Boryl Complexes Research Articles

Reactivity of Diruthenium Bisborylene Complexes: Formation of B-C and B-H Bonds via Borylene Ligand Coupling.

Thermal or photoinduced isomerization of diruthenium bridging bisborylene complexes [{Cp*(H)2Ru}2(μ-BAr)2] (1a, Ar = Ph; 1b, Ar = 3,4,5-F3C6H2) led to nido-ruthenacarboranes 2a and 2b with newly formed B-C and B-H bonds. The reaction mechanism was analyzed by deuterium-labeling experiments and density functional theory calculations. Additionally, 2-fold B-H coupling between borylene and two hydrido ligands of 1a can be achieved, assisted by Lewis base IPr2Me2 to generate a dinuclear bridging borylene complex [(Cp*Ru)2(μ-H)2(μ-BPh)] (3). Our results provide new reactivity patterns for borylene-based functionalizations.

Copper Catalyzed Borylation of Alkynes: An Experimental Mechanistic Study.

The copper catalyzed hydroboration of alkynes with B2pin2 was studied by in detail studies of individual relevant steps along the catalytic pathway. A number of reaction steps were retraced by in situ NMR spectroscopy as well as central intermediates and side-products were isolated and comprehensively characterized. A copper boryl complex is central to the catalytic process by inserting the terminal alkyne substrate into the B-Cu bond. The selectivity of this step - depending on the NHC auxiliary ligand - determines the α/β selectivity observed in the product. The latter complex is protonated by the auxiliary alcohol reagent resulting in hydroboration product formation and formation of a Cu alkoxido complex. Reaction of the latter with B2pin2 results in the regeneration of the central copper boryl complex. This alcoholysis step depends on the acidity of the alcohol, in particular on the relative acidity of the alcohol vs. the alkyne substrate. A number of side reactions leading to the hydrogenation product of the alkyne substrate and a bis hydroborated product were identified and studied in some detail. It is concluded that the performance of a particular catalytic system depends crucially on the relative acidities of the reagents and generalizations may be difficult.

A-Frame-Templated High-Coordinate Platinum(IV) cis-Bis(boryl) Complexes.

The addition of Et2O·BF3 or Me2S·BCl3 to the BNBN-cumulene-bridged Pt(II) A-frame complexes [(μ-1,1-BNBN(TMS)2)(μ-dmpm)2Pt2X2] (TMS = SiMe3, dmpm = CH2(PMe2)2, X = Br 1Br, I 1I) resulted in the oxidative addition of one B-F or B-Cl bond, respectively, to the internal BN bond of the bridging, iminoborane-like B-N≡B-N moiety, and coordination of one Pt(II) center to the resulting adjacent BF2 (complex 2Br-F) or BCl2 (complexes 2Br-Cl and 2I-Cl) moiety, respectively. X-ray crystallographic and multinuclear NMR-spectroscopic data show that the Pt→BF2 interaction in 2Br-F is very weak and merely electrostatic, while the Pt→BCl2 interaction in 2Br-Cl and 2I-Cl is a stronger donor-acceptor bond. In contrast, the reaction of Me2S·BBr3 with 1Br yielded a ca. 3:2 mixture of the analogous B-Br addition product to the iminoborane, 2Br-Br, and the product of a subsequent oxidative addition of one B-Br bond of the chelating BBr2 moiety to the adjacent platinum center, the mixed-valence boranediyl-bridged, Pt(II)-Pt(IV)-bromoboryl complex 3-Br5. The analogous reactions of Me2S·BI3 with 1Br and Me2S·BBr3 with 1I yielded complex product mixtures of Pt(II)-Pt(II)-borane (2Br-I and 2I-Br, respectively) and Pt(II)-Pt(IV)-boryl complexes (3-BrnI5-n, n = 1-3) analogous to 2X-Y and 3-Br5, respectively, the proportion of the latter increasing with the proportion of iodide in the precursor mixture. Both multinuclear NMR-spectroscopic and X-ray crystallographic data show evidence of complex and extensive inter- and intramolecular bromide-iodide exchanges between the soft, iodide-affine platinum centers and the harder, more bromide-affine boron centers. A clue to the mechanism of these halide exchanges is provided by the reactions of BBr2Ar (Ar = 2,4,6-Me3C6H2 (Mes), 2,3,5,6-Me4C6H (Dur)) with 1Br, which yielded the cationic Pt(II)-Pt(II)-borenium analogues of 2Br-Br, the complexes 4Br-Ar, generated by the sterics-induced displacement of the bromide substituent from the chelating Pt→BBrAr moiety, and displaying a rare metal→borenium donor-acceptor bond.

