Robert E. Mulvey

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Diversity of Structures and Bonding in Alkali Metal Ureaphosphanes

Michelle H. Crabbe, Alan R. Kennedy, Catherine E. Weetman, Robert E. Mulvey

Helvetica Chimica Acta > 107 > 8 > n/a - n/a

While organoelement compounds of lithium, sodium and potassium have been much studied for decades and consequently have found forests of applications, those of the heavier alkali metals, rubidium and caesium would barely manage to fill a tree. However, recently the literature has seen some little growth spurts with these metals, hinting at a possible fertile future in areas such as homogeneous catalysis...

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Three Oxidative Addition Routes of Alkali Metal Aluminyls to Dihydridoaluminates and Reactivity with CO₂

Sumanta Banerjee, Gerd M. Ballmann, Matthew J. Evans, Andrea O'Reilly, more

Chemistry – A European Journal > 29 > 56 > n/a - n/a

Three distinct routes are reported to the soluble, dihydridoaluminate compounds, AM[Al(NON^Dipp)(H)₂] (AM=Li, Na, K, Rb, Cs; [NON^Dipp]²⁻=[O(SiMe₂NDipp)₂]²⁻; Dipp=2,6‐iPr₂C₆H₃) starting from the alkali metal aluminyls, AM[Al(NON^Dipp)]. Direct H₂ hydrogenation of the heavier analogues (AM=Rb, Cs) produced the first examples of structurally characterized rubidium and caesium dihydridoaluminates, although...

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Alkali Metal Dihydropyridines in Transfer Hydrogenation Catalysis of Imines: Amide Basicity versus Hydride Surrogacy

Peter A. Macdonald, Sumanta Banerjee, Alan R. Kennedy, Alexander Teijlingen, more

Angewandte Chemie > 135 > 27 > n/a - n/a

Catalytic reduction of a representative set of imines, both aldimines and ketimines, to amines has been studied using transfer hydrogenation from 1,4‐dicyclohexadiene. Unusually, this has been achieved using s‐block pre‐catalysts, namely 1‐metallo‐2‐tert‐butyl‐1,2‐dihydropyridines, 2‐tBuC₅H₅NM, M(tBuDHP), where M=Li–Cs. Reactions have been monitored in C₆D₆ and tetrahydrofuran‐d₈ (THF‐d₈). A definite...

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Alkali Metal Dihydropyridines in Transfer Hydrogenation Catalysis of Imines: Amide Basicity versus Hydride Surrogacy

Peter A. Macdonald, Sumanta Banerjee, Alan R. Kennedy, Alexander Teijlingen, more

Angewandte Chemie International Edition > 62 > 27 > n/a - n/a

Catalytic reduction of a representative set of imines, both aldimines and ketimines, to amines has been studied using transfer hydrogenation from 1,4‐dicyclohexadiene. Unusually, this has been achieved using s‐block pre‐catalysts, namely 1‐metallo‐2‐tert‐butyl‐1,2‐dihydropyridines, 2‐tBuC₅H₅NM, M(tBuDHP), where M=Li–Cs. Reactions have been monitored in C₆D₆ and tetrahydrofuran‐d₈ (THF‐d₈). A definite...

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Incorporating Trimethylaluminium into the Structures of Alkali Metal (Li, Na, K, Cs) dihydropyridines

Shay P. Docherty, Sumanta Banerjee, William Clegg, Fiona J. Palin, more

Zeitschrift für anorganische und allgemeine Chemie > 649 > 5 > n/a - n/a

Co‐complexation of equimolar amounts of 1‐alkali‐metal‐2‐tertbutyldihydropyridines with AlMe₃ in the presence of a polydentate N‐donor ligand has delivered four crystallographically verified alkali‐metal aluminates [donor⋅AM(μ‐tBuDHP)AlMe₃]_n (1, AM=Li, donor=TMEDA, n=1; 2, AM=Na, donor=PMDETA, n=1; 3, AM=K, donor=PMDETA, n=2; 4, AM=Cs, donor=PMDETA, n=∞; TMEDA=N,N,N′,N′‐tetramethylethylenediamine;...

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Hydrocarbon Soluble Alkali‐Metal‐Aluminium Hydride Surrog[ATES]

Sumanta Banerjee, Peter A. Macdonald, Samantha A. Orr, Alan R. Kennedy, more

Chemistry – A European Journal > 28 > 55 > n/a - n/a

A series of group 1 hydrocarbon‐soluble donor free aluminates [AM(^tBuDHP)(TMP)Al(ⁱBu)₂] (AM=Li, Na, K, Rb) have been synthesised by combining an alkali metal dihydropyridyl unit [(2‐^tBuC₅H₅N)AM)] containing a surrogate hydride (sp³ C−H) with [(ⁱBu)₂Al(TMP)]. These aluminates have been characterised by X‐ray crystallography and NMR spectroscopy. While the lithium aluminate forms a monomer, the heavier...

