Impact of the Methylene Bridge Substitution in Chelating NHC-Phosphine Mn(I) Catalyst for Ketone Hydrogenation.

Systematic modification of the chelating NHC-phosphine ligand (NHC = N-heterocyclic carbene) in highly efficient ketone hydrogenation Mn(I) catalyst fac-[(Ph2PCH2NHC)Mn(CO)3Br] has been performed and the catalytic activity of the resulting complexes was evaluated using acetophenone as a benchmark substrate. While the variation of phosphine and NHC moieties led to inferior results than for a parent system, the incorporation of a phenyl substituent into the ligand methylene bridge improved catalytic performance by ca. 3 times providing maximal TON values in the range of 15000-20000. Mechanistic investigation combining experimental and computational studies allowed to rationalize this beneficial effect as an enhanced stabilization of reaction intermediates including anionic hydride species fac-[(Ph2PC(Ph)NHC)Mn(CO)3H]- playing a crucial role in the hydrogenation process. These results highlight the interest of such carbon bridge substitution strategy being rarely employed in the design of chemically non-innocent ligands.

Carbon-Phosphorus Ligands with Extreme Donating Character.

Carbeniophosphines [R2 C+ -PR2 ] and phosphonium ylides [R3 P+ -CR2 - ] are two complementary classes of carbon-phosphorus based ligands defined by their unique donor properties. Indeed, while carbeniophosphines are electron-poor P-ligands due to the positioning of a positive charge near the coordinating P-atom, phosphonium ylides are electron-rich C-ligands due to the presence of a negatively charged coordinating C-atom. Based on this knowledge, this account summarizes our recent contribution on these two classes of carbon-phosphorus ligands, and in particular the strategies developed to lower the donor character of carbeniophosphines and enhance that of phosphonium ylides. This led us to design, at both extremities of the donating scale, extremely electron-poor P-ligands exemplified by imidazoliophosphonites [R2 C+ -P(OR)2 ] and dicarbeniophosphines [(R2 C+ )2 -PR], and extremely electron-rich C-ligands illustrated by pincer architectures exhibiting several phosphonium ylide donor extremities. In the context of carbon-phosphorus analogy, the closely related cases of ligands where the C-atom of a NHC ligand is in close proximity of two positive charges, and that of a phosphonium ylide coordinated through its P-atom are also discussed. An overview of the synthetic methods, coordinating properties, general reactivity and electronic structure of all these C,P-based species is presented here.

Phosphonium Ylides vs Iminophosphoranes: The Role of the Coordinating Ylidic Atom in cis-[Phosphine-Ylide Rh(CO)2] Complexes.

The coordinating properties of two families of ylides, namely, phosphonium ylides and iminophosphoranes, differently substituted at the ylidic center (CH2- vs NiPr-), have been investigated in structurally related cationic phosphine-ylide Rh(CO)2 complexes obtained from readily available phosphine-phosphonium salt precursors derived from an ortho-phenylene bridge. However, while the Rh(CO)2 complex bearing the P+-CH2- donor moiety proved to be stable, the P═NiPr donor end appeared to induce lability to one of the CO groups. All of the RhI carbonyl complexes in both ylide series were fully characterized, including through X-ray diffraction analysis. Based on the experimental and calculated infrared (IR) CO stretching frequencies in Rh(CO)2 complexes, we evidenced that the phosphonium ylide ligand is a stronger donor than the iminophosphorane ligand. However, we also found that the difference in the intrinsic electronic properties can be largely compensated by the introduction of an iPr substituent on the N atom of the iminophosphorane, hence pointing to the noninnocent role of the peripheral substituent and opening novel possibilities to tune the properties of metal complexes containing ylide ligands.

Phosphine-NHC-Phosphonium Ylide Pincer Ligand: Complexation with Pd(II) and Unconventional P-Coordination of the Ylide Moiety.