Carbon dioxide capture and functionalization by bis(N-heterocyclic carbene)-borylene complexes

Derivatives of free monocoordinated borylenes have attracted considerable interest due to their ability to exhibit transition-metal-like reactivity, in particular small molecules capture. However, such complexes are rare as the formation is either endergonic, or the resulting adduct is a transient intermediate that is prone to reaction. Here, we present the synthesis of two bis(N-heterocyclic carbene)-borylene complexes capable of capturing and functionalizing carbon dioxide. The capture and subsequent functionalization of CO2 by the bis(NHC)-disilylamidoborylene 1 is demonstrated by the formation of the bis(NHC)-isocyanatoborylene-carbon dioxide complex 3. Reversible capture of CO2 is observed using the bis(NHC)-mesitylborylene 2, and the persistent bis(NHC)-mesitylborylene-carbon dioxide adduct 4 can be stabilized by hydrogen bonding with boric acid. The reactions of 4 with ammonia-borane and aniline demonstrate that the captured CO2 can be further functionalized.

Zinc borylation and reduction by a diborane(4) species via B-O bond formation.

We report a convenient synthesis of the zinc-boryl complex (NacnacMes)ZnBpin under mild conditions via formal disproportionation of bis(pinacolato)diboron(4), aided thermodynamically by B-O bond formation. This species can be isolated both base-free and as the DMAP adduct (NacnacMes)Zn(DMAP)Bpin and crystallographically characterised in the latter form. Onward reactivity of the base free zinc boryl complex with CO2 occurs reductively, yielding further B-O bonds as well as CO gas. The strength of this driving force can then be harnessed in the reaction between (NacnacMes)ZnBpin and a Zn-O bonded species (NacnacMes)ZnOB{(NDippCH)2}, which yields the metal-metal bonded dimer [(NacnacMes)Zn]2, the overall formation of which utilizes a diboron(4) species as the stoichiometric reductant of Zn(ii) to Zn(i).

Acyclic Boryl Complexes of Copper(I).

Reaction of (6-Dipp)CuOtBu (6-Dipp=C{NDippCH2 }2 CH2 , Dipp=2,6-iPr2 C6 H3 ) with B2 (OMe)4 provided access to (6-Dipp)CuB(OMe)2 via σ-bond metathesis. (6-Dipp)CuB(OMe)2 was characterised by NMR spectroscopy and X-ray crystallography and shown to be a monomeric acyclic boryl of copper. (6-Dipp)CuB(OMe)2 reacted with ethylene and diphenylacetylene to provide insertion compounds into the Cu-B bond which were characterised by NMR spectroscopy in both cases and X-ray crystallography in the latter. It was also competent in the rapid catalytic deoxygenation of CO2 in the presence of excess B2 (OMe)4 . Alongside π-insertion, (6-Dipp)CuB(OMe)2 reacted with LiNMe2 to provide a salt metathesis reaction at boron, giving (6-Dipp)CuB(OMe)NMe2 , a second monomeric acyclic boryl, which also cuproborated diphenylacetylene. Computational interrogation validated these acyclic boryl species to be electronically similar to (6-Dipp)CuBpin.

