On Haptotropic Rearrangements of Diphosphene and Diarsene Ligands in Titanium Complexes.

Dipnictenes of the type RE=ER (E=P, As, Sb, Bi) are the isovalence electronic heavier analogs of alkenes. Although diphosphenes and dipnictenes in general show a variety of binding modes in metal complexes, little is known about haptotropic shift reactions involving these ligands. Herein, we report an unprecedented η2 to η1 rearrangement of the dipnictene ligands in titanocene complexes of the type Cp2Ti(Pn2Ar2) (Pn=P, As; Ar=2,4,6-Me3-C6H2, Mes; 2,6-iPr2-C6H3, Dip; 2,4,6-iPr3-C6H2, Tip), initiated by Lewis basic ligands (L=MeCN, PMe3, AdNC, CO). In the presence of L the dipnictene ligand changes its hapticity from η2 to η1 and complexes of the general form Cp2Ti(L)(Pn2Ar2) with a succinctly different electronic structure are obtained. Electronically, the new complexes are best described as biradicaloids with antiferromagnetically coupled (via a π-bond) [Cp2TiIII]⋅+ and [Pn2Ar2]⋅- fragments. However, the biradical character of these systems is affected by the electronic features of the co-ligand and significantly decreases moving from PMe3/MeCN (σ-donors) to CNAd/CO (σ-donors/π-acceptors).

The Azide-Wittig Reaction.

The introduction of heteroatoms into conjugated organic molecules is an important strategy to tune their reactivity and physical properties. In this realm triazabutadienes (TBDs) of the general from R2C=N-N=NR' are an interesting class of compounds, however, general synthetic protocols for their generation are limited. Based on the serendipitous finding that the sterically encumbered azide Mes*N3 (Mes* = 2,4,6-tBu3C6H2) reacted with PMe3 in the presence of an aromatic aldehyde to form a TBD, we now report on the "Azide-Wittig" reaction. This azide-Wittig reaction is shown to be a versatile tool for the synthesis of a variety of TBDs, tolerating a wide range of aldehydes and organic azides as coupling partners. The preference for azide-Wittig, rather than aza-Wittig reactivity was rationalized using computational methods. This study shows how kinetic control can significantly alter the reaction pathway, thereby switching from an aza-Wittig to an azide-Wittig regime.

Synthesis and Ligand Properties of Chelating Bis(N-heterocyclic carbene)-Stabilized Bis(phosphinidenes).

NHC-phosphinidene (NHCP) adducts are an emerging class of ligands with proven binding ability for main group and transition metal elements. They possess electron-rich P atoms with two lone pairs (LPs) of electrons, making them interesting platforms for the formation of multimetallic complexes. We describe herein a modular, high-yielding synthesis of bis(NHCP)s, starting from alkylidene-bridged bis(NHC)s ((IMe)2CnH2n; n = 1,3) and triphosphirane (PDip)3 (Dip = 2,6-iPr2C6H3) as phosphinidene transfer reagent. The coordination chemistry of [{DipP(IMe)}2CH2], 1, was studied in detail, and complexes [1·FeBr2] and [1·Rh(cod)]Cl were prepared, showing that the ligand has a flexible bite angle. The dicarbonyl complex [1·Rh(CO)2]Cl, with an average value for the CO stretching frequency of 2029 cm-1, indicates a strongly donating ligand when compared to related complexes. The binding ability of the remaining two phosphorus LPs was demonstrated with AuCl(SMe2), giving the heterotrimetallic complex [1·(AuCl)2·Rh(cod)]Cl. Moreover, [1·Rh(cod)]X (X- = Cl, B(3,5-(CF3)2-C6H3)4) was tested in the catalytic hydrogenation of methyl-Z-α-acetamidocinnamate (MAC) and dimethyl itaconate (ItMe2), revealing that the chloride complex was inactive, while the BArF complex demonstrated moderate activity. Additionally, [1·Rh(cod)]Cl was shown to be moderately air- and moisture-stable, slowly decomposing to the corresponding NHC-stabilized bis-dioxophosphorane, which was independently synthesized by treating the free ligand with dry O2.

On the Reactivity of Phosphaalumenes towards C-C Multiple Bonds.

