Reactivities of phosphaalkynes towards diverse bis-silylenes.

Bis-silylenes do not only act as strong chelating σ-donor ligands, but also exhibit cooperative behaviour in the activation of small molecules. Three different P-Si containing molecules were prepared from the reaction between tBuCP and different bis-silylenes, which are bridged by ferrocenediyl, diaminobenzene, or o-carborane.

Phospholyl and Arsolyl Triple-Decker Sandwich Complexes of Europium(II) and Strontium(II).

To study the influence of heteroatoms on the photophysical properties of divalent Eu and Sr complexes, the synthesis of the phospholyl and arsolyl compounds [{(Dtp)(thf)M}2{µ-η8:η8-C8H8}] (M = EuII and SrII; Dtp = 3,4-dimethyl-2,5-bis(tert-butyl)phospholyl) and [{(Dtas)(thf)M}2{µ-η8:η8-C8H8}] (M = EuII and SrII; Dtas = 3,4-dimethyl-2,5-bis(tert-butyl)arsolyl) is reported. Organometallic compounds of divalent europium with P and As heterocyclic ligands have not been described previously. They were prepared by salt elimination reactions from potassium phospholyl or arsolyl, K2C8H8, and EuI2(thf)2 or SrI2. Photophysical properties were investigated alongside a reference cyclopentadienyl complex with a comparable structure. Critically, the influence of the heteroatom on the photoluminescence emission and excitation and quantum yields of the complexes is significant. Density functional theory calculations were performed to rationalize the ligand influences.

Luminescent Tetranuclear Copper(I) and Gold(I) Heterobimetallic Complexes: A Phosphine Acetylide Amidinate Orthogonal Ligand Framework for Selective Complexation.

The synthesis of phosphine acetylide amidinate stabilized copper(I) and gold(I) heterobimetallic complexes was achieved by reacting ligand [{Ph2PC≡CC(NDipp)2}Li(thf)3] (Dipp=2,6-N,N'-diisopropylphenyl) with CuCl and Au(tht))Cl, yielding the eight membered ring [{Ph2PC≡CC(NDipp)2}2Cu2] and the twelve membered ring [{Ph2PC≡CC(NDipp)2}2Au2]. {Ph2PC≡CC(NDipp)2}2Cu2] features a Cu2 unit, which is bridged by two amidinate ligands, served as a metalloligand to synthesize the heterobimetallic CuI/AuI complexes [{(AuX)Ph2PC≡CC(NDipp)2}2Cu2] (X=Cl, C6F5). In these reactions, the central ring structure is retained. In contrast, when the twelve membered ring [{Ph2PC≡CC(NDipp)2}2Au2] was reacted with CuX (X=Cl, Br, I and Mes), the reaction led to the rearrangement of the central ring structure to give [{(AuX)Ph2PC≡CC(NDipp)2}2Cu2] (X=Cl, Br, I and Mes), which feature the same the eight membered Cu2 ring as above. These compounds were also synthesized by a one-pot reaction. The luminescent heterobimetallic complexes were further investigated for their photophysical properties.

Cycloheptatrienyl-Bridged Triple-Decker Complexes.

The first structurally characterized organometallic multidecker sandwich complexes featuring a cycloheptatrienyl ring (Cht, C7H73-) in the coordination sphere are presented. The synthesis of inverse sandwich complexes of the rare earth elements YIII and ErIII with a bridging cycloheptatrienyl ligand of the type [(thf)(BH4)2LnIII(µ-η7:η7-Cht)LnIII(BH4)(thf)2] is described first. The subsequent introduction of the CotTIPS ligand (CotTIPS = 1,4-(iPr3Si)2C8H62-) into the coordination sphere of the rare earth cations resulted in the isolation of unprecedented triple-decker compounds with the formula [(thf)3K{(η8-CotTIPS)LnIII}2(µ-η7:η7-Cht)], bearing a seven-membered aromatic carbon ring as a middle deck. These compounds are also the first examples of rare earth triple-decker complexes not bridged by a Cot derivative, based on purely carbon-based ligands. The magnetic properties of the respective ErIII congeners were investigated in detail, leading to the observation of antiferromagnetic coupling of the ErIII cations and a blocking temperature of 13.5 K. The conversion of the YIII compound [(thf)3K{(η8-CotTIPS)YIII}2(µ-η7:η7-Cht)] with [YIII(Cot)I(thf)2] resulted in ligand rearrangement and the selective formation of the first triple-decker complex ([(η8-CotTIPSYIII)2(µ-η8:η8-Cot)]) featuring two Cot ligands with different substituents in its coordination sphere.

