Pinacol Cross-Coupling Promoted by an Aluminyl Anion.

A simple sequential addition protocol for the reductive coupling of ketones and aldehydes by a potassium aluminyl grants access to unsymmetrical pinacolate derivatives. Isolation of an aluminium ketyl complex presents evidence for the accessibility of radical species. Product release from the aluminium centre was achieved using an iodosilane, forming the disilylated 1,2-diol and a neutral aluminium iodide, thereby demonstrating the steps required to generate a closed synthetic cycle for pinacol (cross) coupling at an aluminyl anion.

Stabilisation of the [SiH6]2- Anion within a Supramolecular Assembly.

The hypercoordinate [SiH6]2- anion is not stable in solution. Here, we report the room temperature, solution stable molecular [SiH6]2- complex, [{KCa(NON)(OEt2)}2][SiH6] (NON=4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethyl-xanthene)), where the [SiH6]2- anion is stabilised within a supramolecular assembly that mimics the solid-state environment of the anion in the lattice of K2SiH6. Solution-state reactivity of the complex towards carbon monoxide, benzaldehyde, azobenzene and acetonitrile is reported, yielding a range of reduction and C-C coupled products.

Li vs Na: Divergent Reaction Patterns between Organolithium and Organosodium Complexes and Ligand-Catalyzed Ketone/Aldehyde Methylenation.

Organosodium chemistry is underdeveloped compared with organolithium chemistry, and all the reported organosodium complexes exhibit similar, if not identical, reactivity patterns to their lithium counterparts. Herein, we report a rare organosodium monomeric complex, namely, [Na(CH2SiMe3)(Me6Tren)] (1-Na) (Me6Tren: tris[2-(dimethylamino)ethyl]amine) stabilized by a tetra-dentate neutral amine ligand Me6Tren. Employing organo-carbonyl substrates (ketones, aldehydes, amides, ester), we demonstrated that 1-Na features distinct reactivity patterns compared with its lithium counterpart, [Li(CH2SiMe3)(Me6Tren)] (1-Li). Based on this knowledge, we further developed a ligand-catalysis strategy to conduct ketone/aldehyde methylenations, using [NaCH2SiMe3]∞ as the CH2 feedstock, replacing the widely used but hazardous/expensive C═O methylenation methods, such as Wittig, Tebbe, Julia/Julia-Kocienski, Peterson, and so on.

Reductive Coupling of a Diazoalkane Derivative Promoted by a Potassium Aluminyl and Elimination of Dinitrogen to Generate a Reactive Aluminium Ketimide.

The reaction of 9-diazo-9H-fluorene (fluN2 ) with the potassium aluminyl K[Al(NON)] ([NON]2- =[O(SiMe2 NDipp)2 ]2- , Dipp=2,6-iPr2 C6 H3 ) affords K[Al(NON)(κN1 ,N3 -{(fluN2 )2 })] (1). Structural analysis shows a near planar 1,4-di(9H-fluoren-9-ylidene)tetraazadiide ligand that chelates to the aluminium. The thermally induced elimination of dinitrogen from 1 affords the neutral aluminium ketimide complex, Al(NON)(N=flu)(THF) (2) and the 1,2-di(9H-fluoren-9-yl)diazene dianion as the potassium salt, [K2 (THF)3 ][fluN=Nflu] (3). The reaction of 2 with N,N'-diisopropylcarbodiimide (iPrN=C=NiPr) affords the aluminium guanidinate complex, Al(NON){N(iPr)C(N=CMe2 )N(CHflu)} (4), showing a rare example of reactivity at a metal ketimide ligand. Density functional theory (DFT) calculations have been used to examine the bonding in the newly formed [(fluN2 )2 ]2- ligand in 1 and the ketimide bonding in 2. The mechanism leading to the formation of 4 has also been studied using this technique.

A Blueprint for the Stabilization of Sub-Valent Alkaline Earth Complexes.

