19F NMR Investigations of the Reaction of B(C6F5)3 with Different Tri(alkyl)aluminum Compounds

Tris(pentafluorophenyl)borane, B(C₆F₅)₃ reacts with triethylaluminum, AlEt₃ to a mixture of Al(C₆F₅)_3−nEt_n and Al₂(C₆F₅)_6−nEt_n compounds depending on the B/Al ratio. From excess borane to excess AlEt₃ the species Al(C₆F₅)₃ → Al(C₆F₅)₂Et Al₂(C₆F₅)₄Et₂ → Al₂(C₆F₅)₃Et₃ → Al₂(C₆F₅)₂Et₄ → Al₂(C₆F₅)Et₅ are formed and differentiated by their para-F signal in ¹⁹F NMR. The reaction between B(C₆F₅)₃ and the higher aluminum alkyls, tri(iso-butyl)aluminum and tri(n-hexyl)aluminum AlR₃ (R = i-Bu, n-C₆H₁₃) is slower and requires AlR₃ excess to shift the C₆F₅ R exchange equilibria to almost complete formation of Al(C₆F₅)R₂ and BR₃. At equimolar ratio the equilibrium lies on the side of the unchanged borane together with its boranate [B(C₆F₅)₃R]⁻ anion. For tri(n-octyl)aluminum even at large Al(n-C₈H₁₇)₃ excess no C₆F₅ alkyl exchange can be observed, but boranate anions form.     

Planar N‐Heterocyclic Carbene Diarylborenium Ions: Synthesis by Cationic Borylation and Reactivity with Lewis Bases

The NHC–borane adduct (IBn)BH₃ ( 1 ) (NHC= N‐heterocyclic carbene; IBn=1,3‐dibenzylimidazol‐2ylidene) reacts with [Ph₃C][B(C₆F₅)₄] through sequential hydride abstraction and dehydrogenative cationic borylation(s) to give singly or doubly ring closed NHC–borenium salts 2 and 3 . The planar doubly ring closed product [C₃H₂(NCH₂C₆H₄)₂B][B(C₆F₅)₄] is resistant to quaternization at boron by Et₂O coordination, but forms classical Lewis acid–base adducts with the stronger donors Ph₃P, Et₃PO, or 1,4‐diazabicyclo[2.2.2]octane (DABCO). Treatment of 3 with tBu₃P selectively yields the unusual oligomeric borenium salt trans‐[(C₃H₂(NCH₂C₆H₄)₂B)₂(C₃H₂(NCHC₆H₄)₂B)][B(C₆F₅)₄] ( 7 ).     

Nickel(II) and palladium(II) complexes with α‐dioxime ligands as catalysts for the vinyl polymerization of norbornene in combination with methylaluminoxane,tris(pentafluorophenyl)borane,or triethylaluminum cocatalyst systems

Nickel(II) and palladium(II) complexes with α‐dioxime ligands dimethylglyoxime, diphenylglyoxime, and 1,2‐cyclohexanedionedioxime represent six new precatalysts for the polymerization of norbornene that can be activated with methylaluminoxane (MAO), the organo‐Lewis acid tris(pentafluorophenyl)borane [B(C₆F₅)₃], and triethylaluminum (TEA) AlEt₃. The palladium but not the nickel precatalysts could also be activated by B(C₆F₅)₃ alone, whereas two of the three nickel precatalysts but none of the palladium systems are somewhat active with only TEA as a cocatalyst. It was possible to achieve very high polymerization activities up to 3.2 · 10⁷ g_polymer/mol_metal · h. With the system B(C₆F₅)₃/AlEt₃, the activation process can be formulated as the following two‐step reaction: (1) B(C₆F₅)₃ and TEA lead to an aryl/alkyl group exchange and result in the formation of Al(C₆F₅)_nEt_3?n and B(C₆F₅)_3?nEt_n; and (2) Al(C₆F₅)_nEt_3?n will then react with the precatalysts to form the active species for the polymerization of norbornene. Variation of the B:Al ratio shows that Al(C₆F₅)Et₂ is sufficient for high activation. Gel permeation chromatography indicated that it was possible to control the molar mass of poly(norbornene)s by TEA or 1‐dodecene as chain‐transfer agents; the molar mass can be varied in the number‐average molecular weight range from 2 · 10³ to 9 · 10⁵ g · mol^?1. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3604–3614, 2002     

