory of Luigi Sacconi. [4] After the compulsory military service, Calderazzo joined the research group of Giulio Natta, a future Nobel laureate in Milan. He was a postdoctoral fellow with F. A. Cotton. His first independent position was at the Cyanamid European Research Institute in Geneva (1963-1968). There he was part of a team of future eminent scholars, including Carlo Floriani. For most of his career he was professor at the University of Pisa.

Research

Figure 4. Crystallographic structure of [H(THF)2][Nb2(u-Cl)3(CO)8] Crystallographic structure of (H(THF)2)(Nb2(u-Cl)3(CO)8).png
Figure 4. Crystallographic structure of [H(THF)2][Nb2(µ-Cl)3(CO)8]

Metal carbonyl chemistry

While in Milan, he discovered V(CO)6. [5] He made seminal contributions to the mechanism of migratory insertion reactions, with emphasis on the stereochemical course of the carbonylation of CH3Mn(CO)5. [6] His team later (in Pisa) developed syntheses of Na[Nb(CO)6] and Na[Ta(CO6)]. [7]

He contributed to the so-called "non classical" carbonyl compounds through studies on gold complexes. [8] [9]

Metal halides

Structure of Au4Cl8 Crystallographic structure of Au4Cl8.png
Structure of Au4Cl8

Calderazzo extended his interest in carbonyl chemistry of the late transition metals halides. [10] His group reported Au4Cl8, a simple mixed-valence gold chloride. [11]

Early metal complexes

Many of his contributions focused on early transition metals. [12] [13] He carried out research on carbon dioxide complexes. [14]

Starting with the preparation of V(η6-1,3,5-C6H3Me3)2, his group prepared many bis-mesitylene derivatives. [15]

Awards and titles

Calderazzo was a member of the editorial or advisor board of international scientific journals. He was a member of the Société Royale de Chemie (1987), Società Chimica Italiana and Accademia Nazionale dei Lincei (1989). He received the A. Miolati award in Inorganic Chemistry in 1988 and the L. Sacconi Medal in 1998.

Related Research Articles

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<span class="mw-page-title-main">Gold(III) chloride</span> Chemical compound

Gold(III) chloride, traditionally called auric chloride, is an inorganic compound of gold and chlorine with the molecular formula Au2Cl6. The "III" in the name indicates that the gold has an oxidation state of +3, typical for many gold compounds. It has two forms, the monohydrate (AuCl3·H2O) and the anhydrous form, which are both hygroscopic and light-sensitive solids. This compound is a dimer of AuCl3. This compound has a few uses, such as an oxidizing agent and for catalyzing various organic reactions.

<span class="mw-page-title-main">Organozinc chemistry</span>

Organozinc chemistry is the study of the physical properties, synthesis, and reactions of organozinc compounds, which are organometallic compounds that contain carbon (C) to zinc (Zn) chemical bonds.

<span class="mw-page-title-main">Gold(I,III) chloride</span> Chemical compound

Gold(I,III) chloride is the inorganic compound with the chemical formula Au4Cl8. It is an example of a mixed valence compound as it contains gold in two oxidation states; square-planar gold(III) and almost linear gold(I). The compound, which is black, is photosensitive as well as air- and moisture-sensitive.

<span class="mw-page-title-main">Sandwich compound</span> Chemical compound made of two ring ligands bound to a metal

In organometallic chemistry, a sandwich compound is a chemical compound featuring a metal bound by haptic, covalent bonds to two arene (ring) ligands. The arenes have the formula CnHn, substituted derivatives and heterocyclic derivatives. Because the metal is usually situated between the two rings, it is said to be "sandwiched". A special class of sandwich complexes are the metallocenes.

<span class="mw-page-title-main">Organotitanium chemistry</span>

Organotitanium chemistry is the science of organotitanium compounds describing their physical properties, synthesis, and reactions. Organotitanium compounds in organometallic chemistry contain carbon-titanium chemical bonds. They are reagents in organic chemistry and are involved in major industrial processes.

