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

A seven-membered N,N'-heterocyclic potassium alumanyl nucleophile is introduced and utilised in the metathetical synthesis of Mg-Al Ca-Al bonded derivatives. Both species have been characterised by experimental theoretical means, allowing a rationalisation greater reactivity heavier group 2 implied an initial assay their reactivity.Al‐Ca‐Wrap: Die Reaktion eines siebengliedrigen cyclischen Alumanyl‐Anions mit einem β‐Diketiminato‐Calciumtetraphenylborat bietet einen leichten Zugang zu...

Abstract Copper‐alumanyl complexes, [LCu‐Al(SiN Dipp )], where L=carbene=NHC iPr (N,N′‐diisopropyl‐4,5‐dimethyl‐2‐ylidene) and Me2 CAAC (1‐(2,6‐diisopropylphenyl)‐3,3,5,5‐tetramethyl‐pyrrolidin‐2‐ylidene) featuring unsupported Al−Cu bonds, have been prepared. Divergent reactivity observed with carbodiimides CO 2 implies an ambiphilicity in the Cu–Al interaction that is dependent on identity of carbene co‐ligand.

Density functional theory was used to investigate the protodeauration of organogold compounds, a process which is thought be final step in gold-catalyzed nucleophilic addition activated π bonds wherein proton added and gold catalyst regenerated. In this context, we have studied two important factors control effectiveness transformation. We find that nature alkenyl group PMe3Au(alkenyl) affects reaction barrier through strength Au–C bond; stronger bond, higher activation energy. This, turn,...

Reaction of [Ru(IPr)2(CO)H]BAr(F)4 with ZnEt2 forms the heterobimetallic species [Ru(IPr)2(CO)ZnEt]BAr(F)4 (2), which features an unsupported Ru-Zn bond. 2 reacts H2 to give [Ru(IPr)2(CO)(η(2)-H2)(H)2ZnEt]BAr(F)4 (3) and [Ru(IPr)2(CO)(H)2ZnEt]BAr(F)4 (4). DFT calculations indicate that activation at proceeds via oxidative cleavage Ru concomitant hydride transfer Zn. can also activate hydridic E-H bonds (E = B, Si), computed mechanisms for facile H/H exchange processes observed in 3 4 are presented.

[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 ethenetetrathiolate complex, )(S2 C)}]2 [3]2 . The dimeric alumoxane )(O)}]2 carbon monoxide oxygen analogue of 3, )(O2 [4]2 containing hitherto unknown ethenetetraolate ligand, [C2 O4 ]4-

Reaction of [Ru(PPh3)3HCl] with LiCH2TMS, MgMe2, and ZnMe2 proceeds chloride abstraction alkane elimination to form the bis-cyclometalated derivatives [Ru(PPh3)(C6H4PPh2)2H][M'] where [M'] = [Li(THF)2]+ (1), [MgMe(THF)2]+ (3), [ZnMe]+ (4), respectively. In presence 12-crown-4, reaction LiCH2TMS yields [Ru(PPh3)(C6H4PPh2)2H][Li(12-crown-4)2] (2). These four complexes demonstrate increasing interaction between M' hydride ligand in [Ru(PPh3)(C6H4PPh2)2H]- anion following trend 2 (no...

The seven-membered cyclic potassium alumanyl species, [{SiNMes }AlK]2 }={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 direct reduction of the iodide precursor, }AlI], or in stepwise manner via intermediate dialumane, }Al]2 . Although dialumane not observed Dipp-substituted analogue (Dipp=2,6-i-Pr2 H3 ), partial oxidation [{SiNDipp , where {SiNDipp N(Dipp)}2 provided extremely encumbered reacts...

Abstract The synthesis of the Cu‐borate complexes [(6Mes)Cu(HBR 3 )] featuring unusual [HBEt ] − ( 5 ) and [HB(C 6 F ligands is described. Experimental computational studies show both compounds feature a direct Cu–H interaction, but that while two‐coordinate, displays an additional, stabilizing Cu–C ipso (C interaction.

Density functional theory has been used to investigate the reactions of 1,5 enynes with alcohols in presence a gold catalyst. We have compared mechanism alcohol addition reaction for enyne that where carbon at position 3 is replaced silicon. find different intermediates are present both cases, and case silicon analogue, intermediate we from calculations any previously proposed literature. For analogue able rationalize observed effects concentration nucleophilicity on product distribution....

CuI(NHC)Br complexes (NHC = N-heterocyclic carbene) undergo a direct reaction with iodobenzene to give 2-arylated benzimidazolium products. The nature of the N-substituent on NHC ligand influences reactivity complex toward arylation. N-Benzyl or N-phenyl substituents facilitate arylation, whereas N-mesityl hinder Density functional theory calculations show that an oxidative addition/reductive elimination pathway involving CuIII species is energetically feasible. A less hindered N-benzyl...

Reaction of a magnesium diboranate complex with triphenylphosphine oxide provides terminal boryl, which is itself potent reagent for the deoxygenative reduction Ph3PO. Computational analysis density functional theory (DFT) indicates that B-B bond activation results from initial coordination P[double bond, length as m-dash]O phosphine to magnesium.

