Mono-, Di-, Tri-, and Tetracarbonyls of Copper(I), Including the Structures of Cu(CO)2(1-Bn-CB11F11) and [Cu(CO)4][1-Et-CB11F11]

Ivanova, Svetlana; Ivanov, S. V.; Miller, Susie M.; Anderson, Oren P.; Солнцев, К. А.; Strauss, Steven H.

doi:10.1021/ic990321f

Cited by 105 publications

(72 citation statements)

References 20 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Permethylation to yield [CB 11 Me 12 ] À gives rise to salts with greater solubility. [98,99] These anions,i nc onjunction with the explosive [CB 11 (CF 3 ) 12 ] À [100] ion and the perfluorinated alkoxyaluminates (discussed later), are among the strongest contenders for the title of "least coordinating anion". [93,94] Halogenation to form [CB 11 H 6 X 6 ] À (X = Cl, Br,o rI ) [95][96][97] further delocalizes the negative charge,a nd these anions exhibit reduced coordinative strength compared to the parent [CB 11 H 12 ] À anion.…”

Section: Carborane and Dodecaborane Anionsmentioning

confidence: 99%

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

et al. 2018

View full text Add to dashboard Cite

This Review gives a comprehensive overview of the most topical weakly coordinating anions (WCAs) and contains information on WCA design, stability, and applications. As an update to the 2004 review, developments in common classes of WCA are included. Methods for the incorporation of WCAs into a given system are discussed and advice given on how to best choose a method for the introduction of a particular WCA. A series of starting materials for a large number of WCA precursors and references are tabulated as a useful resource when looking for procedures to prepare WCAs. Furthermore, a collection of scales that allow the performance of a WCA, or its underlying Lewis acid, to be judged is collated with some advice on how to use them. The examples chosen to illustrate WCA developments are taken from a broad selection of topics where WCAs play a role. In addition a section focusing on transition metal and catalysis applications as well as supporting electrolytes is also included.

show abstract

Section: Carborane and Dodecaborane Anionsmentioning

confidence: 99%

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

et al. 2018

View full text Add to dashboard Cite

show abstract

“…That is probably why metal carbonyl cations have found only limited application in follow-up chemistry,f or example in CO substitutions by such ligands. However,t he advent of modern weakly coordinatinga nions (WCAs), [10] enabled the switch to simple organic solvents like CH 2 Cl 2 ,a nd [Rh(CO) 4 ] + [1-Et-CB 11 F 11 ] À , [11] [Cu(CO) 2 ] + [1-Bn-CB 11 F 11 ] À , [12] or [Cu(CO) 4 ] + [1-Et-CB 11 F 11 ] À [12] were prepared without the use of superacids. They have been stabilized by carborane WCAs, which typically need multi-step syntheses and are often accessible only in as mall scale.…”

Section: Introductionmentioning

confidence: 99%

From an Easily Accessible Pentacarbonylcobalt(I) Salt to Piano‐Stool Cations [(arene)Co(CO)₂]⁺

Meier

Holz

Schmidt

et al. 2017

Chemistry A European J

View full text Add to dashboard Cite

The facile synthesis of a pentacarbonyl cobalt(I) salt without the need for a superacid as solvent is presented. This salt, [Co(CO) ] [Al(OR ) ] {R =C(CF ) }, readily accessible on a multigram scale, undergoes substitution reactions with arenes yielding the hitherto unknown class of two-legged cobalt piano-stool complexes [(arene)Co(CO) ] with four different arene ligands. Such a substitution chemistry would have been impossible in superacid solution, as the arenes used would have been oxidized and/or protonated. Thus, the general approach described herein may have a wide synthetic use. Additionally, the thermochemistry of the piano-stool complexes is shown to be not easy to describe computationally and most of the established DFT methods overestimate the reaction energies. Only CCSD(T) calculations close to the basis set limit gave energies fully agreeing with the experiment.