Heterocycles containing group 13 and 15 elements such as borazines are an integral part of organic, biomedical and materials chemistry. Surprisingly, heterocycles containing P and Al are rare. We have now utilized phosphaalumenes in reactions with alkynes, alkenes and conjugated double bond systems. With sterically demanding alkynes 1,2-phosphaalumetes were afforded, whereas the reaction with HCCH or HCCSiMe3 gave 1,4-phosphaaluminabarrelenes. Using styrene saturated 1,2-phosphaalumates were formed, which reacted further with additional styrene to give different regio-isomers of 1,4-aluminaphosphorinanes. Using ethylene, a 1,4-aluminaphosphorinane is obtained, while with 1,3-butadiene a bicyclic system containing an aluminacyclopentane and a phosphirane unit was synthesized. The experimental work is supported by theoretical studies to shed light on the mechanism governing the formation of these heterocycles.

Synthesis, Coordination Chemistry, and Mechanistic Studies of P,N-Type Phosphaalkene-Based Rh(I) Complexes.

The synthesis of P,N-phosphaalkene ligands, py-CH═PMes* (1, py = 2-pyridyl, Mes* = 2,4,6-tBu-C6H2) and the novel quin-CH═PMes* (2, quin = 2-quinolinyl) is described. The reaction with [Rh(µ-Cl)cod]2 produces Rh(I) bis(phosphaalkene) chlorido complexes 3 and 4 with distorted trigonal bipyramidal coordination environments. Complexes 3 and 4 show a pronounced metal-to-ligand charge transfer (MLCT) from Rh into the ligand P═C π* orbitals. Upon heating, quinoline-based complex 4 undergoes twofold C-H bond activation at the o-tBu groups of the Mes* substituents to yield the cationic bis(phosphaindane) Rh(I) complex 5, which could not be observed for the pyridine-based analogue 3. Using sub- or superstoichiometric amounts of AgOTf the C-H bond activation at an o-tBu group of one or at both Mes* was detected, respectively. Density functional theory (DFT) studies suggest an oxidative proton shift pathway as an alternative to a previously reported high-barrier oxidative addition at Rh(I). The Rh(I) mono- and bis(phosphaindane) triflate complexes 6 and 7, respectively, undergo deprotonation at the benzylic CH2 group of the phosphaindane unit in the presence of KOtBu to furnish neutral, distorted square-planar Rh(I) complexes 8 and 9, respectively, with one of the P,N ligands being dearomatized. All complexes were fully characterized, including multinuclear NMR, vibrational, and ultraviolet-visible (UV-vis) spectroscopy, as well as single-crystal X-ray and elemental analysis.

Metal-Free N-H Bond Activation by Phospha-Wittig Reagents.

N-containing molecules are mostly derived from ammonia (NH3 ). Ammonia activation has been demonstrated for single transition metal centers as well as for low-valent main group species. Phosphinidenes, mono-valent phosphorus species, can be stabilized by phosphines, giving so-called phosphanylidenephosphoranes of the type RP(PR'3 ). We demonstrate the facile, metal-free NH3 activation using ArP(PMe3 ), affording for the first time isolable secondary aminophosphines ArP(H)NH2 . DFT studies reveal that two molecules of NH3 act in concert to facilitate an NH3 for PMe3 exchange. Furthermore, H2 NR and HNR2 activation is demonstrated.

Isolable Phospha- and Arsaalumenes.

The combination of (AlCp*)4, a source of monomeric :AlCp* at elevated temperatures, with DipTerPnPMe3 (Pn = P, As), so-called pnicta-Wittig reagents, at 80 °C cleanly gives the pnictaalumenes DipTerPnAlCp* with polarized Pn-Al double bonds and intramolecular stabilization through interactions of Al with a flanking aryl group of the terphenyl substituent on Pn. In contrast, using MesTerPPMe3, the reaction with 2 equiv of :AlCp3t or :AlCp* afforded the three-membered 2π-aromatic ring systems MesTerP(AlCpx)2 (x = 3t, *).

Cyclo-Dipnictadialanes.

