Radicalizing CO by Mononuclear Palladium(I).

A mononuclear, T-shaped palladium(I) d9 metalloradical (3), stabilized by a bulky carbazole-based PNP-ligand, was obtained by reduction of palladium chloride or thermal Pd-C bond homolysis of the corresponding neopentyl complex. Pressurizing with CO gave the Pd(I) carbonyl complex, which was structurally characterized by X-ray diffraction. Delocalization of the unpaired electron to the carbonyl carbon was detected by EPR spectroscopy and theoretically modeled by DFT and ab initio methods. The partially reduced and radicalized CO slowly reacts with di(tert-butyl) disulfide under homolytic S-S cleavage and C-S bond formation to give the corresponding metallathioester.

Synthesis of Collidine from Dinitrogen via a Tungsten Nitride.

The synthesis of pyridines from dinitrogen in homogeneous solution is known to be challenging considering that an N2 cleavage step needs to be combined with two N-C coupling steps. Herein, a tungsten complex bearing a tailor-made 2,2'-(tBu2As)2-substituted tolane ligand scaffold was shown to split N2 to afford the corresponding tungsten nitride, which is not the case for the corresponding (iPr2As)2-substituted derivative. The former nitride was then reacted with 2,4,6-trimethylpyrylium triflate, which led to the formation of a tungsten oxo complex, along with collidine. Over the course of this reaction, the O atom of the pyrylium starting material was replaced with an N atom via a hitherto unprecedented skeletal editing process.

To Split or Not to Split: [AsCCAs]-Coordinated Mo, W, and Re Complexes and Their Reactivity toward Molecular Dinitrogen.

Molybdenum, tungsten, and rhenium halides bearing a 2,2'-(iPr2As)2-substituted diphenylacetylene ([AsCCAs], 1-As) were prepared and reduced under an atmosphere of dinitrogen in order to activate the latter substrate. In the case of molybdenum, a diiodo (2-As) and a triiodo molybdenum precursor (5) were equally suited for reductive N2 splitting, which led to the isolation of [AsCCAs]Mo≡N(I) (3-As) in each case. For tungsten, [AsCCAs]WCl3 (6) was reduced under N2 to afford {[AsCCAs]WCl2}2(N2) (7), which is best described as a dinuclear π8δ4-configured µ-(η1: η1)-N2-bridged dimer. Attempts to reductively cleave the N2 unit in 7 did not lead to the expected tungsten nitride (8), which had to be prepared independently via the treatment of 7 with sodium azide. To arrive at a π10δ4-configured N2-bridged dimer in a tetragonally distorted ligand environment, [AsCCAs]ReCl3 (9) was reduced in the presence of N2. As expected, a µ-(η1: η1)-N2-bridged dirhenium species, namely, {[AsCCAs]ReCl2}2(N2) (10), was formed, but found to very quickly decompose (presumably via loss of N2), not only under reduced pressure, but also upon irradiation or heating. Hence, an alternative synthetic route to the originally envisioned nitride, [AsCCAs]Re≡N(Cl)2 (11), was developed. While all the aforementioned nitrides (3-As, 8, and 11) were found to be fairly robust, significantly different stabilities were noticed for {[AsCCAs]MCl2}2(N2) (7 for M = W, 10 for M = Re), which is ascribed to the electronically different MN2M cores (π8δ4 for 7 vs π10δ4 for 10) in these µ-(η1: η1)-N2-bridged dimers.

Chiral Bay-Alkynylated Tetraazaperylenes: Photophysics and Chiroptical Properties.

Fully bay-alkynylated octaazaperopyrene dioxide (OAPPDO) derivatives were accessible through Stille cross coupling reaction of the corresponding bay-chlorinated derivatives. This steric congestion of the bay area led to helically chiral fluorophores, and chiral resolution of two derivatives allowed the investigation of their chiroptical properties as well as their kinetics of enantiomerization and the related thermodynamic parameters depending on the size of the terminal alkynyl substituent. An increase of the latter resulted in stable OAPPDO atropisomers at room temperature. The dynamics of the photoexcited states of two of the OAPPDO derivatives were investigated by transient absorption (TA) and time-resolved photoluminescence (tr-PL) spectroscopy.