show abstract

“…[19] Moreover, stable anions of superacids exhibiting chemical inertness and solubility proved very useful in applications including olefin polymerization [20] and the isolation of highly reactive short-lived cations like HC 60 + and C 60 ·+ , [21] C 6 H 7 + , [22] Bu 3 Sn + [23] and Cu(CO) 4 + . [24] Consequently, synthesis of new superacids is highly desirable, because of their scientific and technological importance. Obviously, it is important to form a dense ladder of new superacids in order to meet the needs mentioned above.…”

Section: Introductionmentioning

confidence: 99%

Strong Acidity of Some Polycyclic Aromatic Compounds Annulated to a Cyclopentadiene Moiety and Their Cyano Derivatives – A Density Functional B3LYP Study

Vianello

Maksić

2005

Eur J Org Chem

View full text Add to dashboard Cite

The acidity of the parent 1H‐benz[f]indene (1a), 1H‐benz[e]indene (2a), 1H‐benz[fg]acenaphthylene (3a) and 1H‐cyclopenta[l]phenanthrene (4a) and of their polycyano derivatives is examined in the gas phase and in DMSO by the DFT‐B3LYP methods. It is shown that the parent hydrocarbons exhibit modest acidities, whereas a dramatic increase in acidity is observed upon multiple cyanation leading to hyperstrong neutral organic superacids. It is found that polycyano derivatives undergo prototropic tautomerism with a consequence that the most stable tautomer contains a ketene imine C=C=NH functionality. The origin of their highly pronounced acidity is identified as a very strong anionic resonance effect efficiently assisted by a large number of CN groups in a concerted manner. It is stressed that the polycyanated anions are very stable and have a highly dispersed negative charge, which should lead to a low nucleophilicity and weak coordinating properties, thus making them potentially very useful in academic research and technological applications. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

show abstract

Mono-, Di-, Tri-, and Tetracarbonyls of Copper(I), Including the Structures of Cu(CO)₂(1-Bn-CB₁₁F₁₁) and [Cu(CO)₄][1-Et-CB₁₁F₁₁]

Abstract: A bent dicarbonyl complex and a tetrahedral tetracarbonyl complex of copper(I), isolated using polyfluorocarborane superweak anions, have been structurally and spectroscopically characterized.

Cited by 105 publications

References 20 publications

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

From an Easily Accessible Pentacarbonylcobalt(I) Salt to Piano‐Stool Cations [(arene)Co(CO)₂]⁺

Strong Acidity of Some Polycyclic Aromatic Compounds Annulated to a Cyclopentadiene Moiety and Their Cyano Derivatives – A Density Functional B3LYP Study

Contact Info

Product

Resources

About

Mono-, Di-, Tri-, and Tetracarbonyls of Copper(I), Including the Structures of Cu(CO)2(1-Bn-CB11F11) and [Cu(CO)4][1-Et-CB11F11]

Abstract: A bent dicarbonyl complex and a tetrahedral tetracarbonyl complex of copper(I), isolated using polyfluorocarborane superweak anions, have been structurally and spectroscopically characterized.

Cited by 105 publications

References 20 publications

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

From an Easily Accessible Pentacarbonylcobalt(I) Salt to Piano‐Stool Cations [(arene)Co(CO)2]+

Strong Acidity of Some Polycyclic Aromatic Compounds Annulated to a Cyclopentadiene Moiety and Their Cyano Derivatives – A Density Functional B3LYP Study

Contact Info

Product

Resources

About

Mono-, Di-, Tri-, and Tetracarbonyls of Copper(I), Including the Structures of Cu(CO)₂(1-Bn-CB₁₁F₁₁) and [Cu(CO)₄][1-Et-CB₁₁F₁₁]

From an Easily Accessible Pentacarbonylcobalt(I) Salt to Piano‐Stool Cations [(arene)Co(CO)₂]⁺