Silver cation tagged on 5,7,12,14-tetraphenyl-6,13-diazapentacene and its dihydro-form.

The attachment of silver(I) cations to 5,7,12,14-tetraphenyl-6,13-diazapentacene and its reduced dihydro-form has been studied by electrospray ionization mass spectrometry (ESI-MS). The structure elucidation of the Ag+ complexes has been accomplished in gas-phase collision experiments in conjunction with density functional theory (DFT) calculations. The oxidized form provides a favourable cavity for the Ag+ ion, leading to the [1 : 1] complex with the highest resilience towards dissociation and severely hindering the attainment of a second molecular ligand. When the nitrogen is hydrogenated in the reduced dihydro-form, the cavity is partly blocked. This leads to a less strongly bound [1 : 1] complex ion but facilitates the attachment of a second molecular ligand to the Ag+. The resulting complex is the most stable among the [2 : 1] complexes. DFT calculations provide valuable insight into the geometries of the complex ions. Adding silver(I) to the reduced dihydro-form for cationization also induces its oxidation in solution. The oxidative dehydrogenation reaction, for which a mechanism is proposed, proceeds by first order kinetics and is markedly accelerated by day light.

Retro-Diels-Alder decomposition of norbornadiene mediated by a cationic magnesium complex.

First evidence for the coordination of norbornadiene (nbd) and dicyclopentadiene (dcpd) with the main group metal Mg is provided by the crystal structures of adducts with cationic ß-diketiminate (BDI) Mg complexes. While the dcpd complex is thermally stable, [(BDI)Mg+·nbd][B(C6F5)4-] shows slow room temperature retro-Diels-Alder decomposition to give a complex with the cation (BDI)Mg(C5H5)Mg(BDI)+.

Cationic Aluminium Complexes as Catalysts for Imine Hydrogenation.

Strongly Lewis acidic cationic aluminium complexes, stabilized by ß-diketiminate (BDI) ligands and free of Lewis bases, have been prepared as their B(C6 F5 )4 - salts and were investigated for catalytic activity in imine hydrogenation. The backbone (R1) and N (R2) substituents on the R1,R2 BDI ligand (R1,R2 BDI=HC[C(R1)N(R2)]2 ) influence sterics and Lewis acidity. Ligand bulk increases along the row Me,DIPP BDI

Insights into LiAlH4 Catalyzed Imine Hydrogenation.

Commercial LiAlH4 can be used in catalytic quantities in the hydrogenation of imines to amines with H2 . Combined experimental and theoretical investigations give deeper insight in the mechanism and identifies the most likely catalytic cycle. Activity is lost when Li in LiAlH4 is exchanged for Na or K. Exchanging Al for B or Ga also led to dramatically reduced activities. This indicates a heterobimetallic mechanism in which cooperation between Li and Al is crucial. Potential intermediates on the catalytic pathway have been isolated from reactions of MAlH4 (M=Li, Na, K) and different imines. Depending on the imine, double, triple or quadruple imine insertion has been observed. Prolonged reaction of LiAlH4 with PhC(H)=NtBu led to a side-reaction and gave the double insertion product LiAlH2 [N]2 ([N]=N(tBu)CH2 Ph) which at higher temperature reacts further by ortho-metallation of the Ph ring. A DFT study led to a number of conclusions. The most likely catalyst for hydrogenation of PhC(H)=NtBu with LiAlH4 is LiAlH2 [N]2 . Insertion of a third imine via a heterobimetallic transition state has a barrier of +23.2 kcal mol-1 (ΔH). The rate-determining step is hydrogenolysis of LiAlH[N]3 with H2 with a barrier of +29.2 kcal mol-1 . In agreement with experiment, replacing Li for Na (or K) and Al for B (or Ga) led to higher calculated barriers. Also, the AlH4 - anion showed very high barriers. Calculations support the experimentally observed effects of the imine substituents at C and N: the lowest barriers are calculated for imines with aryl-substituents at C and alkyl-substituents at N.

Unsupported Mg-Alkene Bonding.