An efficient synthesis of two pincer preligands [Ph2PCH(R)ImCH2CH2CH2PPh3]X2 (R = H, X = OTf; R = Ph, X = BF4) was developed. Subsequent reactions with PdCl2 and an excess of Cs2CO3 led to the formation of highly stable cationic ortho-metalated Pd(II) complexes [(P,C,C,C)Pd]X exhibiting phosphine, NHC, phosphonium ylide, and σ-aryl donor extremities. The protonation of one of the latter complexes with R = H affords the Pd(II) complex [(P,C,C)Pd(MeCN)](OTf)2 bearing an unprecedented nonsymmetrical NHC core pincer scaffold with a 5,6-chelating framework. The overall donor properties of this phosphine-NHC-phosphonium ylide ligand were estimated using the experimental νCN stretching frequency in the corresponding [(P,C,C)Pd(CNtBu](OTf)2 derivative and were shown to be competitive with the related bis(NHC)-phosphonium ylide and phenoxy-NHC-phosphonium ylide pincers. The presence of a phenyl substituent in the bridge between phosphine and NHC moieties in the ortho-metalated complex [(P,C,C,C)Pd](BF4) makes possible the deprotonation of this position using LDA to provide a persistent zwitterionic complex [(P,C,C,C)Pd] featuring a rare P-coordinated phosphonium ylide moiety in addition to a conventional C-coordinated one. The comparison of the 31P and 13C NMR data for these C- and P-bound phosphonium ylide fragments within the same molecule was performed for the first time, and the bonding situation in both cases was studied in detail by QTAIM and ELF topological analyses.

The Dichotomy of Mn-H Bond Cleavage and Kinetic Hydricity of Tricarbonyl Manganese Hydride Complexes.

Acid-base characteristics (acidity, pKa, and hydricity, ΔG°H- or kH-) of metal hydride complexes could be a helpful value for forecasting their activity in various catalytic reactions. Polarity of the M-H bond may change radically at the stage of formation of a non-covalent adduct with an acidic/basic partner. This stage is responsible for subsequent hydrogen ion (hydride or proton) transfer. Here, the reaction of tricarbonyl manganese hydrides mer,trans-[L2Mn(CO)3H] (1; L = P(OPh)3, 2; L = PPh3) and fac-[(L-L')Mn(CO)3H] (3, L-L' = Ph2PCH2PPh2 (dppm); 4, L-L' = Ph2PCH2-NHC) with organic bases and Lewis acid (B(C6F5)3) was explored by spectroscopic (IR, NMR) methods to find the conditions for the Mn-H bond repolarization. Complex 1, bearing phosphite ligands, features acidic properties (pKa 21.3) but can serve also as a hydride donor (ΔG≠298K = 19.8 kcal/mol). Complex 3 with pronounced hydride character can be deprotonated with KHMDS at the CH2-bridge position in THF and at the Mn-H position in MeCN. The kinetic hydricity of manganese complexes 1-4 increases in the order mer,trans-[(P(OPh)3)2Mn(CO)3H] (1) < mer,trans-[(PPh3)2Mn(CO)3H] (2) ≈ fac-[(dppm)Mn(CO)3H] (3) < fac-[(Ph2PCH2NHC)Mn(CO)3H] (4), corresponding to the gain of the phosphorus ligand electron-donor properties.

Direct Access to Palladium(II) Complexes Based on Anionic C,C,C-Phosphonium Ylide Core Pincer Ligand.

The reaction of readily available imidazolium-phosphonium salt [MesIm(CH2)3PPh3](OTf)2 with PdCl2 in the presence of an excess of Cs2CO3 afforded selectively in one step the cationic Pd(II) complex [(C,C,C)Pd(NCMe)](OTf) exhibiting an LX2-type NHC-ylide-aryl C,C,C-pincer ligand via formal triple C-H bond activation. The replacement of labile MeCN in the latter by CNtBu and CO fragments allowed to estimate the overall electronic properties of this phosphonium ylide core pincer scaffold incorporating three different carbon-based donor ends by IR spectroscopy, cyclic voltammetry, and molecular orbital analysis, revealing its significantly higher electron-rich character compared to the structurally close NHC core pincer system with two phosphonium ylide extremities. The pincer complex [(C,C,C)Pd(CO)](OTf) represents a rare example of Pd(II) carbonyl species stable at room temperature and characterized by X-ray diffraction analysis. The treatment of isostructural cationic complexes [(C,C,C)Pd(NCMe)](OTf) and [(C,C,C)Pd(CO)](OTf) with (allyl)MgBr and nBuLi led to the formation of zwitterionic phosphonium organopalladates [(C,C,C)PdBr] and [(C,C,C)Pd(COnBu)], respectively.

Experimental and Theoretical Insights into the Electronic Properties of Anionic N-Heterocyclic Dicarbenes through the Rational Synthesis of Their Transition Metal Complexes.