Coordination-Induced Radical Generation: Selective Hydrogen Atom Abstraction via Controlled Ti-C σ-Bond Homolysis.

A method for the generation of transient alkyl radicals via homolytic Ti-C bond cleavage was developed by employing a tailor-made organotitanium half-cage complex. In contrast to established metal-mediated radical initiation protocols via thermal or photochemical M-C σ-bond homolysis, radical formation is triggered solely by coordination of a solvent molecule (thf) to a titanium(IV) center. During the reaction, the nonstabilized alkyl radical is formed along with a persistent titanium(III) metalloradical, thus taming the former transient radical (persistent radical effect). Radical coupling and hydrogen atom abstraction (HAT) reactions have been explored not only experimentally but also computationally and by means of kinetic analysis. Exploiting these findings led to the development of selective HAT transformations, for example, with 9,10-dihydroanthracene. Deuterium labeling studies using selectively deuterated alkyls and 9,10-dihydroanthracene-d4 confirmed a radical pathway, which was underpinned by developing a radical-radical cross-coupling reaction for transferring the alkyl radical to a stable Sn-centered radical. To set the stage for an application in organic synthesis, a 5-endo-trig radical cyclization based on our methodology was established, and a dihydroxylated sesquiterpene was thus prepared in high diastereomeric excess.

Dioxygen Activation and Reduction by a Soluble Iron Phthalocyanine.

Iron ions in a square-planar coordination can bind molecules at the vacant axial positions and are able to transform them in stoichiometric and catalytic reactions. Nature takes advantage of these properties by incorporating iron into porphyrin systems, which play a key role not only in the binding and transport of oxygen, but also in catalytic oxidation and reduction reactions involving cytochrome P450. Although these systems have been studied extensively, there are still unresolved questions regarding the interplay between the iron ions and the surrounding ligands. Phthalocyanines (Pc) create a similar environment for metal atoms and FePc is known for a long time. However, without axial ligands FePc aggregates leading to solids of low solubility. In this work we used a known six-coordinate iron phthalocyanine derivative with bulky substituents and removed the stabilizing axial ligands. The resulting paramagnetic, four-coordinate compound does not aggregate and dissolves well so that NMR spectroscopy can be employed for studying the molecular structure and the reactivity. Solvent molecules bind weakly to the iron centers and oxygen is reduced in the presence of H-atom donors. The stoichiometric and catalytic reactivity with oxygen was studied in more detail.

Zipping up tetraazaperylene: synthesis of tetraazacoronenes via double coupling in the bay positions.

Substituted tetraazacoronene fluorophores have been obtained selectively by double Suzuki-Miyaura cross coupling of symmetrically substituted 1,2-bis(pinacolatoboryl)alkenes with a bay-substituted octaazaperopyrenedioxide (OAPPDO). Subsequent Scholl reaction of the dimethoxyphenylated derivative allowed further π-extension of the azaperylene core, yielding a highly redox-active bis(phenanthro)tetraazacoronene.

Triplet quenching pathway control with molecular dyads enables the identification of a highly oxidizing annihilator class.

Metal complex - arene dyads typically act as more potent triplet energy donors compared to their parent metal complexes, which is frequently exploited for increasing the efficiencies of energy transfer applications. Using unexplored dicationic phosphonium-bridged ladder stilbenes (P-X2+) as quenchers, we exclusively observed photoinduced electron transfer photochemistry with commercial organic photosensitizers and photoactive metal complexes. In contrast, the corresponding pyrene dyads of the tested ruthenium complexes with the very same metal complex units efficiently sensitize the P-X2+ triplets. The long-lived and comparatively redox-inert pyrene donor triplet in the dyads thus provides an efficient access to acceptor triplet states that are otherwise very tricky to obtain. This dyad-enabled control over the quenching pathway allowed us to explore the P-X2+ photochemistry in detail using laser flash photolysis. The P-X2+ triplet undergoes annihilation producing the corresponding excited singlet, which is an extremely strong oxidant (+2.3 V vs. NHE) as demonstrated by halide quenching experiments. This behavior was observed for three P2+ derivatives allowing us to add a novel basic structure to the very limited number of annihilators for sensitized triplet-triplet annihilation in neat water.

