Chemo-selective Stille-type coupling of acyl-chlorides upon phosphine-borane Au(i) catalysis.

Phosphine-boranes do not promote oxidative addition of acyl chlorides to gold, but the phosphine-borane gold triflimide complex [iPr2P(o-C6H4)BCy2]AuNTf2 was found to catalyze the coupling of acyl chlorides and aryl stannanes. The reaction involves aryl/chloride-bridged dinuclear gold(i) complexes as key intermediates, as substantiated by spectroscopic and crystallographic analyses. Similar to Pd(0)/Pd(ii)-catalyzed Stille coupling with phosphine-borane ligands, the gold-catalyzed variant shows complete chemoselectivity for acyl chlorides over aryl iodides and bromides, enabling straightforward access to halogenated aryl ketones.

Lewis Acid-Assisted C(sp3)-C(sp3) Reductive Elimination at Gold.

The phosphine-borane iPr2P(o-C6H4)BFxyl2 (Fxyl = 3,5-(F3C)2C6H3) 1-Fxyl was found to promote the reductive elimination of ethane from [AuMe2(µ-Cl)]2. Nuclear magnetic resonance monitoring revealed the intermediate formation of the (1-Fxyl)AuMe2Cl complex. Density functional theory calculations identified a zwitterionic path as the lowest energy profile, with an overall activation barrier more than 10 kcal/mol lower than without borane assistance. The Lewis acid moiety first abstracts the chloride to generate a zwitterionic Au(III) complex, which then readily undergoes C(sp3)-C(sp3) coupling. The chloride is finally transferred back from boron to gold. The electronic features of this Lewis-assisted reductive elimination at gold have been deciphered by intrinsic bond orbital analyses. Sufficient Lewis acidity of boron is required for the ambiphilic ligand to trigger the C(sp3)-C(sp3) coupling, as shown by complementary studies with two other phosphine-boranes, and the addition of chlorides slows down the reductive elimination of ethane.

Metal-Free Phosphorus-Directed Borylation of C(sp2 )-H Bonds.

Spectacular progress has recently been achieved in transition metal-catalyzed C-H borylation of phosphines as well as directed electrophilic C-H borylation. As shown here, P-directed electrophilic borylation provides a new, straightforward, and efficient access to phosphine-boranes. It operates under metal-free conditions and leverages simple, readily available substrates. It is applicable to a broad range of backbones (naphthyl, biphenyl, N-phenylpyrrole, binaphthyl, benzyl, naphthylmethyl) and gives facile access to various substitution patterns at boron (by varying the boron electrophile or post-derivatizing the borane moiety). NMR monitoring supports the involvement of P-stabilized borenium cations as key intermediates. DFT calculations reveal the existence and stabilizing effect of π-arene/boron interactions in the (biphenyl)(i-Pr)2 P→BBr2 + species.

Lewis pairing and frustration of group 13/15 elements geometrically enforced by (ace)naphthalene, biphenylene and (thio)xanthene backbones.

The synthesis, structure, and reactivity of mixed group 13/group 15 compounds (E13 = B, Al, Ga, In, Tl; E15 = N, P, Sb, Bi) featuring a rigid (ace)naphthalene or (thio)xanthene backbone are discussed in this review. The backbone may either enforce or prevent E15→E13 interactions, resulting in Lewis pairing or frustration. The formation of strong E15→E13 interactions is possible upon peri-substitution of (ace)naphthalenes. This gives the opportunity to access and study highly reactive species, as exemplified by P-stabilised borenium salts and boryl radicals. In turn, rigid expanded spacers such as biphenylenes, (thio)xanthenes and dibenzofurans impose long distances and geometrically prevent E15→E13 interactions. Such P-B derivatives display ambiphilic coordination properties and frustrated Lewis pair behaviour towards small molecules, their preorganised structure favouring reversible interaction/activation. Throughout the review, the importance of the scaffold in enforcing or preventing E15→E13 interactions is highlighted and discussed based on experimental data and theoretical calculations.

1,1-Phosphaboration of C[triple bond, length as m-dash]C and C[double bond, length as m-dash]C bonds at gold.

