Coordination compounds history

G. B. Kauffman, Inorganic Coordination Compounds, Heyden, London, 1981. An excellent volume on the history of coordination compounds prior to 1935. 

The divalent Co(salen) complex (69a) is one of the most versatile and well-studied Co coordination compounds. It has a long and well-documented history and we shall not restate this here. Recent applications of (69a) as both a synthetic oxygen carrier and as a catalyst for organic transformations are described in Sections 6.1.3.1.2 and 6.1.4.1 respectively. Isotropic shifts in the HNMR spectrum of low-spin Co(salphn) (69b) were investigated in deuterated chloroform, DMF, DMSO, and pyridine.319 Solvent-dependent isotropic shifts indicate that the single unpaired electron, delocalized over the tetradentate 7r-electron system in CHCI3, is an intrinsic property of the planar four-coordinate complex. The high-spin/low-spin equilibrium of the... 

Cobalt Inorganic Coordination Chemistry Coordination Chemistry History Macrocyclic Ligands Mixed Valence Compounds Nitrogen Inorganic Chemistry. 

Asymmetric Synthesis by Homogeneous Catalysis Coordination Chemistry History Coordination Organometallic Chemistry Principles Dihydrogen Complexes Related Sigma Complexes Electron Transfer in Coordination Compounds Electron Transfer Reactions Theory Heterogeneous Catalysis by Metals Hydride Complexes of the Transition Metals Euminescence Luminescence Behavior Photochemistry of Organotransition Metal Compounds Photochemistry of Transition Metal Complexes Ruthenium Organometallic Chemistry. 

Gmelin Handbook of Inorganic Chemistry , System No. 39, Part A, History, Occurrence Part B, The Elements Part C, The Compoimds Part D, Coordination Compounds 1938, onwards. 

Tt is well-known that Werner determined the structure of a number of metal complexes by skillfully combining his famous coordination theory with chemical methods (30). Modern physico-chemical methods such as x-ray diffraction and infrared spectroscopy, used in the study of Werner complexes, have paralleled the development of these techniques. The results of these investigations have not only confirmed the validity of Werner s coordination theory but have also provided more detailed structural and bonding information. In early 1932, Damaschun (13) measured the Raman spectra of seven complex ions, such as [Cu(NH3)4]" and [Zn(CN)4j and these may be the first vibrational spectra ever obtained for Werner complexes. In these early days, vibrational spectra were mainly observed as Raman spectra because they were technically much easier to obtain than infrared spectra. In 1939, Wilson 35, 36) developed a new theory, the GF method," which enabled him to analyze the normal vibrations of complex molecules. This theoretical revolution, coupled with rapid developments of commercial infrared and Raman instruments after World War II, ushered in the most fruitful period in the history of vibrational studies of inorganic and coordination compounds. 

N.V. Sidgwick, Coordination compounds and Bhor atom, J. Chem. Soc. CXIII, 725 (1923) The Electronic Theory of Valency, Oxford (1927) W.G. Palmer, Valency, Classical and Modem, Cam bridge (1944) also cited in J.R. Partington, A Short History of Chemistry, 3rd ed., Dover Publications, New York, p. 368 (1989). 

The supersession of the most successful pre-Werner theory of the structure of coordination compounds, the so-called Blomstrand-J0rgensen chain theory, by Alfred Werner s coordination theory constitutes a valuable case study in scientiffc method and the history of chemistry. The highlights of the Werner-J0rgensen controversy and its implications for modem theories of chemical structure are Wretched in this article. 

Figure 16. Samples of compounds of crucial importance in the history of coordination theory. Top photograph (left to right) cw-[CoCl2(NH3)JCl, ciy-[CoCl2(NH3)4]N03 (violeo salts, 1907) racemic, d-, and /-[CoCl(NH3)(en)2]CL (the first coordination compound to be resolved,...

Pmssian blue is a notable coordination compound in that it is the first modem pigment to have a known history and established date of preparation (4). The most... 

Perhaps you have previously encountered coordination compounds (sometimes referred to as transition metal complexes) as part of a general chemistry course. Due to time considerations, this subject is usually covered only briefly, if at all, in such courses. In Part I (Chapters 2-6) of this book, however, coordination chemistry will be the sole focus of our attention. Accordingly, we will be able to discuss systematically the history, nomenclature, structures, bonding theories, reactions, and applications of such compounds. (After a physical chemistry course, more of the mathematical and abstract theoretical details are usually developed.) In this chapter we cover the historical perspective regarding such compounds, introduce some typical ligands, and start to develop a system of nomenclature. 

At the very end of the eighteenth century, Tassaert—a French chemist so obscure in the history of chemistry that his first name remains unknown—observed that ammonia combined with a cobalt ore to yield a reddish-brown product. This was most likely the first known coordination compound. Throughout the first half of the nineteenth century, many other, often beautifully crystalline examples of various cobalt ammonates were prepared. These compounds were strikingly colored, and the names given to them—for example, roseo-, luteo- (from the Latin luteus, meaning deep yellow ), and purpureocobaltic chlorides—reflected these colors. 

Coordination compounds are typically characterized by four or six ligands in a coordination sphere surrounding a metal atom or ion. This chapter starts a systematic investigation of coordination chemistry by putting its history into perspective, introducing some typical ligands, and setting down the basics of a scheme of nomenclature. 

In Chapters 2 and 3, we considered the history, nomenclature, and structures of coordination compounds. In these earlier discussions, we introduced the metal-ligand (M-L) coordinate-covalent bond in which the ligand shares a pair of electrons with the metal atom or ion. Now we are in a position to consider the nature of the M-L bond in greater detail. Is it primarily an ionic interaction between ligand electrons and a positively charged metal cation Or should the M-L bond be more properly described as predominantly covalent in character Whatever the character of the bond, the description of M-L interactions must account for (1) the stability of transition metal complexes, (2) their electronic and magnetic characteristics, and (3) the variety of striking colors displayed by these compounds. 

Vinylphosphines are a valuable class of compounds with a myriad of applications in organic synthesis and catalysis. Vinylphosphines also have a rich history in coordination chemistry due to the geometry and reactivity of this fragment with transition metal centers [414-420]. The proximity and flexibility of the alkene have been used to generate a host of coordination compounds in which the vinylphosphine is coordinated to the metal center through the phosphorus as well as through the alkene. In addition to providing a unique architecture for disCTCte coordination compounds, vinylphosphines are also valuable linkers in the formation of 3D arrays and coordination polymers [421-424],... 

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