A tautomerized ligand enabled meta selective C–H borylation of phenol

Remote meta selective C–H functionalization of aromatic compounds remains a challenging problem in chemical synthesis. Here, we report an iridium catalyst bearing a bidentate pyridine-pyridone (PY-PYRI) ligand framework that efficiently catalyzes this meta selective borylation reaction. We demonstrate that the developed concept can be employed to introduce a boron functionality at the remote meta position of phenols, phenol containing bioactive and drug molecules, which was an extraordinary challenge. Moreover, we have demonstrated that the method can also be applied for the remote C6 borylation of indole derivatives including tryptophan that was the key synthetic precursor for the total synthesis of Verruculogen and Fumitremorgin A alkaloids. The inspiration of this catalytic concept was started from the O–Si secondary interaction, which by means of several more detailed control experiments and detailed computational investigations revealed that an unprecedented Bpin shift occurs during the transformation of iridium bis(boryl) complex to iridium tris(boryl) complex, which eventually control the remote meta selectivity by means of the dispersion between the designed ligand and steering silane group.

Aluminium and Gallium Silylimides as Nitride Sources.

Terminal aluminium and gallium imides of the type K[(NON)M(NR)], bearing heteroatom substituents at R, have been synthesised via reactions of anionic aluminium(I) and gallium(I) reagents with silyl and boryl azides (NON=4,5-bis(2,6-diisopropyl-anilido)-2,7-di-tert-butyl-9,9-dimethyl-xanthene). These systems vary significantly in their lability in solution: the N(Sii Pr3 ) and N(Boryl) complexes are very labile, on account of the high basicity at nitrogen. Phenylsilylimido derivatives provide greater stabilization through the π-acceptor capabilities of the SiR3 group. K[(NON)AlN(Sit BuPh2 )] offers a workable compromise between stability and solubility, and has been completely characterized by spectroscopic, analytical and crystallographic methods. The silylimide species examined feature minimal π-bonding between the imide ligand and aluminium/gallium, with the HOMO and HOMO-1 orbitals effectively comprising orthogonal lone pairs centred at N. Reactivity-wise, both aluminium and gallium silylimides can act as viable sources of nitride, [N]3- , with systems derived from either metal reacting with CO to afford cyanide complexes. By contrast, only the gallium system K[(NON)Ga{N(SiPh3 )}] is capable of effecting a similar transformation with N2 O to yield azide, N3 - , via formal oxide/nitride metathesis. The aluminium systems instead generate RN3 via transfer of the imide fragment [RN]2- .

The Complex Reactivity of [(salen)Fe]2(μ-O) with HBpin and Its Implications in Catalysis.

We report a detailed study into the method of precatalyst activation during alkyne cyclotrimerization. During these studies we have prepared a homologous series of Fe(III)-μ-oxo(salen) complexes and use a range of techniques including UV-vis, reaction monitoring studies, single crystal X-ray diffraction, NMR spectroscopy, and LIFDI mass spectrometry to provide experimental evidence for the nature of the on-cycle iron catalyst. These data infer the likelihood of ligand reduction, generating an iron(salan)-boryl complex as a key on-cycle intermediate. We use DFT studies to interrogate spin states, connecting this to experimentally identified diamagnetic and paramagnetic species. The extreme conformational flexibility of the salan system appears connected to challenges associated with crystallization of likely on-cycle species.

Pitfalls for POCOP-Type Palladium Pincer Complexes in Catalytic Reduction of CO2 with Catecholborane

Reduction of CO2 with catecholborane (HBcat) is known to be catalyzed by nickel hydride complexes supported by a bis(phosphinite)-based or POCOP-type pincer ligand. The objective of this research is to examine how changing the metal center from nickel to palladium would impact the outcome of CO2 reduction. Stoichiometric studies show that the palladium hydride complexes react rapidly with CO2, although the resulting palladium formate complexes can lose CO2 under reduced pressure or in chloroform. In the presence of HBcat, the formate complexes are converted back to the palladium hydride species while the formate group is reduced to CH3OBcat. This process is also accompanied by the formation of palladium bis(catecholato)borate complexes, which diverts some of the HBcat to yield B2(cat)3 and B2H6. For palladium hydrides stabilized by a POCOP-pincer ligand with relatively small phosphorus substituents (e.g., isopropyl or cyclopentyl groups), HBcat cleaves the P–O bonds in the ligand backbone to degrade the catalysts to secondary phosphine complexes. Without CO2, HBcat also undergoes H2 elimination with the Pd–H moiety to form palladium boryl complexes. These side reactions with HBcat and the palladium pincer complexes play profound roles in the catalytic reduction of CO2 with the borane.