Förster resonance energy transfer within single chain nanoparticles.

Single chain nanoparticles (SCNPs) are a highly versatile polymer architecture consisting of single polymer chains that are intramolecularly crosslinked. Currently, SCNPs are discussed as powerful macromolecular architectures for catalysis, delivery and sensors. Herein, we introduce a methodology based on Förster Resonance Energy Transfer (FRET) to evidence the folding of single polymer chains into SCNPs via fluorescence readout. We initially introduce a molecular FRET pair based on a bimane and nitrobenzoxadiazole (NBD) moiety and study its fluorescence properties in different solvents. We subsequently construct a low dispersity polymer chain carrying NBD units, while exploiting the bimane units for intramolecular chain collapse. Upon chain collapse and SCNP formation - thus bringing bimane and NBD units into close proximity - the SCNPs report their folded state by a strong and unambiguous FRET fluorescence signal. The herein introduced reporting of the folding state of SCNPs solely relies on an optical readout, opening avenues to monitoring SCNP folding without recourse to complex analytical methodologies.

[GeRu6(CO)18HI]: A Germanium-Centered Ruthenium Carbonyl Cluster with Aromatic Ring Current.

The carbonyl cluster compound [GeRu6(CO)18HI] is unique in regard to its structure and bonding with a GeRu6 cluster core, a planar GeRu4HI unit, extensive multi-center bonding, and an aromatic ring current similar to benzene (9-10 nA T-1). The open-shell cluster core is a Ge-centered five-membered Ru4(Ru2) ring with CO ligands and an additional H and I atom, each bridging two Ru atoms on opposite sides of the cluster core. The compound is prepared at 130 °C in a weakly-coordinating ionic liquid.

Unique Double and Triple Decker Arrangements of Rare-Earth 9,10-Diborataanthracene Complexes Featuring Single-Molecule Magnet Characteristics.

Herein, we present the first report on the synthesis of rare-earth complexes featuring a 9,10-diborataanthracene ligand. This 14-π-electron ligand is highly reductive and was previously used in small-molecule activation. Salt elimination reactions between dipotassium 9,10-diethyl-9,10-diborataanthracene [K2(DEDBA)] and [LnIII(η8-CotTIPS)(BH4)(thf)x] (CotTIPS=1,4-(iPr3Si)2C8H6) in a 1 : 1 ratio yielded heteroleptic sandwich complexes [K(η8-CotTIPS)LnIII(η6-DEDBA)] (Ln=Y, Dy, Er). These compounds form Lewis-base-free one-dimensional coordination polymers when crystallised from toluene. In contrast, reaction of [K2(DEDBA)] and [LnIII(η8-CotTIPS)(BH4)(thf)x] in a 1 : 2 ratio led to the formation of heteroleptic triple-decker complexes [(η8-CotTIPS)LnIII(µ-η6:η6-DEDBA)LnIII(η8-CotTIPS)] (Ln=Y, Dy, Er). Notably, these are not only the first lanthanide triple-decker compounds featuring a six-membered ring as a deck but also the first trivalent lanthanide triple-decker featuring a heterocycle in the coordination sphere. Magnetic investigations reveal that [K(η8-CotTIPS)LnIII(η6-DEDBA)] (Ln=Dy, Er) and [(η8-CotTIPS)ErIII(µ-η6:η6-DEDBA)ErIII(η8-CotTIPS)] exhibit Single-Molecule Magnet (SMM) behaviour. In the case of [(η8-CotTIPS)LnIII(µ-η6:η6-DEDBA)LnIII(η8-CotTIPS)] (Ln=Dy, Er), the introduction of a second near lanthanide ion results in strong antiferromagnetic interactions, allowing the enhancement of the magnetic characteristic of the system, compared to the quasi isolated counterpart. This research renews the overlooked coordination chemistry of the DBA ligand and expands it to encompass rare-earth elements.