The lithiation of the NHC ligand backbone in Cp(CO)2Mn(IMes) followed by transmetalation on the C4 carbenic position with Cp(CO)2FeI led to the heterobimetallic complex Cp(CO)2Mn(µ-dIMes)Fe(CO)2Cp bearing the anionic ditopic imidazol-2,4-diylidene dIMes ligand. Subsequent treatment of the later with TfOH induced a selective decoordination of the [Cp(CO)2Mn] fragment to form the cationic abnormal NHC complex [Cp(CO)2Fe(aIMes)](OTf), which was further derivatized to the bis(iron) dIMes complex [Cp(CO)2Fe(µ-dIMes)Fe(CO)2Cp](OTf) by reaction with tAmOK and Cp(CO)2FeI. The effect of the metalation at the C4 or C2 position on the imidazole ring on the electronic donation properties of the associated C2 and C4 carbenic centers in the dIMes ligand was quantified through systematic experimental and theoretical studies of IMes, aIMes, and dIMes complexes. The evaluation of the catalytic activity of the series of cationic Fe(II) complexes based on IMes, aIMes, and dIMes ligands in a benchmark ketone hydrosilylation showed the superiority of the bimetallic derivative.

Carbon Ligands: From Fundamental Aspects to Applications.

Ligand design is at the forefront of many advances in various areas of chemistry such as organometallic chemistry, functional materials, and homogeneous catalysis [...].

Hydrosilylation Reactions Catalyzed by Rhenium.

Hydrosilylation is an important process, not only in the silicon industry to produce silicon polymers, but also in fine chemistry. In this review, the development of rhenium-based catalysts for the hydrosilylation of unsaturated bonds in carbonyl-, cyano-, nitro-, carboxylic acid derivatives and alkenes is summarized. Mechanisms of rhenium-catalyzed hydrosilylation are discussed.

NHC Core Phosphonium Ylide-based Palladium(II) Pincer Complexes: The Second Ylide Extremity Makes the Difference.

The coordinating properties of N-heterocyclic carbene (NHC) (A), phenolate (B), and phosphonium ylide (C) moieties were investigated systematically through the preparation of a family of NHC, phosphonium ylide-based pincer ligands, where the third donor extremity can be either an NHC, a phenolate, or a phosphonium ylide. The overall donor character of such ligands [NHC(AaBbCc)] (a + b + c = 2) was analyzed by comparison of the molecular orbitals (energy and shape), oxidation potentials (Epox), and IR νCO and νCN stretching frequencies of their isostructural pincer Pd(II) complexes [NHC(AaBbCc)PdL][OTf] (L = NCCH3, CO, or CNtBu). The three categories of pincer complexes based on phosphonium ylides were easily obtained by acidic treatment of their highly stable ortho-metalated Pd(II) precursors prepared in a single step from readily available N-phosphonio-substituted imidazolium salts. Analysis of IR data indicated that NHC and phenolate ligands have a similar donor character but which remains lower than that of the phosphonium ylide. The impact on catalytic performance of the incorporation of a second strongly donating phosphonium ylide into the ligand architecture was illustrated in the Pd-catalyzed allylation of aldehydes.

NHC Core Pincer Ligands Exhibiting Two Anionic Coordinating Extremities.

The chemistry of NHCcore pincer ligands of LX2 type bearing two pending arms, identical or not, whose coordinating center is anionic in nature, is here reviewed. In this family, the negative charge of the coordinating atoms can be brought either by a carbon atom via a phosphonium ylide (R3P+-CR2-) or by a heteroatom through amide (R2N-), oxide (RO-), or thio(seleno)oxide (RS-, RSe-) donor functionalities. Through selected examples, the synthetic methods, coordination properties, and applications of such tridentate systems are described. Particular emphasis is placed on the role of the donor ends in the chemical behavior of these species.

C-O and C-N Functionalization of Cationic, NCN-Type Pincer Complexes of Trivalent Nickel: Mechanism, Selectivity, and Kinetic Isotope Effect.