Using the AlI precursor Cp3t Al in conjunction with triphosphiranes (PAr)3 (Ar=Mes, Dip, Tip) we have succeeded in preparing Lewis base-free cyclic diphosphadialanes with both the Al and P atoms bearing three substituents. Using the sterically more demanding Dip and Tip substituents the first 1,2-diphospha-3,4-dialuminacyclobutanes were obtained, whereas with Mes substituents [Cp3t Al(µ-PMes)]2 is formed. This divergent reactivity was corroborated by DFT studies, which indicated the thermodynamic preference for the 1,2-diphospha-3,4-dialuminacyclobutane form for sterically more demanding groups on phosphorus. Using Cp*Al we could extend this concept to the corresponding cyclic diarsadialanes [Cp*Al(µ-AsAr)]2 (Ar=Dip, Tip) and additionally add the phosphorus variants [Cp*Al(µ-PAr)]2 (P=Mes, Dip, Tip). The reactivity of one variant [Cp3t Al(µ-PPh)]2 towards NHCs was tested and resulted in double NHC-stabilised [Cp3t (IiPr2 )Al(µ-PPh)]2 .

N-Heterocyclic Olefin-Ligated Palladium(II) Complexes as Pre-Catalysts for Buchwald-Hartwig Aminations.

New N-heterocyclic olefins (NHOs) are described with functionalization on the ligand heterocyclic backbone and terminal alkylidene positions. Various PdII -NHO complexes have been formed and their use as pre-catalysts in Buchwald-Hartwig aminations was explored. The most active system for catalytic C-N bond formation between hindered arylamine and arylhalide substrates was accessed by combining a backbone methylated NHO with [Pd(cinnamyl)Cl]2 in the presence of NaOtBu as a base. In these active systems evidence suggests that catalysis is mediated by colloidal palladium metal, highlighting a different coordination ability of NHOs in comparison with commonly used N-heterocyclic carbene co-ligands.

Metal-Free Nitrogen Fixation at Boron.

No metal needed: Boron does the job! The activation of the inert dinitrogen molecule has fascinated chemists for ages. In a ground-breaking study Braunschweig and co-workers have now demonstrated that N2 activation can be achieved with the aid of the p-block element boron-a reactivity previously restricted to transition metals.

Oxoborane (RBO) Complexation and Concomitant Electrophilic Bond Activation Processes.

Donor-acceptor complexes of the oxoboranes ClB=O and HOB=O were synthesized and each feature short multiply bonded B=O linkages. The retention of high Lewis acidic character within these encapsulated monomeric oxoboranes was manifested by their ability to support C-F and Si-O bond activation/functionalization. The reported ClB=O complexes can be regarded as synthetic surrogates of the [BO]+ cation, an inorganic analogue of CO.

Using N-Heterocyclic Vinyl Ligands to Access Stable Divinylgermylenes and a Germylium Cation.

Two efficient methods are presented to install σ- and π-electron-donating N-heterocyclic vinyl groups onto main-group elements (E): halosilane elimination and base-induced E-C bond formation. Placement of two NHC=CH- ligands (NHC=N-heterocyclic carbene) onto a GeII center affords a two-coordinate germylene, a heavy congener of the elusive divinyl carbenes. The π-donating ability of this vinylic ligand scaffold was further demonstrated by the synthesis of a three-coordinate germylium cation R3 Ge+ .

Synthesis of arylated coumarins by Suzuki-Miyaura cross-coupling. Reactions and anti-HIV activity.

Arylated coumarins were prepared by site-selective Suzuki-Miyaura cross-coupling reaction of the bis(triflate) of 4-methyl-6,7-dihydroxycoumarin. Triarylated coumarins were prepared by Suzuki-Miyaura cross-coupling reactions of 3-bromo-4-methyl-2-oxo-2H-chromene-6,7-diylbis(trifluoromethanesulfonate). The in vitro anti-HIV activity of the products was investigated. Two lead structures with considerable activities were identified.

Synthesis of elusive chloropnictenium ions.