It's not just the size that matters: crystal engineering of lanthanide-based coordination polymers.

Synthesis and characterization of Lewis base free coordination polymers of selected lanthanides are presented. For this purpose, the substituted CotTIPS ligand (CotTIPS = 1,4-bis-triisopropylsilyl-cyclo-octatetraendiide) was used to synthesize homoleptic, anionic multidecker compounds of the type [K{LnIII(ɳ8-CotTIPS)2}]n. Depending on the solvent used for crystallization and the ionic radii of the lanthanide cations, three different categories of one-dimensional heterobimetallic coordination polymers were obtained in the solid state. For the early lanthanides La and Ce a unique helical conformation was obtained by crystallization from toluene, while the ionic radius of Pr seems to be a turning point towards the crystallization of zigzag polymers. For Er a third structural motif, a trapezoidal wave polymer was observed. Additionally, the zigzag polymer for all compounds could be obtained by changing the solvent from toluene to Et2O, reavealing a correlation between solid-state structure and ionic radii as well as solvent. While photoluminescence (PL) properties of Cot-lanthanide compounds are scarce, the La complexes show ligand centered green luminescence, whereas the Ce complexes reveal deep red emission origin from d-f transitions. The Er-compounds are single-molecule magnets, in which the magnetic relaxation of each Er ion occurs isolated from its neighbors at temperatures above 10 K, while below 9 K a strong antiferromagnetic coupling between the Er ions was seen.

Synthesis, Structural Characterization, and Magnetic Properties of Lanthanide Arsolyl Sandwich Complexes.

A series of trivalent lanthanide sandwich complexes [(η5-C4R4As)Ln(η8-C8H8)] using three different arsolyl ligands are reported. The complexes were obtained via salt elimination reactions between potassium arsolyl salts and lanthanide precursors [LnI(COT)(THF)2] (Ln = Sm, Dy, Er; COT = η8-C8H8). The resulting compounds exhibit classical sandwich complex structures with one notable exception. Characterization was conducted in both the solid state using single-crystal X-ray diffraction and in solution for the Sm compounds using NMR spectroscopy. Furthermore, the magnetic properties of an Er complex were investigated, revealing distinctive single-molecule-magnet behavior characterized by an energy barrier of Ueff = 323.3 K. Theoretical calculations were employed to support and interpret the experimental findings, with a comparative analysis performed against previously reported complexes.

Bi- and tridentate coordination behaviour of a novel bis(phosphinimino)methanide ligand.

Herein, we report the synthesis of a novel ferrocenyl-functionalized bis(phosphinimino)methane ligand (CH2 (PPh2 NFc)2 ). Deprotonation of CH2 (PPh2 NFc)2 with KN(SiMe3 )2 gave the dimeric species [K{CH(PPh2 NFc)2 }]2 , which was further reacted with ECl2 (E=Ge, Sn) to yield the tetrylene compounds [{CH(PPh2 NFc)2 }ECl]. The ligand and the resulting tetrylenes were examined for their electrochemical properties with the aid of cyclic voltammetry. Furthermore, the reaction of the tetrylenes [{CH(PPh2 NFc)2 }ECl] with [AuC6 F5 (tht)] resulted in the bimetallic complexes [{(AuC6 F5 )CH(PPh2 NFc)2 }ECl] with an unusual Au coordination on the ligand backbone.

Reactivity of [Cp*Fe(η5 -As5 )] towards Carbenes, Silylenes and Germylenes.