Fine‐Tuning of Lewis Acidity: The Case of Borenium Hydride Complexes Derived from Bis(phosphinimino)amide Boron Precursors

Reactions of bis(phosphinimino)amines LH and L′H with Me₂S ? BH₂Cl afforded chloroborane complexes LBHCl ( 1 ) and L′BHCl ( 2 ), and the reaction of L′H with BH₃ ? Me₂S gave a dihydridoborane complex L′BH₂ ( 3 ) (LH=[{(2,4,6‐Me₃C₆H₂N)P(Ph₂)}₂N]H and L′H=[{(2,6‐iPr₂C₆H₃N)P(Ph₂)}₂N]H). Furthermore, abstraction of a hydride ion from L′BH₂ ( 3 ) and LBH₂ ( 4 ) mediated by Lewis acid B(C₆F₅)₃ or the weakly coordinating ion pair [Ph₃C][B(C₆F₅)₄] smoothly yielded a series of borenium hydride cations: [L′BH]⁺[HB(C₆F₅)₃]^? ( 5 ), [L′BH]⁺[B(C₆F₅)₄]^? ( 6 ), [LBH]⁺[HB(C₆F₅)₃]^? ( 7 ), and [LBH]⁺[B(C₆F₅)₄]^? ( 8 ). Synthesis of a chloroborenium species [LBCl]⁺[BCl₄]^? ( 9 ) without involvement of a weakly coordinating anion was also demonstrated from a reaction of LBH₂ ( 4 ) with three equivalents of BCl₃. It is clear from this study that the sterically bulky strong donor bis(phosphinimino)amide ligand plays a crucial role in facilitating the synthesis and stabilization of these three‐coordinated cationic species of boron. Therefore, the present synthetic approach is not dependent on the requirement of weakly coordinating anions; even simple BCl₄^? can act as a counteranion with borenium cations. The high Lewis acidity of the boron atom in complex 8 enables the formation of an adduct with 4‐dimethylaminopyridine (DMAP), [LBH ? (DMAP)]⁺[B(C₆F₅)₄]^? ( 10 ). The solid‐state structures of complexes 1 , 5 , and 9 were investigated by means of single‐crystal X‐ray structural analysis.     

Lewis Acid Coordination Redirects S-Nitrosothiol Signaling Output

S-Nitrosothiols (RSNOs) serve as air-stable reservoirs for nitric oxide in biology. While copper enzymes promote NO release from RSNOs by serving as Lewis acids for intramolecular electron-transfer, redox-innocent Lewis acids separate these two functions to reveal the effect of coordination on structure and reactivity. The synthetic Lewis acid B(C₆F₅)₃ coordinates to the RSNO oxygen atom, leading to profound changes in the RSNO electronic structure and reactivity. Although RSNOs possess relatively negative reduction potentials, B(C₆F₅)₃ coordination increases their reduction potential by over 1 V into the physiologically accessible +0.1 V vs. NHE. Outer-sphere chemical reduction gives the Lewis acid stabilized hyponitrite dianion trans-[LA-O-N=N-O-LA]²⁻ [LA=B(C₆F₅)₃], which releases N₂O upon acidification. Mechanistic and computational studies support initial reduction to the [RSNO-B(C₆F₅)₃] radical anion, which is susceptible to N−N coupling prior to loss of RSSR.     

Lewis Acid Coordination Redirects S‐Nitrosothiol Signaling Output

S‐Nitrosothiols (RSNOs) serve as air‐stable reservoirs for nitric oxide in biology. While copper enzymes promote NO release from RSNOs by serving as Lewis acids for intramolecular electron‐transfer, redox‐innocent Lewis acids separate these two functions to reveal the effect of coordination on structure and reactivity. The synthetic Lewis acid B(C₆F₅)₃ coordinates to the RSNO oxygen atom, leading to profound changes in the RSNO electronic structure and reactivity. Although RSNOs possess relatively negative reduction potentials, B(C₆F₅)₃ coordination increases their reduction potential by over 1 V into the physiologically accessible +0.1 V vs. NHE. Outer‐sphere chemical reduction gives the Lewis acid stabilized hyponitrite dianion trans‐[LA‐O‐N=N‐O‐LA]^2? [LA=B(C₆F₅)₃], which releases N₂O upon acidification. Mechanistic and computational studies support initial reduction to the [RSNO‐B(C₆F₅)₃] radical anion, which is susceptible to N?N coupling prior to loss of RSSR.     