This report presents the synthesis of new mono- and dicationic NCN-NiIII complexes and describes their reactivities with protic substrates. (NCN is the pincer-type ligand κ N, κ C, κ N-2,6-(CH2NMe2)2-C6H3.) Treating van Koten's trivalent complex (NCN)NiIIIBr2 with AgSbF6 in acetonitrile gives the dicationic complex [(NCN)NiIII(MeCN)3]2+, whereas the latter complex undergoes a ligand-exchange reaction with (NCN)NiIIIBr2 to furnish the related monocationic complex [(NCN)NiIII(Br)(MeCN)]+. These trivalent complexes have been characterized by X-ray diffraction analysis and EPR spectroscopy. Treating these trivalent complexes with methanol and methylamine led, respectively, to C-OCH3 or C-NH(CH3) functionalization of the Ni-aryl moiety in these complexes, C-heteroatom bond formation taking place at the ipso-C. These reactions also generate the cationic divalent complex [(NCN)NiII(NCMe)]+, which was prepared independently and characterized fully. The unanticipated formation of the latter divalent species suggested a comproportionation side reaction between the cationic trivalent precursors and a monovalent species generated at the C-O and C-N bond formation steps; this scenario was supported by direct reaction of the trivalent complexes with the monovalent compound (PPh3)3NiICl. Kinetic measurements and density functional theory analysis have been used to investigate the mechanism of these C-O and C-N functionalization reactions and to rationalize the observed inverse kinetic isotope effect in the reaction of [(NCN)NiIII(Br)(MeCN)]+ with CH3OH/CD3OD.

Phosphine-NHC Manganese Hydrogenation Catalyst Exhibiting a Non-Classical Metal-Ligand Cooperative H2 Activation Mode.

Deprotonation of the MnI NHC-phosphine complex fac-[MnBr(CO)3 (κ2 P,C-Ph2 PCH2 NHC)] (2) under a H2 atmosphere readily gives the hydride fac-[MnH(CO)3 (κ2 P,C-Ph2 PCH2 NHC)] (3) via the intermediacy of the highly reactive 18-e NHC-phosphinomethanide complex fac-[Mn(CO)3 (κ3 P,C,C-Ph2 PCHNHC)] (6 a). DFT calculations revealed that the preferred reaction mechanism involves the unsaturated 16-e mangana-substituted phosphonium ylide complex fac-[Mn(CO)3 (κ2 P,C-Ph2 P=CHNHC)] (6 b) as key intermediate able to activate H2 via a non-classical mode of metal-ligand cooperation implying a formal λ5 -P-λ3 -P phosphorus valence change. Complex 2 is shown to be one of the most efficient pre-catalysts for ketone hydrogenation in the MnI series reported to date (TON up to 6200).

Classification of the Electronic Properties of Chelating Ligands in cis-[LL'Rh(CO)2] Complexes.

By analogy to the Tolman electronic parameter, a ligand electronic parameter, referred to as L2EP, is introduced here for estimating the donating ability of chelating ligands, featuring two coordinating extremities. It is based on the average of the computed infrared stretching frequencies of CO in a series of isostructural rhodium(I)-dicarbonyl complexes, that is linearly correlated to the number x of N-heterocyclic carbene coordinating ends (x = 0, 1, or 2). The L2EP values allow the design of an unified scale for the classification of the electron donation of chelating ligands, based on an ortho-phenylene bridge substituted by two coordinating extremities, which may have a different donating character. Strengths and limitations of the L2EP scale are illustrated for a large diversity of bidentate chelating ligands with coordinating ends ranging from extremely electron-rich phosphonium yldiides to extremely electron-poor amidiniophosphonites.

Phosphenium Versus Pro-Phosphide Character of P-tert-butyl-dicyclopropeniophosphine: Zwitterionic Palladate Complexes of a Dicationic Phosphido Ligand.

With the view to enhancing the unique coordinating ability of the known phenyl-tetrakis(diisopropylamino)dicyclopropeniophosphine (Ph-DCP), replacement of the phenyl substituent by a tert-butyl substituent was envisaged. Both α-dicationic R-DCP phosphines, with R = Ph and tBu, were prepared in 54%-55% yield by substitution of RPCl2 with two equivalents of bis(diisopropylamino)-dicyclopropenylidene (BAC) and metathesis with NaBF4. This method is implicitly consistent with the representation of R-DCPs as BAC-phosphenium adducts. The R-DCP salts were found to coordinate hard and soft Lewis acids such as a promoted oxygen atom (in the singlet spin state) in the corresponding R-DCP oxides, and electron-rich transition-metal centers in η1-R-DCP complexes with AuCl, PtCl3-, or PdCl3-, respectively. Coordination of Ph-DCP with PdCl2, which is a more electron-deficient Pd(II) center, leads to pentachlorinated dinuclear complexes [(Ph-DCP)PdCl2]2Cl-, where the dicoordinate Cl- bridge screens the repelling pairs of positive charges from each other. The same behavior is inferred for the tBu-DCP ligand, from which addition of an excess of (MeCN)2PdCl2 was found to trigger a heterolytic cleavage of the DCP-tBu bond, releasing tBu+ and a dicationic phosphide, DCP-: the latter is evidenced as a ligand in a tetranuclear complex ion [(µ2-DCP-)Pd2Cl4]2, which, upon HCl treatment, dissociates to a doubly zwitterionic dipalladate complex. All the complexes were isolated in 82%-97% yield, and five of them were characterized by X-ray crystallography.