The study of sub-valent Group 2 chemistry is a relatively new research field, being established in 2007 with the report of the first Mg(I) dimers. These species are stabilized by the formation of a Mg-Mg covalent bond; however, the extension of this chemistry to heavier alkaline earth (AE) metals has been frustrated by significant synthetic challenges, primarily associated with the instability of heavy AE-AE interactions. Here we present a new blueprint for the stabilization of heavy AE(I) complexes, based upon the reduction of AE(II) precursors with planar coordination geometries. We report the synthesis and structural characterisation of homoleptic trigonal planar AE(II) complexes of the monodentate amides {N(SiMe3 )2 }- and {N(Mes)(SiMe3 )}- . DFT calculations showed that the LUMOs of these complexes all show some d-character for AE = Ca-Ba. DFT analysis of the square planar Sr(II) complex [Sr{N(SiMe3 )2 }(dioxane)2 ]∞ revealed analogous frontier orbital d-character. AE(I) complexes that could be accessed by reduction of these AE(II) precursors were modelled computationally, revealing exergonic formation in all cases. Crucially, NBO calculations show that some d-character is preserved in the SOMO of theoretical AE(I) products upon reduction, showing that d-orbitals could play a crucial role in achieving stable heavy AE(I) complexes.

Lithium, Tin(II), and Zinc Amino-Boryloxy Complexes: Synthesis and Characterization.

Analogous to the ubiquitous alkoxide ligand, metal boroxide and boryloxy complexes are an underexplored class of hard anionic O- ligand. A new series of amine-stabilized Li, Sn(II), and Zn boryloxy complexes, comprising electron-rich tetrahedral boron centers have been synthesized and characterized. All complexes have been characterized by one-dimensional (1D), two-dimensional (2D), and DOSY NMR, which are consistent with the solid-state structures unambiguously determined via single-crystal X-ray diffraction. Electron-rich µ2- (Sn and Zn) and µ3- (Li) boryloxy binding modes are observed. Compounds 6-9 are the first complexes of this class, with the chelating bis- and tris-phenol ligands providing a scaffold that can be easily functionalized and provides access to the boronic acid pro-ligand, hence allowing facile direct synthesis of the resulting compounds. Computational quantum chemical studies suggest a significant enhancement of the π-donor ability of the amine-stabilized boryloxy ligand because of electron donation from the amine functionality into the p-orbital of the boron atom.

Reduction of Na+ within a {Mg2 Na2 } Assembly.

Ionic compounds containing sodium cations are notable for their stability and resistance to redox reactivity unless highly reducing electrical potentials are applied. Here we report that treatment of a low oxidation state {Mg2 Na2 } species with non-reducible organic bases induces the spontaneous and completely selective extrusion of sodium metal and oxidation of the MgI centers to the more conventional MgII state. Although these processes are also characterized by a structural reorganisation of the initially chelated diamide spectator ligand, computational quantum chemical studies indicate that intramolecular electron transfer is abetted by the frontier molecular orbitals (HOMO/LUMO) of the {Mg2 Na2 } ensemble, which arise exclusively from the 3s valence atomic orbitals of the constituent sodium and magnesium atoms.

A Terphenyl Supported Dioxophosphorane Dimer: the Light Congener of Lawesson's and Woollins' Reagents.

Thermolysis of a 1,3-dioxa-2-phospholane supported by the terphenyl ligand AriPr4 (AriPr4 =[C6 H3 -2,6-(C6 H3 -2,6-iPr2 )]) at 150 °C gives [AriPr4 PO2 ]2 via loss of ethene. [AriPr4 PO2 ]2 was characterised by X-ray crystallography and NMR spectroscopy; it contains a 4-membered P-O-P-O ring and is the isostructural oxygen analogue of Lawesson's and Woollins' reagents. The dimeric structure of [AriPr4 PO2 ]2 was found to persist in solution through VT NMR spectroscopy and DOSY, supported by DFT calculations. The addition of DMAP to the 1,3-dioxa-2-phospholane facilitates the loss of ethene to give AriPr4 (DMAP)PO2 after days at room temperature, with this product also characterised by X-ray crystallography and NMR spectroscopy. Replacement of the DMAP with pyridine induces ethene loss from the 1,3-dioxa-2-phospholane to provide gram-scale samples of [AriPr4 PO2 ]2 in 75 % yield in 2 days at only 100 °C.