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Heavy Alkali Metal Manganate Complexes: Synthesis, Structures and Solvent‐Induced Dissociation Effects

Gerd M. Ballmann, Thomas X. Gentner, Alan R. Kennedy, Eva Hevia, more

Chemistry – A European Journal > 28 > 55 > n/a - n/a

Rare examples of heavier alkali metal manganates [{(AM)Mn(CH₂SiMe₃)(N^‘Ar)₂}_∞] (AM=K, Rb, or Cs) [N^‘Ar=N(SiMe₃)(Dipp), where Dipp=2,6‐iPr₂‐C₆H₃] have been synthesised with the Rb and Cs examples crystallographically characterised. These heaviest manganates crystallise as polymeric zig‐zag chains propagated by AM⋅⋅⋅π‐arene interactions. Key to their preparation is to avoid Lewis base donor solvents...

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Crystallographic Characterisation of Organolithium and Organomagnesium Intermediates in Reactions of Aldehydes and Ketones

Jennifer R. Lynch, Alan R. Kennedy, Jim Barker, Jacqueline Reid, more

Helvetica Chimica Acta > 105 > 9 > n/a - n/a

We report reactions of LiNacNac and NacNacMg(TMP) with common organic substrates (TMP=2,2,6,6‐tetramethylpiperidide). Using bulky β‐diketiminate compound NacNac (Me, Dipp), we have trapped metalated intermediates amenable to X‐ray crystallographic study. LiNacNac and acetone produced the NacNac‐free hexameric diacetone alkoxide [{LiO(MeC(=O)CH₂C(Me)₂}₆]; whereas pinacolone gave the simple monomeric...

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Sigma/pi Bonding Preferences of Solvated Alkali‐Metal Cations to Ditopic Arylmethyl Anions

Annabel Rae, Keelan M. Byrne, Scott A. Brown, Alan R. Kennedy, more

Chemistry – A European Journal > 28 > 18 > n/a - n/a

Arylmethyl anions allow alkali‐metals to bind in a σ‐fashion to the lateral carbanionic centre or a π‐fashion to the aryl ring or in between these extremities, with the trend towards π bonding increasing on descending group 1. Here we review known alkali metal structures of diphenylmethane, fluorene, 2‐benzylpyridine and 4‐benzylpyridine. Next, we synthesise Li, Na, K monomers of these diarylmethyls...

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Structural Studies of Donor‐Free and Donor‐Solvated Sodium Carboxylates

Richard M. Gauld, Ross McLellan, Alan R. Kennedy, Freya J. Carson, more

European Journal of Inorganic Chemistry > 2021 > 16 > 1615 - 1622

Focusing mainly on sodium 2‐ethylhexanoate, this study reveals that the carboxylate exists as a dimer in MeOD solution as evidenced by Diffusion Ordered NMR SpectroscopY (DOSY). Two crystalline varieties with distinct polymeric structures have been synthesised and crystallographically characterised. A mixed 1,10‐phenanthroline–water solvate [{(C₅H₁₀)(C₂H₅)COONa.(H₂O)[1,10‐phen]}₂]_∞ contains dimeric...

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Alkali‐Metal Mediation: Diversity of Applications in Main‐Group Organometallic Chemistry

Thomas X. Gentner, Robert E. Mulvey

Angewandte Chemie International Edition > 60 > 17 > 9247 - 9262

Organolithium compounds have been at the forefront of synthetic chemistry for over a century, as they mediate the synthesis of myriads of compounds that are utilised worldwide in academic and industrial settings. For that reason, lithium has always been the most important alkali metal in organometallic chemistry. Today, that importance is being seriously challenged by sodium and potassium, as the...

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Alkalimetall‐Mediatoren: Vielfältige Anwendungen in der metallorganischen Chemie der Hauptgruppenelemente

Thomas X. Gentner, Robert E. Mulvey

Angewandte Chemie > 133 > 17 > 9331 - 9348

Organolithiumverbindungen stehen seit mehr als einem Jahrhundert an der Spitze der Synthesechemie, da sie die Synthese von einer Vielzahl von Verbindungen ermöglichen, die weltweit im akademischen und industriellen Bereich eingesetzt werden. Aus diesem Grund ist Lithium seit jeher das wichtigste Alkalimetall in der metallorganischen Chemie. Heute wird diese Dominanz durch Natrium und Kalium ernsthaft...