The first intermolecular early main group metal-alkene complexes were isolated. This was enabled by using highly Lewis acidic Mg centers in the Lewis base-free cations (Me BDI)Mg+ and (tBu BDI)Mg+ with B(C6 F5 )4 - counterions (Me BDI=CH[C(CH3 )N(DIPP)]2 , tBu BDI=CH[C(tBu)N(DIPP)]2 , DIPP=2,6-diisopropylphenyl). Coordination complexes with various mono- and bis-alkene ligands, typically used in transition metal chemistry, were structurally characterized for 1,3-divinyltetramethyldisiloxane, 1,5-cyclooctadiene, cyclooctene, 1,3,5-cycloheptatriene, 2,3-dimethylbuta-1,3-diene, and 2-ethyl-1-butene. In all cases, asymmetric Mg-alkene bonding with a short and a long Mg-C bond is observed. This asymmetry is most extreme for Mg-(H2 C=CEt2 ) bonding. In bromobenzene solution, the Mg-alkene complexes are either dissociated or in a dissociation equilibrium. A DFT study and AIM analysis showed that the C=C bonds hardly change on coordination and there is very little alkene→Mg electron transfer. The Mg-alkene bonds are mainly electrostatic and should be described as Mg2+ ion-induced dipole interactions.

Large decanuclear calcium and strontium hydride clusters.

Two large decanuclear hydride clusters of the general formula Ae10H16[N(R)R']4·(PMDTA)2 (Ae = Ca, Sr) were isolated. Both derivatives feature a [Ae10H16]4+ core, consisting of two edge shared metal octahedra with interstitial hydrides, while the other hydrides cap triangular faces.

Early Main Group Metal Catalysts for Imine Hydrosilylation.

The efficient catalytic reduction of imines with phenylsilane is achieved by using the potassium, calcium and strontium based catalysts [(DMAT)K (THF)]∞ , (DMAT)2 Ca⋅(THF)2 and (DMAT)2 Sr⋅(THF)2 (DMAT=2-dimethylamino-α-trimethylsilylbenzyl). Eight different aldimines and the ketimine Ph2 C=NPh could be successfully reduced by PhSiH3 at temperatures between 25-60 °C with catalyst loadings down to 2.5 mol %. Also, simple amides like KN(SiMe3 )2 or Ae[N(SiMe3 )2 ]2 (Ae=Ca, Sr, Ba) catalyze this reaction. Activities increase with metal size. For most substrates the activity increases along the row K

Calcium-Catalyzed Arene C-H Bond Activation by Low-Valent AlI.

The low-valent ß-diketiminate complex (DIPP BDI)Al is stable in benzene but addition of catalytic quantities of [(DIPP BDI)CaH]2 at 20 °C led to (DIPP BDI)Al(Ph)H (DIPP BDI=CH[C(CH3 )N-DIPP]2 , DIPP=2,6-diisopropylphenyl). Similar Ca-catalyzed C-H bond activation is demonstrated for toluene or p-xylene. For toluene a remarkable selectivity for meta-functionalization has been observed. Reaction of (DIPP BDI)Al(m-tolyl)H with I2 gave m-tolyl iodide, H2 and (DIPP BDI)AlI2 which was recycled to (DIPP BDI)Al. Attempts to catalyze this reaction with Mg or Zn hydride catalysts failed. Instead, the highly stable complexes (DIPP BDI)Al(H)M(DIPP BDI) (M=Mg, Zn) were formed. DFT calculations on the Ca hydride catalyzed arene alumination suggest that a similar but more loosely bound complex is formed: (DIPP BDI)Al(H)Ca(DIPP BDI). This is in equilibrium with the hydride bridged complex (DIPP BDI)Al(µ-H)Ca(DIPP BDI) which shows strongly increased electron density at Al. The combination of Ca-arene bonding and a highly nucleophilic Al center are key to facile C-H bond activation.

Magnesium Cyanide or Isocyanide?

Preference for the binding mode of the CN- ligand to Mg (Mg-CN vs. Mg-NC) is investigated. A monomeric Mg complex with a terminal CN ligand was prepared using the dipyrromethene ligand Mes DPM which successfully blocks dimerization. While reaction of (Mes DPM)MgN(SiMe3 )2 with Me3 SiCN gave the coordination complex (Mes DPM)MgN(SiMe3 )2 ⋅NCSiMe3 , reaction with (Mes DPM)Mg(nBu) led to (Mes DPM)MgNC⋅(THF)2 . A Mg-NC/Mg-CN ratio of ≈95:5 was established by crystal-structure determination and DFT calculations. IR studies show absorbances for CN stretching at 2085 cm-1 (Mg-NC) and 2162 cm-1 (Mg-CN) as confirmed by 13 C labeling. In solution and in the solid state, the CN ligand rotates within the pocket. The calculated isomerization barrier is only 12.0 kcal mol-1 and the 13 C NMR signal for CN decoalesces at -85 °C (Mg-NC: 175.9 ppm, Mg-CN: 144.3 ppm). Experiment and theory both indicate that Mg complexes with the CN- ligand should not be named cyanides but are more properly defined as isocyanides.