Triethylantimony(V) complexes with bidentate O,N-, O,O- and tridentate O,N,O′-coordinating o-iminoquinonato/o-quinonato ligands: Synthesis, structure and some properties

The novel triethylantimony(v) o-amidophenolato (AP-R)SbEt₃ (R = i-Pr, 1; R = Me, 2) and catecholato (3,6-DBCat)SbEt₃ (3) complexes have been synthesized and characterized by IR, NMR spectroscopy (AP-R is 4,6-di-tert-butyl-N-(2,6-dialkylphenyl)-o-amidophenolate, alkyl = isopropyl (1) or methyl (2); 3,6-DBCat is 3,6-di-tert-butyl-catecholate). Complexes 1–3 have been obtained by the oxidative addition of corresponding o-iminobenzoquinones or o-benzoquinones to Et₃Sb. The addition of 4,6-di-tert-butyl-N-(3,5-di-tert-butyl-2-hydroxyphenyl)-o-iminobenzoquinone to Et₃Sb at low temperature gives hexacoordinate [(AP-AP)H]SbEt₃ (4) which decomposes slowly in vacuum with the liberation of ethane yielding pentacoordinate complex [(AP-AP)]SbEt₂ (5). [(AP-AP)H]²⁻ is O,N,O′-tridentate amino-bis-(3,5-di-tert-butyl-phenolate-2-yl) dianion and [(AP-AP)]³⁻ is amido-bis-(3,5-di-tert-butyl-phenolate-2-yl) trianion. The decomposition of 4–5 accelerates in the presence of air. o-Amidophenolates 1 and 2 bind molecular oxygen to give spiroendoperoxides Et₃Sb[L-iPr]O₂ (6) or Et₃Sb[L-Me]O₂ (7) containing trioxastibolane rings. This reaction proceeds slowly and reaches the equilibrium at 15–20% conversion five times more than for (AP-R)SbPh₃ analogues. Molecular structures of 1 and 5 were determined by X-ray analysis.     

Catalytic Hydrosilylation of Imines by Aluminum Hydride Cations

In this work, the catalytic activity of electronically unsaturated three coordinated aluminum hydride cations [ L AlH]⁺[HB(C₆F₅)₃]⁻ ( 1 ) and [ L AlH]⁺[B(C₆F₅)₄]⁻ ( 2 ) in hydrosilylation of imines has been disclosed ( L ={(2,6-ⁱPr₂C₆H₃N)P(Ph₂)}₂N). A variety of organo-silanes such as Et₃SiH, MePhSiH₂, PhSiH₃, TMDSO, and PHMS are screened in this endeavour. The amines as products of catalysis were obtained in good to excellent yields after the hydrolysis of silylamine intermediates. Further, a series of controlled experiments systematically designed to investigate the underlying mechanistic pathway through multinuclear NMR analysis showed Lewis adduct formation between cationic aluminum centre and the imine nitrogen, which subsequently undergoes reaction with silane to afford the product. The hydrosilylation of imine performed with Et₃SiH using catalyst 1 with a loading of 2 mol % at 60 °C occurs smoothly. Whereas 2 led to the product formation with Et₃SiH only when used in stoichiometric quantity. Further, to investigate this unique behaviour of 1 NMR investigations were performed and revealed that the anion in 1 competes for hydride delivery and in-situ generates B(C₆F₅)₃ that cooperatively reinforces the catalytic activity of 1 .     