<span class="mw-page-title-main">Group 2 organometallic chemistry</span>

Group 2 organometallic chemistry refers to the organic derivativess of any group 2 element. It is a subtheme to main group organometallic chemistry. By far the most common group 2 organometallic compounds are the magnesium-containing Grignard reagents which are widely used in organic chemistry. Other organometallic group 2 compounds are typically limited to academic interests.

Organoiron chemistry is the chemistry of iron compounds containing a carbon-to-iron chemical bond. Organoiron compounds are relevant in organic synthesis as reagents such as iron pentacarbonyl, diiron nonacarbonyl and disodium tetracarbonylferrate. Although iron is generally less active in many catalytic applications, it is less expensive and "greener" than other metals. Organoiron compounds feature a wide range of ligands that support the Fe-C bond; as with other organometals, these supporting ligands prominently include phosphines, carbon monoxide, and cyclopentadienyl, but hard ligands such as amines are employed as well.

<span class="mw-page-title-main">Half sandwich compound</span> Class of coordination compounds

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<span class="mw-page-title-main">Organotantalum chemistry</span> Chemistry of compounds containing a carbon-to-tantalum bond

Organotantalum chemistry is the chemistry of chemical compounds containing a carbon-to-tantalum chemical bond. A wide variety of compound have been reported, initially with cyclopentadienyl and CO ligands. Oxidation states vary from Ta(V) to Ta(-I).

Metal arene complexes are organometallic compounds of the formula (C6R6)xMLy. Common classes are of the type (C6R6)ML3 and (C6R6)2M. These compounds are reagents in inorganic and organic synthesis. The principles that describe arene complexes extend to related organic ligands such as many heterocycles (e.g. thiophene) and polycyclic aromatic compounds (e.g. naphthalene).

<span class="mw-page-title-main">Allotropes of arsenic</span>

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<span class="mw-page-title-main">Transition metal chloride complex</span> Coordination complex

In chemistry, a transition metal chloride complex is a coordination complex that consists of a transition metal coordinated to one or more chloride ligand. The class of complexes is extensive.

A Fischer carbene is a type of transition metal carbene complex, which is an organometallic compound containing a divalent organic ligand. In a Fischer carbene, the carbene ligand is a σ-donor π-acceptor ligand. Because π-backdonation from the metal centre is generally weak, the carbene carbon is electrophilic.

<span class="mw-page-title-main">Transition metal ether complex</span>

In chemistry, a transition metal ether complex is a coordination complex consisting of a transition metal bonded to one or more ether ligand. The inventory of complexes is extensive. Common ether ligands are diethyl ether and tetrahydrofuran. Common chelating ether ligands include the glymes, dimethoxyethane (dme) and diglyme, and the crown ethers. Being lipophilic, metal-ether complexes often exhibit solubility in organic solvents, a property of interest in synthetic chemistry. In contrast, the di-ether 1,4-dioxane is generally a bridging ligand.

<span class="mw-page-title-main">Carbones</span> Class of molecules

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<span class="mw-page-title-main">Dicarbonyldi-μ-chlorodichlorodiplatinum</span> Chemical compound

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<span class="mw-page-title-main">Carlo Floriani</span> Italian inorganic chemist

Carlo Floriani was an inorganic chemist who gained renown for contributions to organometallic and coordination chemistry. He was born in Casalmaggiore, Cremona (Italy) in 1940 and died in 2005. He held positions at the University of Pisa, Columbia University, and Ecole Polytechnique, Lausanne. He had been a protoge of Fausto Calderazzo.