Potassium Aluminyl Promoted Carbonylation of Ethene.

The potassium aluminyl [K{Al(NONDipp )}]2 ([NONDipp ]2- =[O{SiMe2 NDipp}2 ]2- , Dipp=2,6-iPr2 C6 H3 ) activates ethene towards carbonylation with CO under mild conditions. An isolated bis-aluminacyclopropane compound reacted with CO via carbonylation of an Al-C bond, followed by an intramolecular hydrogen shift to form K2 [Al(NONDipp )(µ-CH2 CH=CO-1κ2 C1,3 -2κO)Al(NONDipp )Et]. Restricting the chemistry to a mono-aluminium system allowed isolation of [Al(NONDipp )(CH2 CH2 CO-κ2 C1,3 )]- , which undergoes thermal isomerisation to form the [Al(NONDipp )(CH2 CH=CHO-κ2 C,O)]- anion. DFT calculations highlight the stabilising influence of incorporated benzene at multiple steps in the reaction pathways.

Reductive Dimerization of CO by a Na/Mg(I) Diamide.

Sodium reduction of [{SiNDipp}Mg] [{SiNDipp} = {CH2SiMe2N(Dipp)}2; Dipp = 2,6-i-Pr2C6H3] provides the Mg(I) species, [{SiNDipp}MgNa]2, in which the long Mg-Mg bond (>3.2 Å) is augmented by persistent Na-aryl interactions. Computational assessment indicates that this molecule is best considered to comprise a contiguous tetrametallic core, a viewpoint borne out by its reaction with CO, which results in ethynediolate formation mediated by the dissimilar metal centers.

Seven-Membered Cyclic Potassium Diamidoalumanyls.

The seven-membered cyclic potassium alumanyl species, [{SiNMes }AlK]2 [{SiNMes }={CH2 SiMe2 N(Mes)}2 ; Mes=2,4,6-Me3 C6 H2 ], which adopts a dimeric structure supported by flanking K-aryl interactions, has been isolated either by direct reduction of the iodide precursor, [{SiNMes }AlI], or in a stepwise manner via the intermediate dialumane, [{SiNMes }Al]2 . Although the intermediate dialumane has not been observed by reduction of a Dipp-substituted analogue (Dipp=2,6-i-Pr2 C6 H3 ), partial oxidation of the potassium alumanyl species, [{SiNDipp }AlK]2 , where {SiNDipp }={CH2 SiMe2 N(Dipp)}2 , provided the extremely encumbered dialumane [{SiNDipp }Al]2 . [{SiNDipp }AlK]2 reacts with toluene by reductive activation of a methyl C(sp3 )-H bond to provide the benzyl hydridoaluminate, [{SiNDipp }AlH(CH2 Ph)]K, and as a nucleophile with BPh3 and RN=C=NR (R=i-Pr, Cy) to yield the respective Al-B- and Al-C-bonded potassium aluminaborate and alumina-amidinate products. The dimeric structure of [{SiNDipp }AlK]2 can be disrupted by partial or complete sequestration of potassium. Equimolar reactions with 18-crown-6 result in the corresponding monomeric potassium alumanyl, [{SiNDipp }Al-K(18-cr-6)], which provides a rare example of a direct Al-K contact. In contrast, complete encapsulation of the potassium cation of [{SiNDipp }AlK]2 , either by an excess of 18-cr-6 or 2,2,2-cryptand, allows the respective isolation of bright orange charge-separated species comprising the 'free' [{SiNDipp }Al]- alumanyl anion. Density functional theory (DFT) calculations performed on this moiety indicate HOMO-LUMO energy gaps in the of order 200-250 kJ mol-1 .