Reactivity of an Intramolecular Fluorophosphonium Fluoroborate

The reactions of the intramolecular frustrated Lewis pair‐adduct Ph₂PC(p‐Tol)?C(C₆F₅)B(C₆F₅)₂(CNtBu) with XeF₂ gave Ph₂P(F)C(p‐Tol)?C(C₆F₅)B(F)(C₆F₅)₂ ( 3 ). This species reacts with two equivalents of Al(C₆F₅)₃?C₇H₈ producing the salt, [Ph₂P(F)C(p‐Tol)?C(C₆F₅)B(C₆F₅)₂][F(Al(C₆F₅)₃)₂] ( 4 ), whereas reaction with HSiEt₃/B(C₆F₅)₃ gave Ph₂P(F)C(p‐Tol)?C(H)B(C₆F₅)₃ ( 5 ). The photolysis of 3 resulted in aromatization affording the phenanthralene derivative Ph₂P(F)C(p‐Tol(o‐C₆F₄))?CB(F)(C₆F₅)₂ ( 6 ).     

[Re{NB(C6F5)3}(Et2dtc)2]2 – Dimerisierung infolge der Ausbildung einer Nitridobrücke

[Re{NB(C₆F₅)₃}(Et₂dtc)₂]₂ – Dimerization as a Consequence of the Formation of a Nitrido Bridge The title compound is formed from [ReN(Et₂dtc)₂] with five‐coordinate Re atom upon reaction with B(C₆F₅)₃. As a consequence of the formation of a nitrido bridge between Re and B the structural trans influence of the nitrido ligand decreases and its trans position which is not occupied in the edduct becomes available for co‐ordination. The dimer is built up by two [Re{NB(C₆F₅)₃}(Et₂dtc)₂] units which are linked by weak bonds between the metal and each one sulphur atom of the neighbouring unit (Re–S: 2.856(6) and 2.835(6) Å, respectively).     

One- and Two-Electron Transfer Oxidation of 1,4-Disilabenzene with Formation of Stable Radical Cations and Dications

Electron-transferable oxidants such as B(C₆F₅)₃/nBuLi, B(C₆F₅)₃/LiB(C₆F₅)₄, B(C₆F₅)₃/LiHBEt₃, Al(C₆F₅)₃/(o-RC₆H₄)AlH₂ (R=N(CMe₂CH₂)₂CH₂), B(C₆F₅)₃/AlEt₃, Al(C₆F₅)₃, Al(C₆F₅)₃/nBuLi, Al(C₆F₅)₃/AlMe₃, (CuC₆F₅)₄, and Ag₂SO₄, respectively were employed for reactions with (L)₂Si₂C₄(SiMe₃)₂(C₂SiMe₃)₂ (L=PhC(NtBu)₂, 1 ). The stable radical cation [ 1 ]^+. was formed and paired with the anions [nBuB(C₆F₅)₃]⁻ (in 2 ), [B(C₆F₅)₄]⁻ (in 3 ), [HB(C₆F₅)₃]⁻ (in 4 ), [EtB(C₆F₅)₃]⁻ (in 5 ), {[(C₆F₅)₃Al]₂(μ-F)]⁻ (in 6 ), [nBuAl(C₆F₅)₃]⁻ (in 7 ), and [Cu(C₆F₅)₂]⁻ (in 8 ), respectively. The stable dication [ 1 ]²⁺ was also generated with the anions [EtB(C₆F₅)₃]⁻ ( 9 ) and [MeAl(C₆F₅)₃]⁻ ( 10 ), respectively. In addition, the neutral compound [(L)₂Si₂C₄(SiMe₃)₂(C₂SiMe₃)₂][μ-O₂S(O)₂] ( 11 ) was obtained. Compounds 2 – 11 are characterized by UV-vis absorption spectroscopy, X-ray crystallography, and elemental analysis. Compounds 2 – 8 are analyzed by EPR spectroscopy and compounds 9 – 11 by NMR spectroscopy. The structure features are discussed on the central Si₂C₄-rings of 1 , [ 1 ]^+., [ 1 ]²⁺, and 11 , respectively.     

Linkage Isomerism Leading to Contrasting Carboboration Chemistry: Access to Three Constitutional Isomers of a Borylated Phosphaalkene

We describe the reactivity of two linkage isomers of a boryl-phosphaethynolate, [B]OCP and [B]PCO (where [B]=N,N’-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaboryl), towards tris- (pentafluorophenyl)borane (BCF). These reactions afforded three constitutional isomers all of which contain a phosphaalkene core. [B]OCP reacts with BCF through a 1,2 carboboration reaction to afford a novel phosphaalkene, E-[B]O{(C₆F₅)₂B}C=P(C₆F₅), which subsequently undergoes a rearrangement process involving migration of both the boryloxy and pentafluorophenyl substituents to afford Z-{(C₆F₅)₂B}(C₆F₅)C=PO[B]. By contrast, [B]PCO undergoes a 1,3-carboboration process accompanied by migration of the N,N’-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaboryl to the carbon centre.     