Lewis acidic alkaline earth metal complexes with a perfluorinated diphenylamide ligand.

Alkaline earth metal (Ae) chemistry with the anion [N(C6F5)2]- has been explored. Deprotonation of the amine (C6F5)2NH, abbreviated in here as NFH, with 0.5 equivalent of AeN''2 (N'' = N(SiMe3)2) is fast and gave, dependent on the solvent, the complexes AeNF2, AeNF2·(THF)2 and AeNF2·(Et2O)2 (Ae = Mg, Ca, Sr). Using a 1/1 ratio, mixed amide complexes were obtained: NFAeN'' (Ae = Mg, Ca, Sr). Crystal structures of the monomers AeNF2·(THF)2 (Ae = Mg, Ca, Sr) and AeNF2·(Et2O)2 (Ae = Mg, Ca) are presented and compared with those of AeN''2·(THF)2. In addition, crystal structures of the homoleptic dimer (MgNF2)2 and the heteroleptic dimers (NFAeN'')2 (Ae = Mg, Ca, Sr) are discussed. All structures are strongly influenced by very short AeF contacts down to circa 2.11 Å (Mg), 2.50 Å (Ca) and 2.73 Å (Sr). AIM analysis illustrates that, although AeF contacts are short, there is no bond-critical-point along this axis, indicating an essentially electrostatic interaction. The monomeric complexes feature strong C6F5C6F5π-stacking, resulting in unusually acute NF-Ae-NF angles as small as 95°. Heteroleptic (NFAeN'')2 complexes retain their dimeric structure in C6D6 solution and there is no indication of ligand scrambling by the Schlenk equilibrium, suggesting that an electron withdrawing ligand may stabilize heteroleptic complexes. According to DFT calculations, the heteroleptic arrangement is 70 kJ mol-1 more stable than the homoleptic dimers. The Lewis acidity of MgNF2 has been quantified with the Gutmann-Beckett method and by calculation of the Fluoride-Ion-Affinity. The latter calculations show that the Lewis acidity of MgNF2 and CaNF2 is comparable to that of B(C6F5)3. Dimeric (MgNF2)2 fully abstracts Et3PO from Et3PO·B(C6F5)3 and may have potential in Lewis acid catalysis.

Nucleophilic Aromatic Substitution at Benzene with Powerful Strontium Hydride and Alkyl Complexes.

Key to the isolation of the first alkyl strontium complex was the synthesis of a strontium hydride complex that is stable towards ligand exchange reactions. This goal was achieved by using the super bulky ß-diketiminate ligand DIPeP BDI (CH[C(Me)N-DIPeP]2 , DIPeP=2,6-diisopentylphenyl). Reaction of DIPeP BDI-H with Sr[N(SiMe3 )2 ]2 gave (DIPeP BDI)SrN(SiMe3 )2 , which was converted with PhSiH3 into [(DIPeP BDI)SrH]2 . Dissolved in C6 D6 , the strontium hydride complex is stable up to 70 °C. At 60 °C, H-D isotope exchange gave full conversion into [(DIPeP BDI)SrD]2 and C6 D5 H. Since H-D exchange with D2 is facile, the strontium hydride complex served as a catalyst for the deuteration of C6 H6 by D2 . Reaction of [(DIPeP BDI)SrH]2 with ethylene gave [(DIPeP BDI)SrEt]2 . The high reactivity of this alkyl strontium complex is demonstrated by facile ethylene polymerization and nucleophilic aromatic substitution with C6 D6 , giving alkylated aromatic products and [(DIPeP BDI)SrD]2 .

Low Valent Magnesium Chemistry with a Super Bulky ß-Diketiminate Ligand.