Tetraazacoronenes and Their Dimers, Trimers and Tetramers.

Tetraazacoronenes were synthesized from bay-functionalized tetraazaperylenes by Zr-mediated cyclization and four-fold Suzuki-Miyaura cross coupling. In the Zr-mediated approach, an η4 -cyclobutadiene-zirconium(IV) complex was isolated as an intermediate to cyclobutene-annulated derivatives. Using bis(pinacolatoboryl)vinyltrimethylsilane as a C2 building block gave the tetraazacoronene target compound along with the condensed azacoronene dimer as well as higher oligomers. The series of extended azacoronenes show highly resolved UV/Vis absorption bands with increased extinction coefficients for the extended aromatic cores and fluorescence quantum yields of up to 80 % at 659 nm.

[AsCCAs]-Coordinated Rhenium Hydrides and Their Reactivities Toward Unsaturated Hydrocarbons, Heterocumulenes, and CO2.

An [AsCCAs] ligand featuring a central alkyne and two flanking arsenic donors was employed for the synthesis of a trihydrido rhenium complex, while the corresponding phosphorus ligand was shown to be less suited. The reactivity of the former trihydride [AsCCAs]ReH3 (3) was examined in detail, which revealed that two alternative reaction channels may be entered in dependence of the substrate. Upon reaction of 3 with PhC≡CPh, ethylene, and CS2, monohydrides of the general formula [AsCCAs]Re(L)H with L = η2-PhC≡CPh (4), η2-H2C═CH2 (5), and η2-CS2 (6) were formed along with H2. In contrast, insertion products of the type [AsCCAs]Re(X)H2 (7-9) were obtained upon treatment of 3 with CyN═C═NCy, PhN═C═O, and Ph2C═C═O, while CO2 failed to react with 3 under identical reaction conditions. Given that several productive reactions between CO2 and hydrido rhenium carbonyls have been reported in the literature, 3 was further derivatized by introducing CO and tBuNC coligands, respectively. This led to the isolation of trans-[AsCCAs]ReH(CO)2 (trans-10) and trans-[AsCCAs]ReH(CNtBu)2 (trans-11), which were shown to thermally isomerize to the corresponding cis-configured products, cis-10 and cis-11. Interestingly, only the cis-complexes were found to react with CO2, which was rationalized by evaluating the relative nucleophilicities of the hydrides in cis-10, trans-10, cis-11, and trans-11 via Fukui analysis. The formates cis-[AsCCAs]Re(OCHO)(CO)2 (12) and cis-[AsCCAs]Re(OCHO)(CNtBu)2 (13) were isolated and shown to contain κ1-O-coordinated formate moieties. Treatment of 12 with [LutH]Cl/B(C6F5)3 (or with Ph3SiCl) led to the liberation of [LutH][OCHO···B(C6F5)3] (or triphenylsilyl formate) with concomitant formation of the expected chloro complex cis-[AsCCAs]ReCl(CO)2 (14). In a closed synthetic cycle, hydride 12 was regenerated from the latter chloride using NaBEt3H as a hydride source.

The Telluraboranes closo-TeB5 Cl5 and closo-TeB11 Cl11 with Exceptionally Long Body Diagonals: Synthetic and Bonding Motifs for Innovative Octahedral and Icosahedral Geometries.

Six-vertex closo-TeB5 Cl5 (1) and twelve-vertex closo-TeB11 Cl11 (2) telluraboranes have been prepared via co-pyrolysis of B2 Cl4 with TeCl4 in vacuo at temperatures between 360 °C and 400 °C. Both compounds are sublimable, off-white solids, and they have been characterized by one- and two-dimensional 11 B NMR and high-resolution mass spectroscopy. Both ab initio/GIAO/NMR and DFT/ZORA/NMR computations support octahedral and icosahedral geometries for 1 and 2, respectively, as expected due to their closo-electron counts. The octahedral structure of 1 has been confirmed by single-crystal X-ray diffraction on an incommensurately modulated crystal. The corresponding bonding properties have been analyzed in terms of the intrinsic bond orbital (IBO) approach. 1 is the first example of a polyhedral telluraborane with a cluster size smaller than 10 vertices.