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Structurally Defined Ring‐Opening and Insertion of Pinacolborane into Aluminium‐Nitrogen Bonds of Sterically Demanding Dialkylaluminium Amides

Victoria A. Pollard, Alan R. Kennedy, Ross McLellan, Duncan Ross, more

European Journal of Inorganic Chemistry > 2021 > 1 > 50 - 53

Dialkylaluminium amides iBu₂Al(TMP) and iBu₂Al(HMDS) can perform catalytic hydroboration of ketones with pinacolborane to form the expected boronic esters. However, repeating the same reactions stoichiometrically without a ketone leads unexpectedly to ring‐opening of pinacolborane and insertion of its open chain into the Al−N(amido) bond. To date there has been limited knowledge on decomposition pathways...

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Back Cover: Isomerization Reactions in Anionic Mesoionic Carbene‐Borates and Control of Properties and Reactivities in the Resulting Co^II Complexes through Agostic Interactions (Angew. Chem. Int. Ed. 1/2021)

Jessica Stubbe, Nicolás I. Neuman, Ross McLellan, Michael G. Sommer, more

Angewandte Chemie International Edition > 60 > 1 > 512 - 512

Anionic borate‐based bi‐mesoionic carbenes based on 1,2,3‐triazol‐4‐ylidenes show unique C−N isomerization reactions. In their Research Article on page 499, Biprajit Sarkar and co‐workers report on the isomerized ligands in Co^II complexes. The picture shows these complexes, which, despite having a similar first coordination sphere, differ in geometry, spin state, and reactivity. All of these differences...

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Isomerization Reactions in Anionic Mesoionic Carbene‐Borates and Control of Properties and Reactivities in the Resulting Co^II Complexes through Agostic Interactions

Jessica Stubbe, Nicolás I. Neuman, Ross McLellan, Michael G. Sommer, more

Angewandte Chemie International Edition > 60 > 1 > 499 - 506

We present herein anionic borate‐based bi‐mesoionic carbene compounds of the 1,2,3‐triazol‐4‐ylidene type that undergo C−N isomerization reactions. The isomerized compounds are excellent ligands for Co^II centers. Strong agostic interactions with the “C−H”‐groups of the cyclohexyl substituents result in an unusual low‐spin square planar Co^II complex, which is unreactive towards external substrates...

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Solvation Effects on the Structure and Stability of Alkali Metal Carbenoids

Katharina Dilchert, Michelle Schmidt, Angela Großjohann, Kai‐Stephan Feichtner, more

Angewandte Chemie International Edition > 60 > 1 > 493 - 498

s‐Block metal carbenoids are carbene synthons and applied in a myriad of organic transformations. They exhibit a strong structure–activity relationship, but this is only poorly understood due to the challenging high reactivity and sensitivity of these reagents. Here, we report on systematic VT and DOSY NMR studies, XRD analyses as well as DFT calculations on a sulfoximinoyl‐substituted model system...

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Isomerisierungsreaktionen in anionischen mesoionischen Carbenboraten und Kontrolle der Eigenschaften und Reaktivität in den entstehenden Co^II‐Komplexen durch agostische Wechselwirkungen

Jessica Stubbe, Nicolás I. Neuman, Ross McLellan, Michael G. Sommer, more

Angewandte Chemie > 133 > 1 > 505 - 513

Wir präsentieren anionische Borat‐basierte bi‐mesoionische Carbenverbindungen vom Typ 1,2,3‐Triazol‐4‐yliden, die C‐N‐Isomerisierungen eingehen können. Die isomerisierten Verbindungen sind ausgezeichnete Liganden für Co^II‐Zentren. Starke agostische Wechselwirkungen, ausgehend von den “C‐H”‐Gruppen der Cyclohexylsubstituenten, führen zu einem unüblichen quadratisch‐planaren Co^II‐Komplex im Low‐Spin‐Zustand,...

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Rücktitelbild: Isomerisierungsreaktionen in anionischen mesoionischen Carbenboraten und Kontrolle der Eigenschaften und Reaktivität in den entstehenden Co^II‐Komplexen durch agostische Wechselwirkungen (Angew. Chem. 1/2021)

Jessica Stubbe, Nicolás I. Neuman, Ross McLellan, Michael G. Sommer, more

Angewandte Chemie > 133 > 1 > 520 - 520

Anionische Borat‐basierte bi‐mesoionische Carbene, die auf 1,2,3‐Triazol‐4‐ylidenen basieren, zeigen einzigartige C‐N‐Isomerisierungsreaktionen. In ihrem Forschungsartikel auf S. 505 berichten Biprajit Sarkar und Mitarbeiter über die isomerisierten Liganden in Co^II‐Komplexen. Das Bild zeigt diese Komplexe, die sich trotz einer sehr ähnlichen ersten Koordinationssphäre in Geometrie, Spinzustand und...