The steric bulk of the well-known DIPP BDI ligand (CH[C(CH3 )N-DIPP]2 , DIPP=2,6-diisopropylphenyl) was increased by replacing isopropyl for isopentyl groups. This very bulky DIPeP BDI ligand could not stabilize the radical species (DIPeP BDI)Mg. : reduction of (DIPeP BDI)MgI with Na gave (DIPeP BDI)2 Mg2 with a rather long Mg-Mg bond of 3.0513(8) Å. Addition of TMEDA prior to reduction gave complex (DIPeP BDI)2 Mg2 (C6 H6 ), which could also be obtained as its THF adduct. It is speculated that combination of a bulky spectator ligand and TMEDA prevents dimerization of the intermediate MgI radical, which then reacts with the benzene solvent. Complex (DIPeP BDI)2 Mg2 (C6 H6 ), which formally contains the anti-aromatic anion C6 H6 2- , reacted with tBuOH as a Brønsted base to 1,3- and 1,4-cyclohexadiene and with H2 as a two electron donor to (DIPeP BDI)2 Mg2 H2 and C6 H6 . It also reductively cleaved the C-F bond in fluorobenzene and gave (DIPeP BDI)MgPh, (DIPeP BDI)MgF, and C6 H6 .

Bulky cationic ß-diketiminate magnesium complexes.

Cationic ß-diketiminate Mg complexes with the bulky tBuBDI ligand and the weakly coordinating anion B(C6F5)4- have been prepared by the reaction of (tBuBDI)MgnBu with [Ph3C]+[B(C6F5)4]-; tBuBDI = CH[C(tBu)N-Dipp]2 and Dipp = 2,6-diisopropylphenyl. Their structures are compared to the previously reported cationic (MeBDI)Mg+ complexes; MeBDI = CH[C(Me)N-Dipp]2. Crystallization of [(tBuBDI)Mg]+[B(C6F5)4]- from chlorobenzene gave a unique (tBuBDI)Mg+·ClC6H5 cation with a rather short MgCl and consequently long C-Cl bond. Crystallization from chlorobenzene/arene solvent mixtures gave (tBuBDI)Mg+·arene complexes (arene = benzene, toluene, m-xylene) but in the presence of mesitylene the chlorobenzene complex was formed. Due to the greater shielding of the metal, none of these complexes display Mg(F5C6)4B- interactions. Crystal structures of the arene complexes show in all cases η2-coordination of the arene ligands. Ring slippage from a more favorable η2-coordination can be explained by the steric bulk of the tBuBDI ligand. The smaller arenes, benzene and toluene, also bind to (tBuBDI)Mg+ in bromobenzene solution. The Lewis acidity of these cationic Mg complexes was determined by the Gutmann-Beckett test. The acceptor number for (tBuBDI)Mg+ (AN = 76.0) is substantially higher than that estimated for (MeBDI)Mg+ (AN = 70.3). Calculation of the atomic NPA charges by DFT shows that the Mg2+ ion in (tBuBDI)Mg+ is slightly more positively charged than the metal in (MeBDI)Mg+, confirming its higher Lewis acidity. The lower benzene complexation energy calculated for (tBuBDI)Mg+versus (MeBDI)Mg+ is due to steric congestion of the metal in the (tBuBDI)Mg+ cation which allows only for Mg(η1)C6H6 instead of Mg(η6)C6H6 bonding. This ring slippage, however, results in a significant polarization of the electron density in the benzene ring, making it susceptible for nucleophilic attack.

Simple Alkaline-Earth Metal Catalysts for Effective Alkene Hydrogenation.

Alkaline earth metal amides (AeN''2 : Ae=Ca, Sr, Ba, N''=N(SiMe3 )2 ) catalyze alkene hydrogenation (80-120 °C, 1-6 bar H2 , 1-10 mol % cat.), with the activity increasing with metal size. Various activated C=C bonds (styrene, p-MeO-styrene, α-Me-styrene, Ph2 C=CH2 , trans-stilbene, cyclohexadiene, 1-Ph-cyclohexene), semi-activated C=C bonds (Me3 SiCH=CH2 , norbornadiene), or non-activated (isolated) C=C bonds (norbornene, 4-vinylcyclohexene, 1-hexene) could be reduced. The results show that neutral Ca or Ba catalysts are active in the challenging hydrogenation of isolated double bonds. For activated alkenes (e.g. styrene), polymerization is fully suppressed due to fast protonation of the highly reactive benzyl intermediate by N''H (formed in the catalyst initiation). Using cyclohexadiene as the H source, the first Ae metal catalyzed H-transfer hydrogenation is reported. DFT calculations on styrene hydrogenation using CaN''2 show that styrene oligomerization competes with styrene hydrogenation. Calculations also show that protonation of the benzylcalcium intermediate with N''H is a low-energy escape route, thus avoiding oligomerization.