Charge Effects in PCP Pincer Complexes of Ni(II) bearing Phosphinite and Imidazol(i)ophosphine Coordinating Jaws: From Synthesis to Catalysis through Bonding Analysis.

This contribution reports on a new family of Ni(II) pincer complexes featuring phosphinite and functional imidazolyl arms. The proligands (R) PIMC(H) OP(R') react at room temperature with Ni(II) precursors to give the corresponding complexes [((R) PIMCOP(R') )NiBr], where (R) PIMCOP(R) =κ(P) ,κ(C) ,κ(P) -{2-(R'2 PO),6-(R2 PC3 H2 N2 )C6 H3 }, R=iPr, R'=iPr (3 b, 84 %) or Ph (3 c, 45 %). Selective N-methylation of the imidazole imine moiety in 3 b by MeOTf (OTf=OSO2 CF3 ) gave the corresponding imidazoliophosphine [((iPr) PIMIOCOP(iPr) )NiBr][OTf], 4 b, in 89 % yield ((iPr) PIMIOCOP(iPr) =κ(P) ,κ(C) ,κ(P) -{2-(iPr2 PO),6-(iPr2 PC4 H5 N2 )C6 H3 }). Treating 4 b with NaOEt led to the NHC derivative [(NHCCOP(iPr) )NiBr], 5 b, in 47 % yield (NHCCOP(iPr) =κ(P) ,κ(C) ,κ(C) -{2-(iPr2 PO),6-(C4 H5 N2 )C6 H3 )}). The bromo derivatives 3-5 were then treated with AgOTf in acetonitrile to give the corresponding cationic species [((R) PIMCOP(R) )Ni(MeCN)][OTf] [R=Ph, 6 a (89 %) or iPr, 6 b (90 %)], [((R) PIMIOCOP(R) )Ni(MeCN)][OTf]2 [R=Ph, 7 a (79 %) or iPr, 7 b (88 %)], and [(NHCCOP(R) )Ni(MeCN)][OTf] [R=Ph, 8 a (85 %) or iPr, 8 b (84 %)]. All new complexes have been characterized by NMR and IR spectroscopy, whereas 3 b, 3 c, 5 b, 6 b, and 8 a were also subjected to X-ray diffraction studies. The acetonitrile adducts 6-8 were further studied by using various theoretical analysis tools. In the presence of excess nitrile and amine, the cationic acetonitrile adducts 6-8 catalyze hydroamination of nitriles to give unsymmetrical amidines with catalytic turnover numbers of up to 95.

The missing entry in the agostic-anagostic series: Rh(I)-η(1)-C interactions in P(CH)P pincer complexes.

The missing entry, namely, the "C-anagostic" or η(1)-C interaction, closing the agostic-anagostic series of metal-CH(aryl) interactions is found in a bis(amidiniophosphine) P(CH)P pincer rhodium complex. The three entries, namely, agostic η(2)-(C,H), anagostic (related to hydrogen bonding, thus recoined here as "H-anagostic"), and C-anagostic interactions, are unambiguously characterized by electron localization function (ELF) topological analysis. Other theoretical tools such as noncovalent interaction (NCI) analysis and multicenter electron delocalization indices (MCIs) support the ELF characterization. A η(2)-(C,H) agostic interaction is evidenced by a disynaptic V(C,H) or trisynaptic V(M,C,H) ELF basin with a significant quantum topological atoms in molecules (QTAIM) atomic contribution of the metal M and a large covariance (in absolute value) with the metal core basin C(M). The C-anagostic η(1)-C interaction is characterized by a disynaptic V(M,C) basin, a weak covariance (in absolute value) of V(C,H) and C(M) populations, and a negligible QTAIM atomic contribution of M to V(C,H). The relevance of these ELF signatures is evidenced in a selected series of related rhodium and osmium complexes.