Ring‐Expanded N‐Heterocyclic Copper(I) Boryl Complexes: The Structures of [(6‐Dipp)CuBcat], [(6‐Dipp)CuBneop], and [(6‐Dipp)CuBhex

Abstractσ‐Bond metathesis reactions between [(6‐Dipp)CuOtBu] (6‐Dipp=:C({Dipp}NCH2)2CH2, Dipp=2,6‐iPr2−C6H3) and three diboranes gave access to three new copper(I) boryl complexes [(6‐Dipp)CuBcat], [(6‐Dipp)CuBneop], and [(6‐Dipp)CuBhex] (cat=1,2‐O2C6H4; neop=(OCH2)2C(CH3)2; hex=OC(CH3)HCH2C(CH3)2O). Whilst [(6‐Dipp)CuBcat] and [(6‐Dipp)CuBneop] formed rapidly in toluene, access to [(6‐Dipp)CuBhex] required heating to 60 °C for days. The complexes were characterised by single‐crystal X‐ray crystallography which showed in all three cases that the systems were monomers and distorted‐linear at the copper atom. The stability of [(6‐Dipp)CuBneop] was found to be comparable to that of [(IPr*)Cu‐Bneop] (IPr*=1,3‐bis(2,6‐(diphenylmethyl)‐4‐methylphenyl)imidazol‐2‐ylidene); it persisted in solution for days with no sign of decomposition. [(6‐Dipp)CuBhex] is a rare crystallographically characterised example of a complex containing a boryl anion supported by the hexylene glycolato ligand.

Nickel boryl complexes and nickel-catalyzed alkyne borylation.

The first nickel bis-boryl complexes cis-[Ni( i Pr2ImMe)2(Bcat)2], cis-[Ni( i Pr2ImMe)2(Bpin)2] and cis-[Ni( i Pr2ImMe)2(Beg)2] are reported, which were prepared via the reaction of a source of [Ni( i Pr2ImMe)2] with the diboron(4) compounds B2cat2, B2pin2 and B2eg2 ( i Pr2ImMe = 1,3-di-iso-propyl-4,5-dimethylimidazolin-2-ylidene; B2cat2 = bis(catecholato)diboron; B2pin2 = bis(pinacolato)diboron; B2eg2 = bis(ethylene glycolato)diboron). X-ray diffraction and DFT calculations strongly suggest that a delocalized, multicenter bonding scheme dictates the bonding situation of the NiB2 moiety in these square planar complexes, reminiscent of the bonding situation of "non-classical" H2 complexes. [Ni( i Pr2ImMe)2] also efficiently catalyzes the diboration of alkynes using B2cat2 as the boron source under mild conditions. In contrast to the known platinum-catalyzed diboration, the nickel system follows a different mechanistic pathway, which not only provides the 1,2-borylation product in excellent yields, but also provides an efficient approach to other products such as C-C coupled borylation products or rare tetra-borylated compounds. The mechanism of the nickel-catalyzed alkyne borylation was examined by means of stoichiometric reactions and DFT calculations. Oxidative addition of the diboron reagent to nickel is not dominant; the first steps of the catalytic cycle are coordination of the alkyne to [Ni( i Pr2ImMe)2] and subsequent borylation at the coordinated and, thus, activated alkyne to yield complexes of the type [Ni(NHC)2(η2-cis-(Bcat)(R)C[double bond, length as m-dash]C(R)(Bcat))], exemplified by the isolation and structural characterization of [Ni( i Pr2ImMe)2(η2-cis-(Bcat)(Me)C[double bond, length as m-dash]C(Me)(Bcat))] and [Ni( i Pr2ImMe)2(η2-cis-(Bcat)(H7C3)C[double bond, length as m-dash]C(C3H7)(Bcat))].