Titanium(IV) Cations with Trigonal Monopyramidal Geometry: Unusual Lewis Acids Supported by a Triaryl Triamidoamine Ligand

Protonolysis of the titanium alkyl complex [Ti(CH₂SiMe₃)(Xy-N₃N)] (Xy-N₃N=[{(3,5-Me₂C₆H₃)NCH₂CH₂}₃N]³⁻) supported by a triamidoamine ligand, with [NEt₃H][B(3,5-Cl₂C₆H₃)₄] or [PhNMe₂H][B(C₆F₅)₄] afforded the cations [Ti(Xy-N₃N)][A] (A⁻=[B(3,5-Cl₂C₆H₃)₄]⁻ ( 1[B(Ar^Cl)₄] ; B(Ar^Cl)₄=tetrakis(3,5-dichlorophenyl)borate); A⁻=[B(C₆F₅)₄]⁻ ( 1[B(Ar^F)₄] ; B(Ar^F)₄=tetrakis[3,5-bis(trifluoromethyl)phenyl]borate). These Lewis acidic cations were reacted with coordinating solvents to afford the cations [Ti(L)(Xy-N₃N)][B(C₆F₅)₄] ( 2-L ; L=Et₂O, pyridine and THF). XRD analysis revealed a trigonal monopyramidal (TMP) geometry for the tetracoordinate cations in 1[B(Ar^X)₄] and trigonal bipyramidal (TBP) geometry for the pentacoordinate cations in 2-L . Variable-temperature NMR spectroscopy showed a dynamic equilibrium for 2-Et₂O in solution, involving the dissociation of Et₂O. Coordination to the titanium(IV) center activated the THF molecule, which, in the presence of NEt₃, underwent ring-opening to give the titanium alkoxide [Ti(O(CH₂)₄NEt₃)(Xy-N₃N)][B(3,5-Cl₂C₆H₃)₄] ( 3 ). Hydride abstraction from C_β,eq of the triamidoamine ligand arm in [Ti(CH₂SiMe₃)(Xy-N₃N)] or [Ti(NMe₂)(Xy-N₃N)] with [Ph₃C][B(3,5-Cl₂C₆H₃)₄] led to the diamidoamine–imine complex [Ti(R){(Xy-N=CHCH₂)(Xy-NCH₂CH₂)₂N}][B(3,5-Cl₂C₆H₃)₄] (R=CH₂SiMe₃ ( 4 a ); R=NMe₂ ( 4 b )). Hydride addition to 4 b with [Li(THF)][HBPh₃] gave [Ti(NMe₂)(Xy-N₃N)], whereas KH deprotonated further to give [Ti(NMe₂){(Xy-NCH=CH)(Xy-NCH₂CH₂)₂N}] ( 5 ). XRD on single crystals of 3 and 4 b confirmed the proposed structures.     

Facile access to the pnictocenium ions [Cp*ECl]+ (E = P, As) and [(Cp*)2P]+: chloride ion affinity of Al(OR(F))3

The pnictocenium salts [Cp*PCl]⁺[μCl]^? ( 1 a ), [Cp*PCl]⁺[ClAl(OR^F)₃]^? ( 1 b ), [Cp*AsCl]⁺[ClAl(OR^F)₃]^? ( 2 ), and [(Cp*)₂P]⁺[μCl]^? ( 3 ), in which Cp*=Me₅C₅, μCl=(^FRO)₃Al? Cl? Al(OR^F)₃, and OR^F=OC(CF₃)₃, were prepared by halide abstraction from the respective halopnictines with the Lewis superacid PhF→Al(OR^F)₃. 1 The X‐ray crystal structures of 1 a , 2 , and 3 established that in the half as well as in the sandwich cations the Cp* rings are attached in an η²‐fashion. By using one or two equivalents of the Lewis acid, the two new weakly coordinating anions [μCl]^? and [ClAl(OR^F)₃]^? resulted. They also stabilize the highly reactive cations in PhF or 1,2‐F₂C₆H₄ solution at room temperature. The chloride ion affinities (CIAs) of a range of classical strong Lewis acids were also investigated. The calculations are based on a set of isodesmic BP86/SV(P) reactions and a non‐isodesmic reference reaction assessed at the G3MP2 level.     