References

  1. P. M. Maitlis, D. B. Dell'Amico. "Fausto Calderazzo: Pioneer in Mechanistic Organometallic Chemistry". 'Organometallics, 2014, 33, 6989–7006. https://doi.org/10.1021/om5011963
  2. Poli, R. (1999). "Celebration of inorganic lives". Coordination Chemistry Reviews. 188: 1–22. doi:10.1016/S0010-8545(99)00081-8.
  3. Lunedì, Luca (June 3, 2014). "È morto Fausto Calderazzo studioso di fama mondiale" [Fausto Calderazzo, world-renowned scholar, has died]. Il Tirreno (in Italian). Retrieved May 13, 2024.
  4. Bertini, Ivano (1992). "Luigi Sacconi february 1911–september 1992". Coordination Chemistry Reviews. 120: ix–xii. doi:10.1016/0010-8545(92)80044-R.
  5. Ercoli, R.; Calderazzo, F.; Alberola, A. (1960). "Synthesis of Vanadium Hexacarbonyl". Journal of the American Chemical Society. 82 (11): 2966–2967. doi:10.1021/ja01496a073.
  6. Calderazzo, Fausto (1977). "Synthetic and Mechanistic Aspects of Inorganic Insertion Reactions. Insertion of Carbon Monoxide". Angewandte Chemie International Edition in English. 16 (5): 299–311. doi:10.1002/anie.197702991.
  7. F. Calderazzo, G. Pampaloni. "Metal Carbonyl Complexes of Group VB Metals". J. Organomet. Chem., 1986, 303, 111-120. https://doi.org/10.1016/0022-328X(86)80116-4.
  8. Dell'Amico, Daniela Belli; Calderazzo, Fausto; Robino, Pierluigi; Segre, Annalaura (1991). "Halogenocarbonyl Complexes of Gold". Journal of the Chemical Society, Dalton Transactions (11): 3017. doi:10.1039/DT9910003017.
  9. Bistoni, Giovanni; Rampino, Sergio; Scafuri, Nicola; Ciancaleoni, Gianluca; Zuccaccia, Daniele; Belpassi, Leonardo; Tarantelli, Francesco (2016). "How π Back-Donation Quantitatively Controls the CO Stretching Response in Classical and Non-Classical Metal Carbonyl Complexes". Chemical Science. 7 (2): 1174–1184. doi:10.1039/C5SC02971F. PMC   5975789 . PMID   29910872.
  10. Dell'Amico, Daniela Belli; Calderazzo, Fausto; Marchetti, Fabio; Ramello, Stefano (1996). "Molecular Structure of [Pd6Cl12] in Single Crystals Chemically Grown at Room Temperature". Angewandte Chemie International Edition in English. 35 (12): 1331–1333. doi:10.1002/anie.199613311.
  11. Dell'Amico, Daniela Belli; Calderazzo, Fausto; Marchetti, Fabio; Merlino, Stefano; Perego, Giovanni (1977). "X-Ray Crystal and Molecular Structure of Au4Cl8, the Product of the Reduction of Au2Cl6 by Au(CO)Cl". Journal of the Chemical Society, Chemical Communications: 31. doi:10.1039/C39770000031.
  12. Calderazzo, Fausto; Englert, Ulli; Guarini, Alessandro; Marchetti, Fabio; Pampaloni, Guido; Segre, Annalaura (1994). "[Zr3Cp2(O2CN i Pr2)6(μ-O)(μ-CCO)], the First Crystallographically Established Ketenylidene Complex; A Model for CO Reductive Cleavage on Metal Surfaces". Angewandte Chemie International Edition in English. 33 (11): 1188–1189. doi:10.1002/anie.199411881.
  13. Calderazzo, Fausto; Pampaloni, Guido (1995). "Aromatic hydrocarbons, carbocyclic ligands spanning several oxidation states in both Main Group and transition elements. Recent advances with Early Transition d Elements". Journal of Organometallic Chemistry. 500 (1–2): 47–60. doi:10.1016/0022-328X(95)00505-K.
  14. Dell'Amico, Daniela Belli; Calderazzo, Fausto; Labella, Luca; Marchetti, Fabio; Pampaloni, Guido (2003). "Converting Carbon Dioxide into Carbamato Derivatives". Chemical Reviews. 103 (10): 3857–3898. doi:10.1021/cr940266m. PMID   14531715.
  15. G. Pampaloni. "Aromatic hydrocarbons as ligands. Recent advances in the synthesis, the reactivity, and the applications of bis(η6-arene) complexes". Coord. Chem. Rev., 2010, 254, 402-419. https://doi.org/10.1016/j.ccr.2009.05.014.