A historical perspective on Dewar's landmark contribution to organometallic chemistry

Mingos, D. Michael P.

doi:10.1016/s0022-328x(01)01155-x

Cited by 184 publications

(83 citation statements)

References 31 publications

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“…By studying a variety of metal-alkene complexes, Chatt and Duncanson [31] [32] This compound owes its stability to the very weakly coordinating anion, which is fully in accord with Chatts notion that silveralkene complexes become more stable the more ionized the silver salt is. [31b] It is generally accepted that back-donation increases with the principal quantum number of the metal center, and frequently the stabilities of the complexes of a specific alkene follow the same trend.…”

Section: Theory Of Metal-olefin Bondingmentioning

confidence: 73%

Chiral Olefins as Steering Ligands in Asymmetric Catalysis

2008

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Metal-catalyzed asymmetric processes offer one of the most straightforward ways to introduce stereogenic centers. Hence, the development of novel chiral ligands that can effectively induce asymmetry in reactions is crucial in modern organic synthesis. While many established chiral ligands bind to a metal through heteroatoms, structures that coordinate to metals through carbon atoms have received little attention so far. Here, we highlight the increasing number of such chiral chelating olefin ligands as well as their application in a variety of metal-catalyzed transformations.

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Section: Theory Of Metal-olefin Bondingmentioning

confidence: 73%

Chiral Olefins as Steering Ligands in Asymmetric Catalysis

2008

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“…This is the geometry that is predicted by the Dewar-Chatt-Duncanson model 3 used to describe the bonding in compounds of the type referred to as olefin complexes, of which Zeise's salt is the best-known example and for which C 2 H 4 · · ·AgCl is a prototype. Evidence for the formation of olefin complexes in solution through the reaction of Ag + with a range of unsaturated substances has been adduced as a result of investigations of distribution equilibria between an aqueous and an organic phase, for example.…”

Section: Introductionmentioning

confidence: 99%

A prototype transition-metal olefin complex C2H4⋯AgCl synthesised by laser ablation and characterised by rotational spectroscopy and ab initio methods

Stephens

Tew

Mikhailov

et al. 2011

The Journal of Chemical Physics

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C(2)H(4)···Ag-Cl has been synthesised in the gas phase in a pulsed-jet, Fourier-transform microwave spectrometer by the reaction of laser-ablated metallic silver with carbon tetrachloride to give AgCl, which subsequently reacts with ethene to give the complex. The ground-state rotational spectra of six isotopologues (C(2)H(4)···(107)Ag(35)Cl, C(2)H(4)···(109)Ag(35)Cl, C(2)H(4)···(107)Ag(37)Cl, C(2)H(4)···(109)Ag(37)Cl, (13)C(2)H(4)···(107)Ag(35)Cl, and (13)C(2)H(4)···(109)Ag(35)Cl) were recorded and analysed to give rotational constants A(0), B(0), and C(0), centrifugal distortion constants Δ(J) and Δ(JK), and Cl nuclear quadrupole coupling constants χ(aa)(Cl) and χ(bb)(Cl)-χ(cc)(Cl). These spectroscopic constants were interpreted in terms of a geometry for C(2)H(4)···Ag-Cl of C(2V) symmetry in which the AgCl molecule lies along the C(2) axis of ethene that is perpendicular to the C(2)H(4) plane. The Ag atom forms a bond to the midpoint (*) of the ethene π bond. A partial r(s)-geometry and a r(0)-geometry were determined, with the values r(*···Ag) = 2.1719(9) Å, r(C-C) = 1.3518(4) Å, and r(Ag-Cl) = 2.2724(8) Å obtained in the latter case. The C-C bond lengthens on formation of the complex. Detailed ab initio calculations carried out at the CCSD(T)/cc-pVQZ level of theory give results in good agreement with experiment and also reveal that the ethene molecule undergoes a small angular distortion. The distortion is such that the four H atoms move in a direction away from Ag but remain coplanar. The two C atoms are no longer contained in this plane, however. The electric charge redistribution when C(2)H(4)···Ag-Cl is formed and the strength of the π···Ag bond are discussed.

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“…1(I)e(III) and Table 1, the bonding originates by mixing of Ca 4s and 3d orbitals with the nanotubes 2p orbital, and simultaneously, there exists a donation and back donation between the metal and the nanotubes. Upon this findings, the bonding between the Ca atom and the nanotube obey Dewar i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 7 4 3 1 e7 4 3 7 coordination [48]. Moreover, the E bind of the Ca atom on the perfect, Cv, and Nv structures are À1.17, À3.80, and À2.47 eV/ Ca, respectively and exothermic.…”

Section: Resultsmentioning

confidence: 80%