Martin's Phosphino-Triol Revisited: Unexpected P-C Bond Cleavage Reactions and Their Suppression via Complexation of Al3+ and Sc3.

A revised synthesis of Martin's phosphino-triols (two derivatives) is reported. Once isolated, these thermally sensitive triols were shown to disassemble selectively via an unexpected P-C bond cleavage reaction. This degradation pathway was effectively suppressed via complexation of Al3+ and Sc3+. In the resulting half-cage complexes, the ligand scaffold is bound to each metal (Al3+ and Sc3+, respectively) via all four donor atoms. So far, this κ4-P,O,O',O″-coordination mode has not been observed for any other phosphino-triol.

Selective Reduction of CO2 to a Tantalum Formate Complex and Release of Methyl Formate from the Tantalum(V) Center.

A cyclometalated NHC-coordinated hydrido tantalum alkoxide was found to selectively react with CO2 to afford the genuine tantalum formate (NHC)(HCOO)Ta(ORF)3 with ORF = OC(CF3)2CH3. In the solid state, the presence of a κ2-O,O-formate moiety was established by single-crystal X-ray diffraction and ATR-IR spectroscopy, while NMR experiments and DFT modeling studies suggest that the κ1-O-coordination mode is preferred in solution. Despite the accessibility of the latter κ1-O-formate in solution, no over-reduction to a dinuclear methylene diolate was observed. Upon treatment with MeOTf, the κ1-O-formate was methylated selectively, which led to the formation of a tantalum triflate complex along with methyl formate. This is a rare example in which a value-added oxygen-containing organic product (here HCOOMe) is released from an oxophilic early transition metal (here TaV).

Molybdenum-Mediated N2 -Splitting and Functionalization in the Presence of a Coordinated Alkyne.

A new [PCCP]-coordinated molybdenum platform comprising a coordinated alkyne was employed for the cleavage of molecular dinitrogen. The coordinated η2 -alkyne was left unaffected during this reduction. DFT calculations suggest that the reaction proceeds via an initially generated terminal N2 -complex, which is converted to a dinuclear µ-(η1 :η1 )-N2 -bridged intermediate prior to N-N bond cleavage. Protonation, alkylation and acylation of the resulting molybdenum nitrido complex led to the corresponding N-functionalized imido complexes. Upon oxidation of the N-acylated imido derivative in MeCN, a fumaronitrile fragment was built up via C-C coupling of MeCN to afford a dinuclear molybdenum complex. The key finding that the strong N≡N bond may be cleaved in the presence of a weaker, but spatially constrained C≡C bond contradicts the widespread paradigm that coordinated alkynes are in general more reactive than gaseous N2 .

A 2,2'-diphosphinotolane as a versatile precursor for the synthesis of P-ylidic mesoionic carbenes via reversible C-P bond formation.

A metal-templated synthetic route to cyclic (aryl)(ylidic) mesoionic carbenes (CArY-MICs) featuring an endocyclic P-ylide is presented. This approach, which requires metal templates with two cis-positioned open coordination sites, is based on the controlled cyclisation of a P,P'-diisopropyl-substituted 2,2'-diphosphinotolane (1) and leads to chelate complexes coordinated by a phosphine donor and the CArY-MIC carbon atom. The C-P bond formation involved in the former partial cyclisation of 1 proceeds under mild conditions and was shown to be applicable all over the d-block. In the presence of a third fac-positioned open coordination site, the P-C bond formation was found to be reversible, as shown for a series of molybdenum complexes. DFT modelling studies are in line with an interpretation of the target compounds as CArY-MICs.

Reductive Hydrogenation under Single-Site Control: Generation and Reactivity of a Transient NHC-Stabilized Tantalum(III) Alkoxide.