This work describes the synthesis and full characterization of elusive chloropnictenium ion salts of the type [(R)Ar*N(SiMe)ECl][A] ((R)Ar* = 2,6-(CHPh2)-4-R-C6H2, R = Me, tBu; E = Sb, Bi; A(-) = GaCl4, Al(OCH(CF3)2)4). In these species the cation is significantly stabilized by weak arene interactions to flanking phenyl groups of the (R)Ar* moiety. In this context the bonding situation has been studied by computational means and the reactivity towards the Lewis base 4-dimethylaminopyridine (dmap) was investigated.

Encapsulating Inorganic Acetylene, HBNH, Using Flanking Coordinative Interactions.

A stable donor-acceptor coordination complex of the elusive parent inorganic iminoborane HBNH (a structural analogue of acetylene) is reported. This species was generated via thermally induced N2 elimination/1,2-H migration from a hydrido(azido)borane adduct NHC⋅BH2N3 (NHC=N-heterocyclic carbene) in the presence of a fluorinated triarylborane. The mechanism of this process was also investigated by computational and isotopic labeling studies. This transformation represents a new and potentially modular route to unsaturated inorganic building blocks for advanced material synthesis.

Phosphaarsenes - Combining Phospha- and Arsa-Wittig-Reagents.

Dipnictenes of the type RPn=PnR (Pn=P, As, Sb, Bi) can be viewed as dimers of the corresponding pnictinidenes R-Pn. Phosphanylidene- and arsanylidenephosphoranes (R-Pn(PMe3); Pn=P, As) have been shown to be versatile synthetic surrogates for the delivery of pnictinidene fragments. We now report that thermal treatment of 1 : 1 mixtures of R-P(PMe3) and R'-As(PMe3) gives access to arsaphosphenes of the type RP=AsR'. Three examples are presented and the properties and reactivity of Mes*P=AsDipTer (1) (Mes*=2,4,6-tBu3-C6H2; DipTer=2,6-(2,6-iPr2C6H3)2-C6H3) were studied in detail. Solid state 31P NMR spectroscopy revealed a large 31P NMR chemical shift anisotropy with a span of ca. 920 ppm for 1 while computational methods were employed to investigate this pronounced magnetic deshielding of the P atom in 1. In the presence of the carbene IMe4 (IMe4=:C(MeNCMe)2) 1 is shown to be split into the corresponding NHC adducts Mes*P(IMe4) and DipTerAs(IMe4), which is additionally shown for diarsenes.

1,3-Dipolar cyclisation reactions of nitriles with sterically encumbered cyclic triphosphanes: synthesis and electronic structure of phosphorus-rich heterocycles with tunable colour.

We describe the synthesis, solid state and electronic structures of a series of tunable five-membered cationic and charge-neutral inorganic heterocycles featuring a P3CN core. 1-Aza-2,3,4-triphospholenium cations [(PR)3N(H)CR']+, [1R]+ (R' = Me, Ph, 4-MeOC6H4, 4-CF3C6H4) were formed as triflate salts by the formal [3 + 2]-cyclisation reactions of strained cyclic triphosphanes (PR)3 (R = t Bu, 2,4,6-Me3C6H2 (Mes), 2,6- i Pr2C6H3 (Dipp), 2,4,6- i Pr3C6H2 (Tipp)) with nitriles R'CN in the presence of triflic acid. The corresponding neutral free bases (PR)3NCR' (2R) were readily obtained by subsequent deprotonation with NEt3. The P3CN cores in 2R show an envelope conformation typical for cyclopentenes and present as yellow to orange compounds in the solid state as well as in solution depending on both substituents R and R' in (PR)3NCR'. The P3CN cores in [1R]+ show a significant deviation from planarity with increasing steric bulk of the R groups at phosphorus, which results in a decrease in the HOMO-LUMO gap and distinct low-energy UV-Visible absorption bands. This allows access to colours spanning red, blue, indigo, and magenta. TD-DFT calculations provide valuable insight into this phenomenon and indicate an intramolecular charge-transfer from the HOMO located on the P3 framework to the N[double bond, length as m-dash]C-R'-based LUMO in the cationic species. The cations [1R]+ represent rare examples of phosphorus-rich heterocycles with tunable colour, which can be incorporated into polymers by post-polymerization modification to afford coloured polymers, which demonstrate utility as both proton and ammonia sensors.