Facile Benzene Reduction by a Ca2+ /AlI Lewis Acid/Base Combination.

Attempted synthesis of the donor-acceptor complex (BDI)Ca+ ←AlI (BDI) complex by reaction of (BDI)Ca+ in the form of its B(C6 F5 )4 - salt with (BDI)AlI in benzene led to dearomatization of the solvent and formation of (BDI)Ca+ (C6 H6 )AlIII (BDI) (BDI=CH[C(CH3 )N-Dipp]2 , Dipp=2,6-diisopropylphenyl). The C6 H6 2- anion is strongly puckered and its boat form features four long (ca. 1.50 Å) and two short (ca. 1.34 Å) C-C bond distances. The flagpole positions of the C6 H6 2- anion chelate an AlIII cation giving a norbornadiene-like fragment with Al in the 7-position. The C=C double bonds of this alumina-norbornadiene strongly coordinate to the Ca2+ metal ion. The complex is stable in solution up to 80 °C. Several mechanisms for its formation are discussed including a highly likely frustrated Lewis pair type mechanism in which benzene is activated by the Lewis acid (BDI)Ca+ followed by nucleophilic attack by the Lewis base (BDI)AlI .

Highly Lewis acidic cationic alkaline earth metal complexes.

Cationic Lewis base-free ß-diketiminate (BDI) complexes of Mg and Ca have been isolated as their B(C6F5)4- salts. The cation (BDI)Mg+ shows an extraordinarily strong Lewis acidity that can compete with strong Lewis acids like B(C6F5)3 and (BDI)AlMe+. Its highly electrophilic nature is exemplified by isolation of an 3-hexyne adduct.

Unsupported metal silyl ether coordination.

Simple silyl ethers like O(SiMe3)2 in contrast to normal ethers are inert to metal bonding; however, a "naked", highly Lewis-acidic, cationic Mg species enforces complexation. DFT calculations indicate that agostic interactions and van der Waals attraction significantly contribute to the stability of this first example of unsupported metal silyl ether coordination.

LiAlH4 : From Stoichiometric Reduction to Imine Hydrogenation Catalysis.

Imine-to-amine conversion with catalytic instead of stoichiometric quantities of LiAlH4 is demonstrated (85 °C, catalyst loading≥2.5 mol %, pressure≥1 bar). The effects of temperature, pressure, solvent, and catalyst modifications, as well as the substrate scope are discussed. Experimental investigations and preliminary DFT calculations suggest that the catalytically active species is generated in situ: LiAlH4 +Ph(H)C=NtBu→LiAlH2 [N(tBu)CH2 Ph]2 . A cooperative mechanism in which Li and Al both play a prominent role is proposed.

Simple Access to the Heaviest Alkaline Earth Metal Hydride: A Strongly Reducing Hydrocarbon-Soluble Barium Hydride Cluster.

Reaction of Ba[N(SiMe3 )2 ]2 with PhSiH3 in toluene gave simple access to the unique Ba hydride cluster Ba7 H7 [N(SiMe3 )2 ]7 that can be described as a square pyramid spanned by five Ba2+ ions with two flanking BaH[N(SiMe3 )2 ] units. This heptanuclear cluster is well soluble in aromatic solvents, and the hydride 1 H NMR signals and coupling pattern suggests that the structure is stable in solution. At 95 °C, no coalescence of hydride signals is observed but the cluster slowly decomposes to undefined barium hydride species. The complex Ba7 H7 [N(SiMe3 )2 ]7 is a very strong reducing agent that already at room temperature reacts with Me3 SiCH=CH2 , norbornadiene, and ethylene. The highly reactive alkyl barium intermediates cannot be observed and deprotonate the (Me3 Si)2 N- ion, as confirmed by the crystal structure of Ba14 H12 [N(SiMe3 )2 ]12 [(Me3 Si)(Me2 SiCH2 )N]4 .

Calcium stilbene complexes: structures and dual reactivity.

Addition of a calcium hydride complex to diphenylacetylene gave a complex in which the stilbene dianion symmetrically bridges two Ca2+ ions. DFT calculations discuss the effect of the metal stilbene coordination. The stilbene complex reacts as a base (with H2) or an electron donor (with I2) and catalyzes the reduction of diphenylacetylene.