Controlling Al-M Interactions in Group 1 Metal Aluminyls (M = Li, Na, and K). Facile Conversion of Dimers to Monomeric and Separated Ion Pairs.

The aluminyl compounds [M{Al(NONDipp)}]2 (NONDipp = [O(SiMe2NDipp)2]2-, Dipp = 2,6-iPr2C6H3), which exist as contacted dimeric pairs in both the solution and solid states, have been converted to monomeric ion pairs and separated ion pairs for each of the group 1 metals, M = Li, Na, and K. The monomeric ion pairs contain discrete, highly polarized Al-M bonds between the aluminum and the group 1 metal and have been isolated with monodentate (THF, M = Li and Na) or bidentate (TMEDA, M = Li, Na, and K) ligands at M. The separated ion pairs comprise group 1 cations that are encapsulated by polydentate ligands, rendering the aluminyl anion, [Al(NONDipp)]- "naked". For M = Li, this structure type was isolated as the [Li(TMEDA)2]+ salt directly from a solution of the corresponding contacted dimeric pair in neat TMEDA, while the polydentate [2.2.2]cryptand ligand was used to generate the separated ion pairs for the heavier group 1 metals M = Na and K. This work shows that starting from the corresponding contacted dimeric pairs, the extent of the Al-M interaction in these aluminyl systems can be readily controlled with appropriate chelating reagents.

Dihydrogen Activation by Lithium- and Sodium-Aluminyls.

To date, aluminyl anions have been exclusively isolated as their potassium salts. We report herein the synthesis of the lithium and sodium aluminyls, M2 [Al(NONDipp )]2 (M=Li, Na. NONDipp =[O(SiMe2 NDipp)2 ]2- ; Dipp=2,6-iPr2 C6 H3 ). Both compounds crystallize from non-coordinating solvent as "slipped" contacted dimeric pairs with strong M⋅⋅⋅π(aryl) interactions. Isolation from Et2 O solution affords the monomeric ion pairs (NONDipp )Al-M(Et2 O)2 , which contain discrete Al-Li and Al-Na bonds. The ability of the full series of Li, Na and K aluminyls to activate dihydrogen is reported.

Ambiphilic Al-Cu Bonding.

Copper-alumanyl complexes, [LCu-Al(SiNDipp )], where L=carbene=NHCiPr (N,N'-diisopropyl-4,5-dimethyl-2-ylidene) and Me2 CAAC (1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethyl-pyrrolidin-2-ylidene) and featuring unsupported Al-Cu bonds, have been prepared. Divergent reactivity observed with carbodiimides and CO2 implies an ambiphilicity in the Cu-Al interaction that is dependent on the identity of the carbene co-ligand.

Nucleophilic Magnesium Silanide and Silaamidinate Derivatives.

Density functional theory (DFT) calculations demonstrate that the previously reported reaction of [(BDI)Mg-n-Bu] (BDI = HC{(Me)CN-Dipp}2; Dipp = 2,6-diisopropylphenyl) with the silaborane Me2PhSi-Bpin provides the magnesium silanide derivative [(BDI)MgSiMe2Ph], through the intermediacy of a short-lived silyl-pinacolato-organoborate species. The nucleophilic character of the resultant silanide anion is assayed through a series of reactions with RN═C═NR (R = i-Pr, Cy, t-Bu) and p-tolN═C═N-p-tol. When they are performed in a strict 1:1 stoichiometry, all four reactions result in silyl addition to the carbodiimide carbon center and formation of the corresponding ß-diketiminato magnesium silaamidinate complexes. Although the performance of the reaction of [(BDI)MgSiMe2Ph] with 2 equiv of p-tolylcarbodiimide also results in the formation of a silaamidinate anion, the second equivalent is observed to engage with the nucleophilic γ-methine carbon of the BDI ligand to provide a tripodal diimino-iminoamidate ligand. This behavior is judged to be a consequence of the enhanced electrophilicity of the N-aryl-substituted carbodiimide reagent, a viewpoint supported by a further reaction with the N-isopropyl silaamidinate complex [(BDI)Mg(i-PrN)2CSiMe2Ph]. This latter reaction not only provides an identical diimino-iminoamidate ligand but also results in 2-fold insertion of p-tolN═C═N-p-tol into a Mg-N bond between the magnesium center and the silaamidinate anion.