Pd8(PDip)6: Cubic, Unsaturated, Zerovalent.

Atomically precise nanoclusters hold promise for supramolecular assembly and (opto)electronic- as well as magnetic materials. Herein, this work reports that treating palladium(0) precursors with a triphosphirane affords strongly colored Pd8(PDip)6 that is fully characterized by mass spectrometry, heteronuclear and Cross-Polarization Magic-Angle Spinning (CP-MAS) NMR-, infrared (IR), UV-vis, and X-ray photoelectron (XP) spectroscopies, single-crystal X-Ray diffraction (sc-XRD), mass spectrometry, and cyclovoltammetry (CV). This coordinatively unsaturated 104-electron Pd(0) cluster features a cubic Pd8-core, µ4-capping phosphinidene ligands, and is air-stable. Quantum chemical calculations provide insight to the cluster's electronic structure and suggest 5s/4d orbital mixing as well as minor Pd─P covalency. Trapping experiments reveal that cluster growth proceeds via insertion of Pd(0) into the triphosphirane. The unsaturated cluster senses ethylene and binds isocyanides, which triggers the rearrangement to a tetrahedral structure with a reduced frontier orbital energy gap. These experiments demonstrate facile cluster manipulation and highlight non-destructive cluster rearrangement as is required for supramolecular assembly.

Triphosphiranes as phosphinidene-transfer agents - synthesis of regular and chelating NHC phosphinidene adducts.

In this contribution we describe the general use of aryl-substituted triphosphiranes (Ar3P3; Ar = Mes, Dip, Tip) as phosphinidene transfer reagents towards N-heterocyclic carbenes (NHCs) to give a library of twelve N-heterocyclic carbene phosphinidene adducts of the type ArPNHC (NHCPs), in which the NHCs have varying steric profiles, allowing a systematic evaluation of their structural and NMR-spectroscopic properties. In the next series of experiments we utilized 1,3- and 1,4-phenylene bridged bis-NHCs to access a new class of chelating bis(NHCP)s, of which three derivatives could be structurally characterized. The 1,4-phenylene derivatives were shown to be susceptible to P-CNHC bond cleavage when irradiated with an LED (396 nm), providing a rare example of phosphinidene release from NHCPs. The coordination chemistry of 1,3-phenylene bridged bis(NHCP)s towards GeCl2(dioxane) and GaI3 was investigated and revealed the formation of ion-separated cationic complexes, with significant charge transfer from the ligand to the metal center according to NBO analyses.

On the Reactivity of Mes*P(PMe3 ) towards Aluminum(I) Compounds - Evidence for the Intermediate Formation of Phosphaalumenes.

Phosphaalumenes are the heavier isoelectronic analogs of alkynes and have eluded facile synthesis until recently. We have reported that the combination of a phosphinidene transfer agent, Ar TerP(PMe3 ) (Ar Ter=2,6-Ar2 -C6 H3 ), with (Cp*Al)4 (Cp*=C5 (CH3 )5 ) afforded the phosphaalumenes Ar TerPAlCp* as isolable, violet, thermally stable compounds. In here we describe attempts to utilize Mes*P(PMe3 ) (Mes*=2,4,6-tBu3 -C6 H2 ) as a phosphinidene source in combination with different Al(I) precursors, namely Dip NacnacAl (Dip Nacnac=HC[C(Me)NDip]2 , Dip=2,6-iPr2 -C6 H3 ), (Cp*Al)4 and Cp3t Al (Cp3t =1,2,4-tBu3 -C5 H2 ). In all cases the formation of phosphaalumenes was not observed, however, their intermediate formation is indicated by formation of the dimer [Cp*Al(µ-PMes*)]2 (2) and C-H-bond activation products along the putative P=Al bond, giving unusual 1,2-P,Al-tetrahydronaphtalene derivatives 1 and 4, clearly underlining the role the sterically demanding group on phosphorus plays in these transformations. The reactivity studies are supported by theoretical studies, demonstrating a thermodynamic preference for the C-H activation products. Additionally, we show that there are potential pitfalls in the synthesis of Cp*2 AlH, the precursor to make (Cp*Al)4 and give recommendations how to circumvent these.