A hampered oxidative addition of pre-coordinated pincer ligands can favour alternative pathways of activation.

Pre-coordination to a transition metal by the terminal donor groups of a tri-dentate ligand is a common strategy to stabilise elusive groups, to achieve unprecedented bond activation and to develop novel modes of metal-ligand-cooperation for catalysis. In the current manuscript, we demonstrate that the oxidative addition of a central E-H-bond after pre-coordination to the metal centre is disfavoured for metals with d10 electron configuration. For exemplary pincer ligands and metals with d10 electron configuration, quantum chemical calculations suggest a second barrier, which is associated with the rearrangement of the saw-horse structure, obtained after oxidative addition, to the expected square planar geometry for the resulting d8 electron configuration. In the case of PBP-type ligands with a central L2BH2-group (L = R3P) the reaction with Pt0 precursors proceeds via an alternative pathway of activation, which involves the backside attack of a nucleophile to the boron atom, which facilitates the nucleophilic attack of the Pt0 centre and formation of a boryl complex (LBH2). As the corresponding reaction with a PtII precursor leads to B-H- instead of B-L-activation and formation of complex 2 with a L2BH donor, our results show that ligand-stabilized borylenes (L2BH) can in principle be converted to boryls (LBH2) via boronium salts (L2BH2+).

Iron-Catalyzed Cross-Electrophile Coupling of Inert C–O Bonds with Alkyl Bromides

Iron-Catalyzed Cross-Electrophile Coupling of Inert C–O Bonds with Alkyl Bromides

Copper-Catalyzed Borylation of Acyl Chlorides with an Alkoxy Diboron Reagent: A Facile Route to Acylboron Compounds.

Herein, the copper‐catalyzed borylation of readily available acyl chlorides with bis(pinacolato)diboron, (B2pin2) or bis(neopentane glycolato)diboron (B2neop2) is reported, which provides stable potassium acyltrifluoroborates (KATs) in good yields from the acylboronate esters. A variety of functional groups are tolerated under the mild reaction conditions (room temperature) and substrates containing different carbon‐skeletons, such as aryl, heteroaryl and primary, secondary, tertiary alkyl are applicable. Acyl N‐methyliminodiacetic acid (MIDA) boronates can also been accessed by modification of the workup procedures. This process is scalable and also amenable to the late‐stage conversion of carboxylic acid‐containing drugs into their acylboron analogues, which have been challenging to prepare previously. A catalytic mechanism is proposed based on in situ monitoring of the reaction between p‐toluoyl chloride and an NHC‐copper(I) boryl complex as well as the isolation of an unusual lithium acylBpinOBpin compound as a key intermediate.

Catalytic dehydrocoupling of methylamine borane using Yamashita's [Ir(PBP)] boryl complex – characterisation of a novel highly fluxional Ir tetrahydride

Catalytic dehydropolymerisation of methylamine borane using the boryl pincer complex [(PBP)Ir(H)(Cl)]/NaOtBu proceeds via an unusual highly fluxional Ir tetrahydride.

Robust dicopper(i) μ-boryl complexes supported by a dinucleating naphthyridine-based ligand.