Comparative reactivity of different types of stable cyclic and acyclic mono- and diamino carbenes with simple organic substrates.

A series of stable carbenes, featuring a broad range of electronic properties, were reacted with simple organic substrates. The N,N-dimesityl imidazolylidene (NHC) does not react with isocyanides, whereas anti-Bredt di(amino)carbene (pyr-NHC), cyclic (alkyl)(amino)carbene (CAAC), acyclic di(amino)carbene (ADAC), and acyclic (alkyl)(amino)carbene (AAAC) give rise to the corresponding ketenimines. NHCs are known to promote the benzoin condensation, and we found that the CAAC, pyr-NHC, and ADAC react with benzaldehyde to give the ketone tautomer of the Breslow intermediate, whereas the AAAC first gives the corresponding epoxide and ultimately the Breslow intermediate, which can be isolated. Addition of excess benzaldehyde to the latter does not lead to benzoin but to a stable 1,3-dioxolane. Depending on the electronic properties of carbenes, different products are also obtained with methyl acrylate as a substrate. The critical role of the carbene electrophilicity on the outcome of reactions is discussed.

Counterion Effects in [Ru(bpy)3](X)2-Photocatalyzed Energy Transfer Reactions.

Photocatalysis that uses the energy of light to promote chemical transformations by exploiting the reactivity of excited-state molecules is at the heart of a virtuous dynamic within the chemical community. Visible-light metal-based photosensitizers are most prominent in organic synthesis, thanks to their versatile ligand structure tunability allowing to adjust photocatalytic properties toward specific applications. Nevertheless, a large majority of these photocatalysts are cationic species whose counterion effects remain underestimated and overlooked. In this report, we show that modification of the X counterions constitutive of [Ru(bpy)3](X)2 photocatalysts modulates their catalytic activities in intermolecular [2 + 2] cycloaddition reactions operating through triplet-triplet energy transfer (TTEnT). Particularly noteworthy is the dramatic impact observed in low-dielectric constant solvent over the excited-state quenching coefficient, which varies by two orders of magnitude depending on whether X is a large weakly bound (BArF 4 -) or a tightly bound (TsO-) anion. In addition, the counterion identity also greatly affects the photophysical properties of the cationic ruthenium complex, with [Ru(bpy)3](BArF 4)2 exhibiting the shortest 3MLCT excited-state lifetime, highest excited state energy, and highest photostability, enabling remarkably enhanced performance (up to >1000 TON at a low 500 ppm catalyst loading) in TTEnT photocatalysis. These findings supported by density functional theory-based calculations demonstrate that counterions have a critical role in modulating cationic transition metal-based photocatalyst potency, a parameter that should be taken into consideration also when developing energy transfer-triggered processes.

Two active species from a single metal halide precursor: a case study of highly productive Mn-catalyzed dehydrogenation of amine-boranes via intermolecular bimetallic cooperation.

Metal-metal cooperation for inert bond activation is a ubiquitous concept in coordination chemistry and catalysis. While the great majority of such transformations proceed via intramolecular mode in binuclear complexes, to date only a few examples of intermolecular small molecule activation using usually bimetallic frustrated Lewis pairs (Mδ+⋯M'δ-) have been reported. We introduce herein an alternative approach for the intermolecular bimetallic cooperativity observed in the catalytic dehydrogenation of amine-boranes, in which the concomitant activation of N-H and B-H bonds of the substrate via the synergetic action of Lewis acidic (M+) and basic hydride (M-H) metal species derived from the same mononuclear complex (M-Br). It was also demonstrated that this system generated in situ from the air-stable Mn(i) complex fac-[(CO)3(bis(NHC))MnBr] and NaBPh4 shows high activity for H2 production from several substrates (Me2NHBH3, tBuNH2BH3, MeNH2BH3, NH3BH3) at low catalyst loading (0.1% to 50 ppm), providing outstanding efficiency for Me2NHBH3 (TON up to 18 200) that is largely superior to all known 3d-, s-, p-, f-block metal derivatives and frustrated Lewis pairs (FLPs). These results represent a step forward towards more extensive use of intermolecular bimetallic cooperation concepts in modern homogeneous catalysis.