One of the most attractive routes for the preparation of reactive tantalum(III) species relies on the efficient salt-free hydrogenolysis of tantalum(V) alkyls or tantalum(V) alkylidenes, a process known as reductive hydrogenation. For silica-crafted tantalum alkyls and alkylidenes, this process necessarily proceeds at well-separated tantalum centers, while related reductive hydrogenations in homogeneous solution commonly involve dimeric complexes. Herein, an NHC scaffold was coordinated to a novel tri(alkoxido)tantalum(V) alkylidene to circumvent the formation of dimers during reductive hydrogenation. Employing this new model system, a key intermediate of the process, namely a hydrido-tantalum alkyl, was isolated for the first time and shown to exhibit a bidirectional reactivity. Upon being heated, the latter complex was found to undergo either an α-elimination or a reductive alkane elimination. In the (overall unproductive) α-elimination step, H2 and the parent alkylidene were regenerated, while the sought-after transient d2-configured tantalum(III) derivative was produced along the reaction coordinate of the reductive alkane elimination. The reactive low-valence metal center was found to rapidly attack one of the NHC substituents via an oxidative C-H activation, which led to the formation of a cyclometalated tantalum(V) hydride. The proposed elemental steps are in line with kinetic data, deuterium labeling experiments, and density functional theory (DFT) modeling studies. DFT calculations also indicated that the S = 0 spin ground state of the Ta(III) center plays a crucial role in the cyclometalation reaction. The cyclometalated Ta(V) hydride was further investigated and reacted with several alkenes and alkynes. In addition to a rich insertion and isomerization chemistry, these studies also revealed that the former hydride may undergo a formal cycloreversion and thus serve as a tantalum(III) synthon, although the original tantalum(III) intermediate is not involved in this process. The latter reactivity was observed upon reaction with internal alkynes and led to the corresponding η2-alkyne derivatives via vinyl intermediates, which rearrange via a remarkable, hitherto unprecedented, hydrogen shift reaction.

P-Protected Diphosphadibenzo[ a, e]pentalenes and Their Mono- and Dicationic P-Bridged Ladder Stilbenes.

The previously elusive diphosphadibenzo[ a, e]pentalene core skeleton was assembled via a surprisingly straightforward cyclization pathway starting from R2P-substituted 2,2'-diphosphinotolanes (R = Ph, iPr). The resulting P-protected diylidic compounds 4 (R = Ph, iPr) were converted to the corresponding P-bridged ladder stilbenes via two consecutive oxidation steps: upon selective one-electron oxidation, the persistent radical monocations 5 (R = Ph, iPr) were obtained and further oxidized to afford the respective fluorescent and air-stable dications 6 (R = Ph, iPr).

A Tautomeric λ3/λ5-Phosphane Pair and Its Ambiphilic Reactivity.

The central phosphorus atom of a novel hydroxyl-functionalized triarylphosphane was shown to reversibly insert into one of the molecule's O-H bonds, which forms the basis for a tautomeric λ3/λ5-phosphane equilibrium. For the first time, this equilibrium was detected for a λ3-triarylphosphane and the underlying dynamic process was elucidated by NMR spectroscopy. On the basis of reactivity studies, a nucleophilic character was assigned to the minor species present in solution, the λ3-phosphane. Upon methylation, for example, the λ3-form was selectively removed from the equilibrium and converted to the corresponding phosphonium salt. However, upon generation of an alkoxide via proton abstraction, the electrophilic character of the λ5-phosphane in the equilibrium became evident since the alkoxide was found to attack the molecule's phosphorus atom. This intramolecular reaction led to the selective formation of a new anionic λ6-hydridospirophosphane.

Benzylene-linked [PNP] scaffolds and their cyclometalated zirconium and hafnium complexes.

