Fausto Calderazzo | |
|---|---|
 Calderazzo in 2004 | |
| Born | March 8, 1930 |
| Died | June 1, 2014 (aged 84) |
| Nationality | Italian |
| Education | |
| Awards |
|
| 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]
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.
![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](http://upload.wikimedia.org/wikipedia/commons/thumb/0/01/Crystallographic_structure_of_%28H%28THF%292%29%28Nb2%28%C2%B5-Cl%293%28CO%298%29.png/225px-Crystallographic_structure_of_%28H%28THF%292%29%28Nb2%28%C2%B5-Cl%293%28CO%298%29.png)
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]
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]
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]
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.
Ernst Otto Fischer was a German chemist who won the Nobel Prize for pioneering work in the area of organometallic chemistry.
A transition metal carbene complex is an organometallic compound featuring a divalent carbon ligand, itself also called a carbene. Carbene complexes have been synthesized from most transition metals and f-block metals, using many different synthetic routes such as nucleophilic addition and alpha-hydrogen abstraction. The term carbene ligand is a formalism since many are not directly derived from carbenes and most are much less reactive than lone carbenes. Described often as =CR2, carbene ligands are intermediate between alkyls (−CR3) and carbynes (≡CR). Many different carbene-based reagents such as Tebbe's reagent are used in synthesis. They also feature in catalytic reactions, especially alkene metathesis, and are of value in both industrial heterogeneous and in homogeneous catalysis for laboratory- and industrial-scale preparation of fine chemicals.
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.
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.
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.
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.
Group 2 organometallic chemistry refers to the chemistry of compounds containing carbon bonded to any group 2 element. 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 rare and 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.
Half sandwich compounds, also known as piano stool complexes, are organometallic complexes that feature a cyclic polyhapto ligand bound to an MLn center, where L is a unidentate ligand. Thousands of such complexes are known. Well-known examples include cyclobutadieneiron tricarbonyl and (C5H5)TiCl3. Commercially useful examples include (C5H5)Co(CO)2, which is used in the synthesis of substituted pyridines, and methylcyclopentadienyl manganese tricarbonyl, an antiknock agent in petrol.
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).
Hexaphosphabenzene is a valence isoelectronic analogue of benzene and is expected to have a similar planar structure due to resonance stabilization and its sp2 nature. Although several other allotropes of phosphorus are stable, no evidence for the existence of P6 has been reported. Preliminary ab initio calculations on the trimerisation of P2 leading to the formation of the cyclic P6 were performed, and it was predicted that hexaphosphabenzene would decompose to free P2 with an energy barrier of 13−15.4 kcal mol−1, and would therefore not be observed in the uncomplexed state under normal experimental conditions. The presence of an added solvent, such as ethanol, might lead to the formation of intermolecular hydrogen bonds which may block the destabilizing interaction between phosphorus lone pairs and consequently stabilize P6. The moderate barrier suggests that hexaphosphabenzene could be synthesized from a [2+2+2] cycloaddition of three P2 molecules. Currently, this is a synthetic endeavour which remains to be conquered.
Arsenic in the solid state can be found as gray, black, or yellow allotropes. These various forms feature diverse structural motifs, with yellow arsenic enabling the widest range of reactivity. In particular, reaction of yellow arsenic with main group and transition metal elements results in compounds with wide-ranging structural motifs, with butterfly, sandwich and realgar-type moieties featuring most prominently.
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.
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.
Arene complexes of univalent gallium, indium, and thallium are complexes featuring the centric (η6) coordination of the metal to the arene. Although arene complexes of transitional metals have long been reported, arene complexes of the main group elements remain scarce. This might be partly explained by the difference in energy of the d and p orbitals.
trans-Dicarbonyldi-μ-chlorodichlorodiplatinum is the first ever isolated metal-carbonyl complex. It was first synthesized by Paul Schützenberger in 1868. This discovery of [Pt(CO)Cl2]2 opened the door for the exploration of metal-carbonyl complexes and represents a significant breakthrough in the field of organometallic chemistry. Though [Pt(CO)Cl2]2 itself is not used in industry, metal carbonyls are an important class of catalysts for a wide range of industrial processes including hydroformylation amongst others. As such, the discovery of [Pt(CO)Cl2]2 was an important milestone both in the synthesis of organometallic compounds and in the development of many important catalysts widely used today.
A hydrotelluride or tellanide is an ion or a chemical compound containing the [HTe]− anion which has a hydrogen atom connected to a tellurium atom. HTe is a pseudohalogen. Organic compounds containing the -TeH group are called tellurols. "Tellanide" is the IUPAC name from the Red Book, but hydrogen(tellanide)(1−) is also listed. "Tellanido" as a ligand is not named, however ditellanido is used for HTeTe−.
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.