Polymerization of acrylonitrile by catalytic systems consisting of triphenylphosphine and a lewis acid

Polymerization of acrylonitrile in the presence of systems that consisted of triphenylphosphine (PPh₃) and a Lewis acid R_mMX_n (ZnCl₂, Me₃Al, Et₃Al, Et₂AlCl, EtAlCl₂, AlCl₃) was studied. The systems that contained Me₃Al and Et₃Al (i.e., Lewis acid of moderate acidity) were the most efficient catalysts. Conductometric measurements carried out in the polymerization systems showed the presence of ions. The presence of phosphonium cation in the polyacrylonitrile chain formed by the PPh₃–R_mMX_n catalytic systems was determined by IR, ¹H-NMR, and ³¹P-NMR spectroscopy. The average molecular weight measurements and kinetic chain lengths of polyacrylonitrile formed within the reaction time in the presence of PPh₃–Et₃Al showed that transfer reactions occur. According to the results obtained, the polymerization reaction of acrylonitrile by PPh₃–R_mMX_n involved a zwitterion formed by the attack of PPh₃ on acrylonitrile complexed by Lewis acid [Ph₃P^⊕? CH₂? C^?H? C?N → MR_mX_n] and the anion [CH₂?C^?? C?N] formed by the proton abstraction from the monomer.     

Group 6 Transition‐Metal/Boron Frustrated Lewis Pair Templates Activate N2 and Allow its Facile Borylation and Silylation

The reaction of trans ‐[M(N₂)₂(dppe)₂] (M=Mo, 1_Mo , M=W, 1_W ) with B(C₆F₅)₃ ( 2 ) provides the adducts [(dppe)₂M=N=N‐B(C₆F₅)₃] ( 3 ) which can be regarded as M/B transition‐metal frustrated Lewis pair (TMFLP) templates activating dinitrogen. Easy borylation and silylation of the activated dinitrogen ligands in complexes 3 with a hydroborane and hydrosilane occur by splitting of the B−H and Si−H bonds between the N₂ moiety and the perfluoroaryl borane. This reactivity of 3 is reminiscent of conventional frustrated Lewis pair chemistry and constitutes an unprecedented approach for the functionalization of dinitrogen.     

Inherent Stability Limits of Intramolecular Boron Nitrogen Lewis Acid–Base Pairs

The reaction of (C₆F₅)₂BH ( 1 ) with N,N‐dimethylallylamine ( 2 ), N,N‐diethylallylamine ( 3 ) and 1‐allylpiperidine ( 4 ) afforded the five‐membered ring systems (C₆F₅)₂B(CH₂)₃NR₂ (R=Me ( 5 ), Et ( 6 )) and (C₆F₅)₂B(CH₂)₃N(CH₂)₅ ( 7 ) with an intramolecular dative B? N bond. A different product was obtained from the reaction of (C₆F₅)₂BH ( 1 ) with N,N‐diisopropylallylamine ( 8 ), which afforded the seven‐membered ring system (C₆F₅)₂B(CH₂)₃N(iPr)CH(Me)CH₂ ( 9 ) under extrusion of dihydrogen. All compounds were characterised by elemental analysis, NMR spectroscopy and single‐crystal X‐ray diffraction experiments. Density functional theory (DFT) studies were performed to rationalise the different reaction mechanism for the formation of products 6 and 9 . The bonding situation of compound 9 was analysed in terms of its electron density topology to describe the delocalised nature of a borane– enamine adduct.     