Copper boryl species have been widely invoked as reactive intermediates in Cu-catalysed C–H borylation reactions, but their isolation and study have been challenging. Use of the robust dinucleating ligand DPFN (2,7-bis(fluoro-di(2-pyridyl)methyl)-1,8-naphthyridine) allowed for the isolation of two very thermally stable dicopper(i) boryl complexes, [(DPFN)Cu2(μ-Bpin)][NTf2] (2) and [(DPFN)Cu2(μ-Bcat)][NTf2] (4) (pin = 2,3-dimethylbutane-2,3-diol; cat = benzene-1,2-diol). These complexes were prepared by cleavage of the corresponding diborane via reaction with the alkoxide [(DPFN)Cu2(μ-OtBu)][NTf2] (3). Reactivity studies illustrated the exceptional stability of these boryl complexes (thermal stability in solution up to 100 °C) and their role in the activation of C(sp)–H bonds. X-ray diffraction and computational studies provide a detailed description of the bonding and electronic structures in these complexes, and suggest that the dinucleating character of the naphthyridine-based ligand is largely responsible for their remarkable stability.

Insertion chemistry of iron(II) boryl complexes.

Iron(II) boryl complexes of the pyrrole-based pincer ligand, CyPNP (CyPNP = anion of 2,5-bis(dicyclohexylphophinomethyl)pyrrole) have been synthesized and their insertion reactivity interrogated. Compounds of the type [Fe(BE)(CyPNP)] (E = pinacholato or catecholato) can be generated by treatment of the precursors, [Fe(OPh)(py)(CyPNP)] or [FeMe(CyPNP)], with B2E2. The boryl complexes are meta stable, but permit additional reactivity with several unsaturated substrates. Reaction with alkynes, RCCR', leads to rapid insertion into the Fe-B bond to generate stable vinyl boronate complexes of the type [Fe(C{R}C{R'}BE)(CyPNP)] (R, R' = H, Me, Ph, -CCPh). Each of the compounds is five-coordinate in the solid state by virtue of coordination of one of the oxygen atoms of the boronate ester. Similar reaction with nitriles, RCN (R = Ph, Me), results in facile de-cyanation to produce the correpsonding hydrocarbon complexes, [FeR(CyPNP)]. In the case of the bulky nitrile 1-AdCN, the insertion intermediate, [Fe(C{Ad}NBpin)(CyPNP)], has been isolated and structurally characterized. Treatment of the boryl complexes with styrene derivatives results in initial insertion to give an alkylboronate complex followed by either β-H elimination or protonation to give the products of C-H borylation and hydroboration, respectively.

A Ni0 σ-Borane Complex Bearing a Rigid Bidentate Borane/Phosphine Ligand: Boryl Complex Formation by Oxidative Dehydrochloroborylation and Catalytic Activity for Ethylene Polymerization.

While of interest, synthetically feasible access to boryl ligands and complexes remains limited, meaning such complexes remain underexploited in catalysis. For bidentate boryl ligands, oxidative addition of boranes to low-valent IrI or Pt0 are the only examples yet reported. As part of our interest in developing improved group 10 ethylene polymerization catalysts, we present here an optimized synthesis of a novel, rigid borane/phosphine ligand and its Ni0 σ-borane complex. From the latter, an unprecedented oxidative dehydrochloroborylation, to give a NiII boryl complex, was achieved. Furthermore, this new B/P ligand allowed the nickel-catalyzed polymerization of ethylene, which suggests that Ni0 σ-hydroborane complexes act as masked NiII boryl hydride reagents.

A Ni0 σ‐Borane Complex Bearing a Rigid Bidentate Borane/Phosphine Ligand: Boryl Complex Formation by Oxidative Dehydrochloroborylation and Catalytic Activity for Ethylene Polymerization

AbstractWhile of interest, synthetically feasible access to boryl ligands and complexes remains limited, meaning such complexes remain underexploited in catalysis. For bidentate boryl ligands, oxidative addition of boranes to low‐valent IrI or Pt0 are the only examples yet reported. As part of our interest in developing improved group 10 ethylene polymerization catalysts, we present here an optimized synthesis of a novel, rigid borane/phosphine ligand and its Ni0 σ‐borane complex. From the latter, an unprecedented oxidative dehydrochloroborylation, to give a NiII boryl complex, was achieved. Furthermore, this new B/P ligand allowed the nickel‐catalyzed polymerization of ethylene, which suggests that Ni0 σ‐hydroborane complexes act as masked NiII boryl hydride reagents.