The addition of PPh2 H, PPhMeH, PPhH2 , P(para-Tol)H2 PMesH2 and PH3 to the two-coordinate Ni0 N-heterocyclic carbene species [Ni(NHC)2 ] (NHC=IiPr2 IMe4 IEt2 Me2 ) affords a series mononuclear, terminal phosphido nickel complexes. Structural characterisation nine these compounds shows that they have unusual trans [H-Ni-PR2 or novel [R2 P-Ni-PR2 geometries. bis-phosphido complexes are more accessible when smaller NHCs (IMe4 >IEt2 >IiPr2 phosphines employed. P-P activation diphosphines R2...

Reaction of Al–E (E = S, Se) multiple bonds with CO functionalities generates new C–E bonds.

Two equivalents of CO₂ react with a terminal Al–Te bond to form the tellurodicarbonate ligand.

DFT calculations have been carried out in order to rationalize and predict the ring-opening regioselectivity of substituted cyclopropenes presence gold(I) catalysts. It has shown that these processes is driven by relative π-donor ability substituents on cyclopropene double bond (C1 C2). A stronger substituent at C2 favors Au(I)-induced polarization toward C1, resulting preferential breaking C1-C3 bond. An excellent correlation between ΔE(++) difference C1-C2 p(π) orbital population was...

Abstract [K{Al(NON Dipp )}] 2 (NON =[O(SiMe NDipp) ] 2− , Dipp=2,6‐ i Pr C 6 H 3 ) reacts with CS to afford the trithiocarbonate species [K(OEt )][Al(NON )(CS )] 1 or ethenetetrathiolate complex, )(S C)}] [ . The dimeric alumoxane )(O)}] carbon monoxide oxygen analogue of )(O 4 containing hitherto unknown ethenetetraolate ligand, [C O 4−

We report the convergent reaction pathways between [RhH(PPh3)4] and POP ketone (1) alcohol (2) ligands that terminate in formation of an α-hydroxylalkyl rhodium(I) complex (3), representing two halves a formal reduction/oxidation pathway 1 2. In case hydride transfer to 1, (3) proceeds via rare hydrido(η2-carbonyl) (4). C–H activation 2 at proligand's central methine position, rather than O–H hydroxy motif, followed by loss dihydrogen also generates (3). The validity postulated is probed...

Abstract The hydride complex [Ru(IPr) 2 (CO)H][BAr F 4 ], 1 , reacts with InMe 3 loss of CH to form (CO)(InMe)(Me)][BAr featuring an unsupported Ru−In bond unsaturated Ru and In centres. H give (CO)(η ‐H )(InMe)(H)][BAr 5 while CO induces formation the indyl (CO) (InMe )][BAr 7 . These observations highlight ability Me shuttle between centres are supported by DFT calculations on mechanism its reactions CO. An analysis Ru‐In bonding in these species is also presented. Reaction GaMe involves...

Abstract Copper‐alumanyl complexes, [LCu‐Al(SiN Dipp )], where L=carbene=NHC iPr (N,N′‐diisopropyl‐4,5‐dimethyl‐2‐ylidene) and Me2 CAAC (1‐(2,6‐diisopropylphenyl)‐3,3,5,5‐tetramethyl‐pyrrolidin‐2‐ylidene) featuring unsupported Al−Cu bonds, have been prepared. Divergent reactivity observed with carbodiimides CO 2 implies an ambiphilicity in the Cu–Al interaction that is dependent on identity of carbene co‐ligand.

Reaction of the dimeric calcium hydride, [(BDI)CaH]2 (1), with Ph3SnH ensues elimination H2 to provide [(BDI)Ca-μ2-H-(SnPh3)Ca(BDI)] (3) and [(BDI)Ca(SnPh3)]2 (4) alongside dismutation Ph4Sn, Sn(0). DFT analysis indicates that stannyl anion formation occurs through deprotonation retention dinuclear species throughout reactions.

A combined experimental and computational study of the structure reactivity two [RuZn

Reactions of B(C6F5)3 with the β-diketiminato (BDI) alkaline-earth phosphidoborane complexes, 1a [(BDI)Ca(H3B·PPh2)] and 1b [(BDI)Mg(H3B·PPh2)]2 (BDI = [HC{C(CH3)N(2,6-iPr-C6H3)}2]-) result in formation phosphinodiboronate complexes 4a [(BDI)Ca(η6-toluene){H3B·PPh2·B(C6F5)3}] 4b [(BDI)Mg{H3B·PPh2·B(C6F5)3}]. Calcium complex is stable aromatic solvents at room temperature does not display well-defined onward reactivity elevated temperatures. Magnesium undergoes a transformation to provide...

The synthesis of the Cu-borate complexes [(6Mes)Cu(HBR3)] featuring unusual [HBEt3]− (5) and [HB(C6F5)3]− (6) ligands is described. Experimental computational studies show both compounds feature a direct Cu–H interaction, but that while 5 two-coordinate, 6 displays an additional, stabilizing Cu–Cipso(C6F5) interaction.

We have investigated computationally the gold and palladium cocatalyzed reaction of alkynes with vinylstannane. Our work has involved a careful thorough exploration different mechanistic possibilities. find that acting alone as catalyst leads to very high barrier, consistent experimental observation there is no in presence just palladium. However, involvement gold(I) complex lowers barrier considerably, vinylstannylation can proceed modest activation energy about 10 kcal/mol. key finding...