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Lösungsmitteleinflüsse auf die Struktur und Stabilität von Alkalimetallcarbenoiden

Katharina Dilchert, Michelle Schmidt, Angela Großjohann, Kai‐Stephan Feichtner, more

Angewandte Chemie > 133 > 1 > 498 - 504

s‐Block‐Metallcarbenoide sind Carbensynthons und werden in einer Vielzahl organischer Reaktionen eingesetzt. Hierbei besitzen Carbenoide eine enge Struktur‐Reaktivitäts‐Beziehung, die jedoch aufgrund der hohen Reaktivität und Empfindlichkeit dieser Reagenzien bisher nur wenig verstanden ist. Hier berichten wir von systematischen VT‐ und DOSY‐NMR‐Studien, Strukturanalysen sowie DFT‐Rechnungen anhand...

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Synthesis, Structure, and DFT Analysis of the THF Solvate of 2‐Picolyllithium: A 2‐Picolyllithium Solvate with Significant Carbanionic Character

Etienne V. Brouillet, Alan R. Kennedy, Tobias Krämer, Robert E. Mulvey, more

Zeitschrift für anorganische und allgemeine Chemie > 646 > 13 > 726 - 733

Previous studies of different solvates of 2‐methylpyridyllithium (2‐picolyllithium) have uncovered electronic structures corresponding to aza‐allyl and enamido resonance forms of the metallated pyridine‐based compounds. Here, we report the synthesis and characterization of [2‐CH₂Li(THF)₂C₅H₄N], a new THF solvate. X‐ray crystallographic studies reveal a dimeric arrangement featuring a non‐planar eight‐membered...

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Search results for: Robert E. Mulvey

Diversity of Structures and Bonding in Alkali Metal Ureaphosphanes

Three Oxidative Addition Routes of Alkali Metal Aluminyls to Dihydridoaluminates and Reactivity with CO₂

Alkali Metal Dihydropyridines in Transfer Hydrogenation Catalysis of Imines: Amide Basicity versus Hydride Surrogacy

Alkali Metal Dihydropyridines in Transfer Hydrogenation Catalysis of Imines: Amide Basicity versus Hydride Surrogacy

Incorporating Trimethylaluminium into the Structures of Alkali Metal (Li, Na, K, Cs) dihydropyridines

Hydrocarbon Soluble Alkali‐Metal‐Aluminium Hydride Surrog[ATES]

Heavy Alkali Metal Manganate Complexes: Synthesis, Structures and Solvent‐Induced Dissociation Effects

Crystallographic Characterisation of Organolithium and Organomagnesium Intermediates in Reactions of Aldehydes and Ketones

Sigma/pi Bonding Preferences of Solvated Alkali‐Metal Cations to Ditopic Arylmethyl Anions

Structural Studies of Donor‐Free and Donor‐Solvated Sodium Carboxylates

Alkali‐Metal Mediation: Diversity of Applications in Main‐Group Organometallic Chemistry

Alkalimetall‐Mediatoren: Vielfältige Anwendungen in der metallorganischen Chemie der Hauptgruppenelemente

Structurally Defined Ring‐Opening and Insertion of Pinacolborane into Aluminium‐Nitrogen Bonds of Sterically Demanding Dialkylaluminium Amides

Back Cover: Isomerization Reactions in Anionic Mesoionic Carbene‐Borates and Control of Properties and Reactivities in the Resulting Co^II Complexes through Agostic Interactions (Angew. Chem. Int. Ed. 1/2021)

Isomerization Reactions in Anionic Mesoionic Carbene‐Borates and Control of Properties and Reactivities in the Resulting Co^II Complexes through Agostic Interactions

Solvation Effects on the Structure and Stability of Alkali Metal Carbenoids

Isomerisierungsreaktionen in anionischen mesoionischen Carbenboraten und Kontrolle der Eigenschaften und Reaktivität in den entstehenden Co^II‐Komplexen durch agostische Wechselwirkungen

Rücktitelbild: Isomerisierungsreaktionen in anionischen mesoionischen Carbenboraten und Kontrolle der Eigenschaften und Reaktivität in den entstehenden Co^II‐Komplexen durch agostische Wechselwirkungen (Angew. Chem. 1/2021)

Lösungsmitteleinflüsse auf die Struktur und Stabilität von Alkalimetallcarbenoiden

Synthesis, Structure, and DFT Analysis of the THF Solvate of 2‐Picolyllithium: A 2‐Picolyllithium Solvate with Significant Carbanionic Character

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