Molybdenum(VI) Bis(imido) Complexes: From Frustrated Lewis Pairs to Weakly Coordinating Cations

Molybdenum(VI) bis(imido) complexes [Mo(NtBu)₂(L^R)₂] (R=H 1 a ; R=CF₃ 1 b ) combined with B(C₆F₅)₃ ( 1 a /B(C₆F₅)₃, 1 b /B(C₆F₅)₃) exhibit a frustrated Lewis pair (FLP) character that can heterolytically split H−H, Si−H and O−H bonds. Cleavage of H₂ and Et₃SiH affords ion pairs [Mo(NtBu)(NHtBu)(L^R)₂][HB(C₆F₅)₃] (R=H 2 a ; R=CF₃ 2 b ) composed of a Mo(VI) amido imido cation and a hydridoborate anion, while reaction with H₂O leads to [Mo(NtBu)(NHtBu)(L^R)₂][(HO)B(C₆F₅)₃] (R=H 3 a ; R=CF₃ 3 b ). Ion pairs 2 a and 2 b are catalysts for the hydrosilylation of aldehydes with triethylsilane, with 2 b being more active than 2 a . Mechanistic elucidation revealed insertion of the aldehyde into the B−H bond of [HB(C₆F₅)₃]⁻. We were able to isolate and fully characterize, including by single-crystal X-ray diffraction analysis, the inserted products Mo(NtBu)(NHtBu)(L^R)₂][{PhCH₂O}B(C₆F₅)₃] (R=H 4 a ; R=CF₃ 4 b ). Catalysis occurs at [HB(C₆F₅)₃]⁻ while [Mo(NtBu)(NHtBu)(L^R)₂]⁺ (R=H or CF₃) act as the cationic counterions. However, the striking difference in reactivity gives ample evidence that molybdenum cations behave as weakly coordinating cations (WCC).     

Complexation and Versatile Reactivity of a Highly Lewis Acidic Cationic Mg Complex with Alkynes and Phosphines

[(BDI)Mg⁺][B(C₆F₅)₄⁻] ( 1 ; BDI=CH[C(CH₃)NDipp]₂; Dipp=2,6-diisopropylphenyl) was prepared by reaction of (BDI)MgnPr with [Ph₃C⁺][B(C₆F₅)₄⁻]. Addition of 3-hexyne gave [(BDI)Mg⁺ ⋅ (EtC≡CEt)][B(C₆F₅)₄⁻]. Single-crystal X-ray analysis, NMR investigations, Raman spectra, and DFT calculations indicate a significant Mg-alkyne interaction. Addition of the terminal alkynes PhC≡CH or Me₃SiC≡CH led to alkyne deprotonation by the BDI ligand to give [(BDI-H)Mg⁺(C≡CPh)]₂ ⋅ 2 [B(C₆F₅)₄⁻] ( 2 , 70 %) and [(BDI-H)Mg⁺(C≡CSiMe₃)]₂ ⋅ 2 [B(C₆F₅)₄⁻] ( 3 , 63 %). Addition of internal alkynes PhC≡CPh or PhC≡CMe led to [4+2] cycloadditions with the BDI ligand to give {Mg⁺C(Ph)=C(Ph)C[C(Me)=NDipp]₂}₂ ⋅ 2 [B(C₆F₅)₄⁻] ( 4 , 53 %) and {Mg⁺C(Ph)=C(Me)C[C(Me)=NDipp]₂}₂ ⋅ 2 [B(C₆F₅)₄⁻] ( 5 , 73 %), in which the Mg center is N,N,C-chelated. The (BDI)Mg⁺ cation can be viewed as an intramolecular frustrated Lewis pair (FLP) with a Lewis acidic site (Mg) and a Lewis (or Brønsted) basic site (BDI). Reaction of [(BDI)Mg⁺][B(C₆F₅)₄⁻] ( 1 ) with a range of phosphines varying in bulk and donor strength generated [(BDI)Mg⁺ ⋅ PPh₃][B(C₆F₅)₄⁻] ( 6 ), [(BDI)Mg⁺ ⋅ PCy₃][B(C₆F₅)₄⁻] ( 7 ), and [(BDI)Mg⁺ ⋅ PtBu₃][B(C₆F₅)₄⁻] ( 8 ). The bulkier phosphine PMes₃ (Mes=mesityl) did not show any interaction. Combinations of [(BDI)Mg⁺][B(C₆F₅)₄⁻] and phosphines did not result in addition to the triple bond in 3-hexyne, but during the screening process it was discovered that the cationic magnesium complex catalyzes the hydrophosphination of PhC≡CH with HPPh₂, for which an FLP-type mechanism is tentatively proposed.