The benzylene-linked [PNP] scaffolds HN(CH2-o-C6H4PPh2)2 ([A]H) and HN(C6H4-o-CH2PPh2)2 ([B]H) have been used for the synthesis of zirconium and hafnium complexes. For both ligands, the dimethylamides [A]M(NMe2)3 ([A]1-M) and [B]M(NMe2)3 ([B]1-M) were prepared and converted to the iodides [A]MI3 ([A]2-M) and [B]MI3 ([B]2-M) (M = Zr, Hf). Starting from these iodides, the corresponding benzyl derivatives [A]MBn3 ([A]3-M) and [B]MBn3 ([B]3-M) (M = Zr, Hf) were obtained via reaction with Bn2Mg(OEt2)2. For zirconium, the benzylic ligand positions in [A]3-Zr and [B]3-Zr were found to cyclometalate readily, which led to the corresponding κ4-[PCNP]ZrBn2 complexes [A]4-Zr and [B]4-Zr. As these complexes failed to hydrogenate cleanly, cyclometalated derivatives with only one alkyl substituent were targeted and the mixed benzyl chlorides κ4-[PCNP]MBnCl ([B]5-M, M = Zr, Hf) were obtained in the case of ligand [B]. Upon hydrogenation of [B]5-Zr, the η6-tolyl complex [B]Zr(η6-C7H8)Cl ([B]6-Zr) was generated cleanly, but the corresponding hafnium complex [B]5-Hf was found to decompose unselectively in the presence of H2. Using a closely related carbazole-based [PNP] ligand, Gade and co-workers have shown recently that zirconium η6-arene complexes similar to [B]6-Zr may serve as zirconium(ii) synthons, namely when reacted with 2,6-Dipp-NC (L) or pyridine (py). Both these substrates were shown to react cleanly with [B]6-Zr, which led to the formation of the bis-isocyanide complex [B]ZrCl(L)2 ([B]7-Zr) and the 2,2'-bipyridine derivative [B]ZrCl(bipy) ([B]8-Zr), respectively. Upon reaction of [B]Zr(η6-C7H8)Cl ([B]6-Zr) with NaBEt3H, the cyclometalated derivative κ4-[PCNP]Zr(η6-C7H8) ([B]9-Zr) was isolated. In an attempt to synthesise terminal hydrides, complexes [A]MI3 ([A]2-M) were treated with KBEt3H, which led to the isolation of the cyclometalated hydrido complexes κ4-[PCNP]M(H)(κ3-Et3BH) ([A]10-M; M = Zr, Hf) featuring a κ3-bound triethyl borohydride moiety.

Synthesis of NPN-Coordinated Tantalum Alkyl Complexes and Their Hydrogenolysis: Isolation of a Terminal Tantalum Hydride Incorporating a Doubly Cyclometalated NPN Scaffold.

The closely related benzylene-linked diaminophosphines PhP(CH2C6H4-o-NHPh)2 (AH2) and PhP(C6H4-o-CH2NHXyl)2 (BH2 with Xyl = 3,5-Me2C6H3) were employed for the synthesis of tantalum(V) alkyls, which were then studied with respect to hydrogenolysis. In the case of AH2, the tantalum trimethyl complex [Ta(A)Me3] (1) and the tantalum hydrocarbyl complex [Ta(A)(CH2SiMe3)(η2-EtC≡CEt)] (2) were prepared from the ligand's dilithium salt (A)Li2(diox). Upon hydrogenolysis of 1 and 2, the formation of methane and SiMe4, respectively, was observed, but well-defined tantalum hydrides could not be detected. In the case of BH2, the cyclometalated species [Ta(B*)(NMe2)2] (3 with B* = κ4-N,P,N,C-(PhP(C6H4-o-CH2NXyl)(C6H4-o-CHNXyl))3-) was isolated and converted to the corresponding diiodo species [Ta(B*)I2] (4). Treatment of 4 with LiCH2SiMe3 resulted in the isolation of the corresponding dialkyl complex [Ta(B*)(CH2SiMe3)2] (5), which was converted to the doubly cyclometalated monoalkyl complexes [Ta(B**)(CH2SiMe3)(PMe3)] (6 with B** = κ5-C,N,P,N,C-(PhP(C6H4-o-CHNXyl)2)4-) and [Ta(B**)(CH2SiMe3)(dmpe)] (7) via reaction with PMe3 and dmpe, respectively. In contrast to 5 and 6, 7 was found to react cleanly with dihydrogen to afford the corresponding terminal tantalum(V) hydride [Ta(B**)(H)(dmpe)] (8). Upon reaction of 7 with D2, the deuteride [Ta(d2-B**)(D)(dmpe)] (9) was obtained and found to contain deuterium atoms in the methine positions of both tantalaaziridine subunits. The partially deuterated derivatives [Ta(B**)(D)(dmpe)] (10) and [Ta(d2-B**)(H)(dmpe)] (11) were generated via reaction of 8 and 9 with PhSiD3 and PhSiH3, respectively. Prior to the addition of gaseous D2 or H2, no H/D scrambling was observed in 10 or 11, indicating that the exchange of the methine positions proceeds via addition of D2 or H2 across the tantalaaziridine Ta-C bonds.