The phosphine-borane iPr2P(o-C6H4)BFXyl2 (Fxyl = 3,5-(F3C)2C6H3) was found to react with gold(i) alkynyl and vinyl complexes via an original 1,1-phosphaboration process. Zwitterionic complexes resulting from Au to B transmetallation have been authenticated as key intermediates. X-ray diffraction analyses show that the alkynyl-borate moiety remains pendant while the vinyl-borate is side-on coordinated to gold. According to DFT calculations, the phosphaboration then proceeds in a trans stepwise manner via decoordination of the phosphine, followed by anti nucleophilic attack to the π-CC bond activated by gold. The boron center acts as a relay and tether for the organic group.

Strong metal-borane interactions in low-valent cyclopentadienyl rhodium complexes.

The first examples of half-sandwich Rh(i) complexes stabilized by borane coordination have been prepared and structurally characterized. As substantiated by NMR spectroscopy and single-crystal X-ray diffraction, the phosphine-borane ligand iPr2P-(o-C6H4)-BFxyl2 1 [Fxyl = 3,5-(F3C)2C6H3] engages in tight η3-BCC or η1-B coordination, depending on the metal environment.

A sterically congested 1,2-diphosphino-1'-boryl-ferrocene: synthesis, characterization and coordination to platinum.

A new class of tritopic ferrocene-based ambiphilic compounds has been prepared by assembling diphosphino- and boryl-substituted cyclopentadienides at iron. The presence of five sterically demanding substituents on the ferrocene platform induces conformational constraints, as is apparent from XRD and NMR data, but does not prevent the chelating coordination to platinum. The Lewis acid moiety is pendant in both the free ligand and the platinum complex.

Gold(I) Complexes of the Geminal Phosphinoborane tBu2PCH2BPh2.

In this work, we explored the coordination properties of the geminal phosphinoborane tBu2PCH2BPh2 (2) toward different gold(I) precursors. The reaction of 2 with an equimolar amount of the sulfur-based complex (Me2S)AuCl resulted in displacement of the SMe2 ligand and formation of linear phosphine gold(I) chloride 3. Using an excess of ligand 2, bisligated complex 4 was formed and showed dynamic behavior at room temperature. Changing the gold(I) metal precursor to the phosphorus-based complex, (Ph3P)AuCl impacted the coordination behavior of ligand 2. Namely, the reaction of ligand 2 with (Ph3P)AuCl led to the heterolytic cleavage of the gold-chloride bond, which is favored over PPh3 ligand displacement. To the best of our knowledge, 2 is the first example of a P/B-ambiphilic ligand capable of cleaving the gold-chloride bond. The coordination chemistry of 2 was further analyzed by density functional theory calculations.

Planar-Chiral 1,1'-Diboryl Metallocenes: Diastereoselective Synthesis from Boryl Cyclopentadienides and Spin Density Analysis of a Diborylcobaltocene.

The reaction of nonsubstituted alkali metal cyclopentadienides with haloboranes leads to ∼90:10 mixtures of isomeric diene products that can be deprotonated to give simple boryl cyclopentadienides. We extended this transformation to the sterically hindered lithium tert-butylcyclopentadienide 1 using FBMes2 (Mes = 2,4,6-trimethylphenyl) and ClBCy2 as electrophiles. The boryl group is selectively introduced in the remote position to minimize steric congestion. The new boryl dienes are obtained as mixtures of isomers, and subsequent deprotonation with MeLi or LiHMDS affords the lithium 1,3-disubstituted cyclopentadienides 5a,b in yields over 95%. Direct assembling of tert-butylated boryl cyclopentadienides with MCl2 (M = Fe, Co) selectively leads to 1,1'-planar chiral ferrocenes 6a,b and cobaltocene 7. To shed light into the diastereoselective formation of 6a, DFT calculations were performed. The potential energy surface was scrutinized so as to identify and compare its diastereoisomers and conformers. This stereoselectivity is attributed to minimized steric repulsions between the tert-butyl and the BMes2 groups in the eclipsed conformation of the racemic diastereoisomers. The X-ray structures of boryl diene 2a and diboryl ferrocene 6a are reported. The electronic structure of cobaltocene 7 was analyzed by EPR and DFT calculations. The spin density of this unique open-shell complex is mainly localized on the Co center, but significant spin density is also found on the boron atoms, indicating substantial delocalization of the unpaired electron over the Lewis acid moieties. Consistently, the singly occupied molecular orbital is a combination of a Co-centered 3d orbital with π(BC) orbitals on each CpBMes2 rings. There is only weak, if any, direct M···B interaction in 6 and 7.