The reaction behavior of [Cp*Fe(η5 -As5 )] (I) (Cp*=C5 Me5 ) towards carbenes and their heavier analogs was investigated. The reaction of I with NHCs (NHCs=N-heterocyclic carbenes) results in the first substitution products of polyarsenic ligand complexes by NHCs [Cp*Fe(η4 -As5 NHC)] (1 a: NHC=IMe=1,3,4,5-tetramethylimidazolin-2-ylidene, 1 b: NHC=IMes=1,3-bis(2,4,6-trimethylphenyl)-imidazolin-2-ylidene). In contrast, the reaction of I with Et CAAC (Et CAAC=2,6-diisopropylphenyl)-4,4-diethyl-2,2-dimethyl-pyrrolidin-5-ylidene) leads to a fragmentation and the formation of an unprecedented As6 -sawhorse-type compound [As2 (AsEt CAAC)4 ] (2). The reaction of (LE)2 (L=PhC(Nt Bu)2 ; E=Si, Ge) with I resulted in a rearrangement and an insertion of LE fragments, forming unique silicon- (4: [Cp*Fe(η4 -As4 SiL)], 5 a: [Cp*Fe(η4 -As6 SiL)) and germanium-containing (5 b: [Cp*Fe(η4 -As6 GeL)) cyclic polyarsenic ligand complexes.

Single Chain Nanoparticles in Catalysis.

Over the last six decades folded polymer chains-so-called Single Chain Nanoparticles (SCNPs)-have evolved from the mere concept of intramolecularly crosslinked polymer chains to tailored nanoreactors, underpinned by a plethora of techniques and chemistries to tailor and analyze their morphology and function. These monomolecular polymer entities hold critical promise in a wide range of applications. Herein, we highlight the exciting progress that has been made in the field of catalytically active SCNPs in recent years.

Role of Bis(phosphinimino)methanides as Universal Ligands in the Coordination Sphere of Metals across the Periodic Table.

The coordination chemistry of bis(phosphinimino)methanide ligands is widespread and accompanies a large number of metal ions in the periodic table ranging from lithium to neptunium. This unique class of ligand systems show copious coordination chemistry with the main-group, transition, rare-earth, and actinide metals and are considered to be among the most attractive ligand systems to researchers. The bis(phosphinimino)methanide metal complexes offer an extensive range of applications in various fields and have been demonstrated as one of the universal ligand systems to stabilize the metal ions in not only their usual but also their unusual oxidation states. The main-group and transition metal chemistry using bis(phosphinimino)methanides as ligands was last updated almost a decade ago. In this review, we provide a comprehensive overview of various state-of-the-art bis(phosphinimino)methanide-supported metal complexes by dealing with their synthesis, characterization, reactivity, and catalytic studies which were not included in the last critical reviews.

Heteroleptic copper(I) complexes with coumarin-substituted aminodiphosphine and diimine ligands: synthesis and photophysical studies.

The synthesis of heteroleptic Cu(I) complexes with coumarin-functionalized aminodiphosphine and diimine ligands is described. The complexes show yellow to deep-red phosphorescence in the solid state at ambient temperature with quantum yields up to 21%. The emission color of the complexes can be tuned by systematic modifications in the ligand system.

Synthesis and properties of cyclic sandwich compounds.

Cyclic nanometre-scale sandwich complexes assembled from individual building blocks were synthesized. Sandwich complexes, in which a metal ion is π-coordinated by two planar aromatic organic rings belong to the foundations of organometallic chemistry. They have been successfully used in a wide variety of applications ranging from catalysis, synthesis and electrochemistry to nanotechnology, materials science and medicine1,2. Extending the sandwich structural motif leads to linear multidecker compounds, in which aromatic organic rings and metal atoms are arranged in an alternating fashion. However, the extension to a cyclic multidecker scaffold is unprecedented. Here we show the design, synthesis and characterization of an isomorphous series of circular sandwich compounds, for which the term 'cyclocenes' is suggested. These cyclocenes consist of 18 repeating units, forming almost ideally circular, closed rings in the solid state, that can be described by the general formula [cyclo-MII(µ-η8:η8-CotTIPS)]18 (M = Sr, Sm, Eu; CotTIPS = 1,4-(iPr3Si)2C8H62-). Quantum chemical calculations lead to the conclusion that a unique interplay between the ionic metal-to-ligand bonds, the bulkiness of the ligand system and the energy gain on ring closure, which is crucially influenced by dispersion interactions, facilitate the formation of these cyclic systems. Up to now, only linear one-dimensional multidecker sandwich compounds have been investigated for possible applications such as nanowires3-10. This textbook example of cyclic sandwich compounds is expected to open the door for further innovations towards new functional organometallic materials.

