Bernard L. Shaw

Last updated

Bernard Leslie Shaw, FRS (28 March 1930 - 8 November 2020) was an English chemist who made notable contributions to organometallic chemistry. He was Professor of Inorganic and Structural Chemistry at the University of Leeds. [1]

Contents

Early life

Shaw was born on 28 March 1930 in Springhead then in the West Riding of Yorkshire. His parents were Tom and Vera Shaw. He was educated at Hulme Grammar School in Oldham.

Shaw married Mary Elizabeth Neild in 1951.

Career

Shaw studied at the University of Manchester where he gained a BSc and a PhD. After three years in the Civil Service at the Torry Research Station in Aberdeen and five years at ICI he was appointed Lecturer in the Department of Inorganic and Structural Chemistry at the University of Leeds in 1962. He was promoted to Reader in 1966 and to a Personal Chair in 1971. He was made head of the university's department of Inorganic Chemistry in 1990 and Emeritus Professor upon his retirement in 1995.

Shaw was at various times a Visiting Professor at the University of Western Ontario, Carnegie Mellon University (1969), the American National University (1983) and the University of Auckland (1986). He was Lecturer at the Royal Society of Chemistry in 1987-88.[ citation needed ]

Scientific contributions

Together with his longtime collaborator Joseph Chatt, Shaw contributed to the development of organoplatinum chemistry. They reported the first platinum hydride, PtHCl(PEt3)2. This colourless, volatile solid was the first non-organometallic hydride (i.e., lacking a metal-carbon bond). [2]

With an interest in cyclometallation, [3] he discovered one of the first pincer complexes via the orthometalation of 1,3-C6H4(CH2PBut2)2. [4]

Pincer complex prepared by Shaw et al. ShawPincer.png
Pincer complex prepared by Shaw et al.

Honours and awards

Death

Shaw died on 8 November 2020, aged 90.

Related Research Articles

Ferrocene is an organometallic compound with the formula Fe(C
5
H
5
)
2
. The molecule consists of two cyclopentadienyl rings bound on opposite sides of a central iron atom. It is an orange solid with a camphor-like odor, that sublimes above room temperature, and is soluble in most organic solvents. It is remarkable for its stability: it is unaffected by air, water, strong bases, and can be heated to 400 °C without decomposition. In oxidizing conditions it can reversibly react with strong acids to form the ferrocenium cation Fe(C
5
H
5
)+
2
.

Phenanthroline

Phenanthroline (phen) is a heterocyclic organic compound. It is a white solid that is soluble in organic solvents. It is used as a ligand in coordination chemistry, forming strong complexes with most metal ions. It is often sold as the monohydrate.

Oxidative addition and reductive elimination are two important and related classes of reactions in organometallic chemistry. Oxidative addition is a process that increases both the oxidation state and coordination number of a metal centre. Oxidative addition is often a step in catalytic cycles, in conjunction with its reverse reaction, reductive elimination.

Palladium(II) acetate

Palladium(II) acetate is a chemical compound of palladium described by the formula [Pd(O2CCH3)2]n, abbreviated [Pd(OAc)2]n. It is more reactive than the analogous platinum compound. Depending on the value of n, the compound is soluble in many organic solvents and is commonly used as a catalyst for organic reactions.

<i>Dalton Transactions</i> Academic journal

Dalton Transactions is a peer-reviewed scientific journal publishing original (primary) research and review articles on all aspects of the chemistry of inorganic, bioinorganic, and organometallic compounds. It is published weekly by the Royal Society of Chemistry. The journal was named after the English chemist, John Dalton, best known for his work on modern atomic theory. Authors can elect to have accepted articles published as open access. The editor is Andrew Shore. Dalton Transactions was named a "rising star" by In-cites from Thomson Scientific in 2006.

1,5-Cyclooctadiene is a cyclic hydrocarbon with the chemical formula C8H12; specifically [–(CH
2
)
2
–CH=CH–]2.

Malcolm Leslie Hodder Green was Professor of Inorganic Chemistry at the University of Oxford. He made many contributions to organometallic chemistry.

Carbon–hydrogen bond functionalization is a type of reaction in which a carbon–hydrogen bond is cleaved and replaced with a carbon–X bond. The term usually implies that a transition metal is involved in the C-H cleavage process. Reactions classified by the term typically involve the hydrocarbon first to react with a metal catalyst to create an organometallic complex in which the hydrocarbon is coordinated to the inner-sphere of a metal, either via an intermediate "alkane or arene complex" or as a transition state leading to a "M−C" intermediate. The intermediate of this first step can then undergo subsequent reactions to produce the functionalized product. Important to this definition is the requirement that during the C–H cleavage event, the hydrocarbyl species remains associated in the inner-sphere and under the influence of "M".

Hexamethyltungsten

Hexamethyltungsten is the chemical compound W(CH3)6 also written WMe6. Classified as a transition metal alkyl complex, hexamethyltungsten is an air-sensitive, red, crystalline solid at room temperature; however, it is extremely volatile and sublimes at −30 °C. Owing to its six methyl groups it is extremely soluble in petroleum, aromatic hydrocarbons, ethers, carbon disulfide, and carbon tetrachloride.