Diverse reactivity of borenium cations with >N-H compounds.

The Ph2P-stabilized borenium reacts cleanly with PhNH2, NH3 and HNTf2 to give a variety of boron compounds, namely the amino-substituted borenium (substitution reaction at B), the neutral phosphine-borane , the mixed P/N-stabilized boronium and the dicationic boron species . Remote modulation of the Lewis acidity at boron has been studied by preparing the related iPr2P-stabilized borenium and reacting it with dihydrogen.

A Significant but Constrained Geometry Pt→Al Interaction: Fixation of CO2 and CS2, Activation of H2 and PhCONH2.

Reaction of the geminal PAl ligand [Mes2PC(═CHPh)AltBu2] (1) with [Pt(PPh3)2(ethylene)] affords the T-shape Pt complex [(1)Pt(PPh3)] (2). X-ray diffraction analysis and DFT calculations reveal the presence of a significant Pt→Al interaction in 2, despite the strain associated with the four-membered cyclic structure. The Pt···Al distance is short [2.561(1) Å], the Al center is in a pyramidal environment [Σ(C-Al-C) = 346.6°], and the PCAl framework is strongly bent (98.3°). Release of the ring strain and formation of X→Al interactions (X = O, S, H) impart rich reactivity. Complex 2 reacts with CO2 to give the T-shape adduct 3 stabilized by an O→Al interaction, which is a rare example of a CO2 adduct of a group 10 metal and actually the first with η(1)-CO2 coordination. Reaction of 2 with CS2 affords the crystalline complex 4, in which the PPtP framework is bent, the CS2 molecule is η(2)-coordinated to Pt, and one S atom interacts with Al. The Pt complex 2 also smoothly reacts with H2 and benzamide PhCONH2 via oxidative addition of H-H and H-N bonds, respectively. The ensuing complexes 5 and 7 are stabilized by Pt-H→Al and Pt-NH-C(Ph) = O→Al bridging interactions, resulting in 5- and 7-membered metallacycles, respectively. DFT calculations have been performed in parallel with the experimental work. In particular, the mechanism of reaction of 2 with H2 has been thoroughly analyzed, and the role of the Lewis acid moiety has been delineated. These results generalize the concept of constrained geometry TM→LA interactions and demonstrate the ability of Al-based ambiphilic ligands to participate in TM/LA cooperative reactivity. They extend the scope of small molecule substrates prone to such cooperative activation and contribute to improve our knowledge of the underlying factors.

Complexes of ambiphilic ligands: reactivity and catalytic applications.

Since the mid 2000's, the incorporation of Lewis acid moieties in ligands for transition metals has been studied extensively. So-called ambiphilic ligands were shown to possess rich and unusual coordination properties and special focus was given to the coordination of Lewis acids as σ-acceptor ligands (concept of Z-type ligands). Recent studies have demonstrated that the presence of Lewis acids at or nearby transition metals can also strongly impact their reactivity. These results are surveyed in this review. The stoichiometric transformations and catalytic applications of complexes deriving from ambiphilic ligands are presented. The different roles the Lewis acid can play are discussed.

A Phosphine-Coordinated Boron-Centered Gomberg-Type Radical.

The P-coordinated boryl radical [Ph2P(naphthyl)BMes]˙ (Mes=mesityl) was prepared by (electro)chemical reduction of the corresponding borenium salt or bromoborane. Electron paramagnetic resonance (EPR) analysis in solution and DFT calculations indicate large spin density on boron (60-70%) and strong P-B interactions (P→B σ donation and B→P negative hyperconjugation). The radical is persistent in solution and participates in a Gomberg-type dimerization process. The associated quinoid-type dimer has been characterized by single-crystal X-ray diffraction.