[BO2 ]- as a Synthon for the Generation of Boron-Centered Carbamate and Carboxylate Isosteres.

Oxoborane carbamate and carboxylate analogues result from the in situ trapping of [BO2 ]- produced by elimination of 2,3-dimethyl-2-butene from a pinacolatoboryl anion.

Carbon-Carbon Bond Forming Reactions Promoted by Aluminyl and Alumoxane Anions: Introducing the Ethenetetraolate Ligand.

[K{Al(NONDipp )}]2 (NONDipp =[O(SiMe2 NDipp)2 ]2- , Dipp=2,6-iPr2 C6 H3 ) reacts with CS2 to afford the trithiocarbonate species [K(OEt2 )][Al(NONDipp )(CS3 )] 1 or the ethenetetrathiolate complex, [K{Al(NONDipp )(S2 C)}]2 [3]2 . The dimeric alumoxane [K{Al(NONDipp )(O)}]2 reacts with carbon monoxide to afford the oxygen analogue of 3, [K{Al(NONDipp )(O2 C)}]2 [4]2 containing the hitherto unknown ethenetetraolate ligand, [C2 O4 ]4- .

A Stable Calcium Alumanyl.

A seven-membered N,N'-heterocyclic potassium alumanyl nucleophile is introduced and utilised in the metathetical synthesis of Mg-Al and Ca-Al bonded derivatives. Both species have been characterised by experimental and theoretical means, allowing a rationalisation of the greater reactivity of the heavier group 2 species implied by an initial assay of their reactivity.

The Importance of Kinetic and Thermodynamic Control when Assessing Mechanisms of Carboxylate-Assisted C-H Activation.

The reactions of substituted 1-phenylpyrazoles (phpyz-H) at [MCl2Cp*]2 dimers (M = Rh, Ir; Cp* = C5Me5) in the presence of NaOAc to form cyclometalated Cp*M(phpyz)Cl were studied experimentally and with density functional theory (DFT) calculations. At room temperature, time-course and H/D exchange experiments indicate that product formation can be reversible or irreversible depending on the metal, the substituents, and the reaction conditions. Competition experiments with both para- and meta-substituted ligands show that the kinetic selectivity favors electron-donating substituents and correlates well with the Hammett parameter giving a negative slope consistent with a cationic transition state. However, surprisingly, the thermodynamic selectivity is completely opposite, with substrates with electron-withdrawing groups being favored. These trends are reproduced with DFT calculations that show C-H activation proceeds by an AMLA/CMD mechanism. H/D exchange experiments with the meta-substituted ligands show ortho-C-H activation to be surprising facile, although (with the exception of F substituents) this does not generally lead to ortho-cyclometalated products. Calculations suggest that this can be attributed to the difficulty of HOAc loss after the C-H activation step due to steric effects in the 16e intermediate that would be formed. Our study highlights that the use of substituent effects to assign the mechanism of C-H activation in either stoichiometric or catalytic reactions may be misleading, unless the energetics of the C-H cleavage step and any subsequent reactions are properly taken into account. The broader implications of our study for the assignment of C-H activation mechanisms are discussed.

Azulene-Derived Fluorescent Probe for Bioimaging: Detection of Reactive Oxygen and Nitrogen Species by Two-Photon Microscopy.

Two-photon fluorescence microscopy has become an indispensable technique for cellular imaging. Whereas most two-photon fluorescent probes rely on well-known fluorophores, here we report a new fluorophore for bioimaging, namely azulene. A chemodosimeter, comprising a boronate ester receptor motif conjugated to an appropriately substituted azulene, is shown to be an effective two-photon fluorescent probe for reactive oxygen species, showing good cell penetration, high selectivity for peroxynitrite, no cytotoxicity, and excellent photostability.