1,2-Bis(dimethylarsino)benzene

1,2-Bis(dimethylarsino)benzene (diars) is the organoarsenic compound with the formula C6H4(As(CH3)2)2. The molecule consists of two dimethylarsino groups attached to adjacent carbon centers of a benzene ring. It is a chelating ligand in coordination chemistry. This colourless oil is commonly abbreviated "diars."

Joseph Chatt was a renowned British researcher in the area of inorganic and organometallic chemistry. His name is associated with the description of the pi-bond between transition metals and alkenes, the Dewar–Chatt–Duncanson model.

Metallacycle

In organometallic chemistry, a metallacycle is a derivative of a carbocyclic compound wherein a metal has replaced at least one carbon center; this is to some extent similar to heterocycles. Metallacycles appear frequently as reactive intermediates in catalysis, e.g. olefin metathesis and alkyne trimerization. In organic synthesis, directed ortho metalation is widely used for the functionalization of arene rings via C-H activation. One main effect that metallic atom substitution on a cyclic carbon compound is distorting the geometry due to the large size of typical metals.

Bis(diphenylphosphino)methane

1,1-Bis(diphenylphosphino)methane (dppm), is an organophosphorus compound with the formula CH2(PPh2)2. Dppm, a white, crystalline powder, is used in inorganic and organometallic chemistry as a ligand. It is more specifically a chelating ligand because it is a ligand that can bond to metals with two phosphorus donor atoms. The natural bite angle is 73°.

Transition metal hydrides are chemical compounds containing a transition metal bonded to hydrogen. Most transition metals form hydride complexes and some are significant in various catalytic and synthetic reactions. The term "hydride" is used loosely: some so-called hydrides are acidic (e.g., H2Fe(CO)4), whereas some others are hydridic, having H-like character (e.g., ZnH2).

Organoplatinum chemistry is the chemistry of organometallic compounds containing a carbon to platinum chemical bond, and the study of platinum as a catalyst in organic reactions. Organoplatinum compounds exist in oxidation state 0 to IV, with oxidation state II most abundant. The general order in bond strength is Pt-C (sp) > Pt-O > Pt-N > Pt-C (sp3). Organoplatinum and organopalladium chemistry are similar, but organoplatinum compounds are more stable and therefore less useful as catalysts.

Organorhenium chemistry describes the compounds with Re−C bonds. Because rhenium is a rare element, relatively few applications exist, but the area has been a rich source of concepts and a few useful catalysts.

Iron tetracarbonyl hydride

Iron tetracarbonyl hydride is the organometallic compound with the formula H2Fe(CO)4. This compound was the first transition metal hydride discovered. The complex is stable at low temperatures but decomposes rapidly at temperatures above –20 °C.

Peter Michael Maitlis, FRS is a retired British organometallic chemist.

Sodium <i>tert</i>-butoxide

Sodium tert-butoxide is the chemical compound with the formula (CH3)3CONa. It is a strong base and a non-nucleophilic base. It is flammable and moisture sensitive. It is sometimes written in chemical literature as sodium t-butoxide. It is similar in reactivity to the more common potassium tert-butoxide.

Karen Ila Goldberg is an American chemist, currently the Vagelos Professor of Energy Research at University of Pennsylvania. Goldberg is most known for her work in inorganic and organometallic chemistry. Her most recent research focuses on catalysis, particularly on developing catalysts for oxidation, as well as the synthesis and activation of molecular oxygen. In 2018, Goldberg was elected to the National Academy of Sciences.

References

  1. University of Leeds, obituary
  2. J. Chatt, L. A. Duncanson, B. L. Shaw "A Volatile Chlorohydride of Platinum" Proc. Chem. Soc. , 1957, 329-368. doi : 10.1039/PS9570000329
  3. Najeeb A. Al-Salem, H. David Empsall, Richard Markham, Bernard L. Shaw, Brian Weeks "Formation of large chelate rings and cyclometallated products from diphosphines of type But2P(CH2)nPBut2 (n= 5–8) and Ph2P(CH2)5PPh2 with palladium and platinum chlorides: factors affecting the stability and conformation of large chelate rings" J. Chem. Soc., Dalton Trans. , 1979, 1972-1982. doi : 10.1039/DT9790001972
  4. Christopher J. Moulton, Bernard L. Shaw "Transition metal–carbon bonds. Part XLII. Complexes of nickel, palladium, platinum, rhodium and iridium with the tridentate ligand 2,6-bis[(di-t-butylphosphino)methyl]phenyl" J. Chem. Soc., Dalton Trans. , 1976, 1020-1024. doi : 10.1039/DT9760001020
  5. "Tilden Prizes Previous Winners". Royal Society of Chemistry. Retrieved 14 January 2017.
  6. "Bernard Shaw-Biography". Royal Society. Retrieved 14 January 2017.