A Stable but Highly Reactive Phosphine-Coordinated Borenium: Metal-free Dihydrogen Activation and Alkyne 1,2-Carboboration.

Borenium cations have been found to be valuable analogues of boranes as a result of their cationic character which imparts high electrophilicity. Herein, we report the synthesis, characterization, and reactivity of a new type of borenium cation employing a naphthyl bridge and a strong intramolecular P→B interaction. The cation reacts with H2 in the presence of PtBu3 (frustrated Lewis pair (FLP) approach) but also on its own. The mechanism of the reaction between the borenium cation and H2 in the absence of PtBu3 has been investigated using deuterium-labeling experiments and DFT calculations. Both experiments and calculations imply the side-on coordination of H2 to the B center, followed by heterolytic splitting and B-C bond cleavage. An uncommon syn 1,2-carboboration has also been observed upon reaction of the borenium ion with 3-hexyne.

Dative Au→Al interactions: crystallographic characterization and computational analysis.

Hitherto unknown Au→Al interactions have been evidenced upon coordination of the geminal phosphorus-aluminum Lewis pair Mes2 PC(=CHPh)AltBu2 (Mes=2,4,6-trimethylphenyl). Four different gold(I) complexes featuring alkyl (Me), aryl (Ph, C6F5), and alkynyl (C≡CPh) co-ligands have been prepared. X-ray diffraction analyses show that P→Au→Al bridging coordination induces noticeable bending of the ligand (the PCAl bond angle shrinks by 13°). This new type of transition metal→Lewis acid interaction has been analyzed by DFT calculations.

Novel zwitterionic complexes arising from the coordination of an ambiphilic phosphorus-aluminum ligand to gold.

Coordination of Mes2PC(=CHPh)AltBu2 to metal chlorides has been studied. Bridging P→M-Cl→Al coordinations were observed with Rh and Pd fragments, while chloride abstraction systematically occurred with gold. The resulting zwitterionic complexes have been fully characterized and analyzed by DFT calculations.

Phosphino-boryl-naphthalenes: geometrically enforced, yet Lewis acid responsive P → B interactions.

Three naphthyl-bridged phosphine-borane derivatives 2-BCy2, 2-BMes2, and 2-BFlu, differing in the steric and electronic properties of the boryl moiety, have been prepared and characterized by spectroscopic and crystallographic means. The presence and magnitude of the P → B interactions have been assessed experimentally and theoretically. The naphthyl linker was found to enforce the P → B interaction despite steric shielding, while retaining enough flexibility to respond to the Lewis acidity of boron.

Reactions of phosphine-boranes and related frustrated Lewis pairs with transition metal complexes.

Over the last few years, the coordination of phosphine-boranes and related Frustrated Lewis Pairs to transition metals has attracted considerable interest. These polyfunctional, ambiphilic ligands are very versatile. In particular, the Lewis acid site may participate in different ways to coordination, directly at the metal or in near periphery. These recent achievements are presented and discussed in this chapter.

Coordination of a diphosphine-phosphine oxide to Au, Ag and Rh: when polyfunctionality rhymes with versatility.

Gold, silver and rhodium complexes of the diphosphine-phosphine oxide DPPO = {[o-iPr(2)P-(C(6)H(4))](2)P(O)Ph} have been prepared and characterized. Thanks to its polyfunctional character, DPPO features versatile coordination properties. According to crystallographic data, only one phosphine moiety is engaged in coordination towards (AuCl) and [RhCl(nbd)]. However, NMR data indicate fluxional behavior in solution, as the result of the exchange between the free and coordinated phosphines around the metal. Chelating coordination via the two phosphine sites is observed towards (Au(+)) and (AgCl) with PMP bite angles varying from 122° to 159°. According to X-ray and theoretical analyses, the oxygen atom of the central phosphine oxide moiety points towards the metal but does not interact significantly with it. Tridentate coordination via the two phosphines as well as the oxygen atom of DPPO occurs with [Rh(CO)(+)], leading to an original PO(P)P pincer structure.