Mono-cyclononatetraenyl lanthanide complexes.

The synthesis of the first half-sandwich complexes based on the cyclononatetraenyl (Cnt = C9H9-) ligand ([LnIII(η9-Cnt)(η3-BH4)2(thf)] (Ln = La, Ce)) is reported. The title compounds were obtained from the reaction of [Ln(BH4)3(thf)3] and [K(Cnt)]. Further solvation of [LnIII(η9-Cnt)(η3-BH4)2(thf)] with tetrahydrofuran (THF) resulted in a reversible decoordination of the Cnt ring and the formation of the ionic species [LnIII(η3-BH4)2(thf)5][Cnt]. Removal of THF from [LaIII(η9-Cnt)(η3-BH4)2(thf)] gave the polymeric compound [LaIII(µ-η2:η2-BH4)2(η3-BH4)(η9-Cnt)]n.

Diverse Reactions of Formazanate/Formazan with Tetrylenes: Reduction, C-H Bond Activation, Substitution and Addition.

The reactivity of the formazanate potassium salt [LtBu K(thf)] (LtBu= PhNNC(4-t BuPh)NNPh) with the group 14 chlorotetrylenes [{PhC(t BuN)2 }ECl] (E=Si, Ge, Sn) was investigated. Three corresponding compounds with unique configurations were formed, demonstrating the diverse reactivity of the system. In addition to the anticipated salt metathesis reactions of the potassium salt with the chlorine function of tetrylenes, unexpected reduction/insertion steps into the N=N bond of the formazanate (Si, Ge) and subsequent C-H activation (Ge) were also observed. Furthermore, when the neutral formazan ligand [LtBu H] was exposed to silylenes [{PhC(t BuN)2 }SiCl] and [LPh SiNMePy], substitution and addition reactions occurred. These discoveries significantly enrich the diversity of formazanate/formazan redox chemistry, opening up new avenues for exploration in this field.

Visible-Light-Induced Control over Reversible Single-Chain Nanoparticle Folding.

We introduce a class of single-chain nanoparticles (SCNPs) that respond to visible light (λmax =415 nm) with complete unfolding from their compact structure into linear chain analogues. The initial folding is achieved by a simple esterification reaction of the polymer backbone constituted of acrylic acid and polyethylene glycol carrying monomer units, introducing bimane moieties, which allow for the photochemical unfolding, reversing the ester-bond formation. The compaction and the light driven unfolding proceed cleanly and are readily followed by size exclusion chromatography (SEC) and diffusion ordered NMR spectroscopy (DOSY), monitoring the change in the hydrodynamic radius (RH ). Importantly, the folding reaction and the light-induced unfolding are reversible, supported by the high conversion of the photo cleavage. As the unfolding reaction occurs in aqueous systems, the system holds promise for controlling the unfolding of SCNPs in biological environments.

Snapshots of sequential polyphosphide rearrangement upon metallatetrylene addition.

Insertion and functionalization of gallasilylenes [LPhSi-Ga(Cl)LBDI] (LPh = PhC(NtBu)2; LBDI = [{2,6-iPr2C6H3NCMe}2CH]) into the cyclo-E5 rings of [Cp*Fe(η5-E5)] (Cp* = η5-C5Me5; E = P, As) are reported. Reactions of [Cp*Fe(η5-E5)] with gallasilylene result in E-E/Si-Ga bond cleavage and the insertion of the silylene in the cyclo-E5 rings. [(LPhSi-Ga(Cl)LBDI){(η4-P5)FeCp*}], in which the Si atom binds to the bent cyclo-P5 ring, was identified as a reaction intermediate. The ring-expansion products are stable at room temperature, while isomerization occurred at higher temperature, and the silylene moiety further migrates to the Fe atom, forming the corresponding ring-construction isomers. Furthermore, reaction of [Cp*Fe(η5-As5)] with the heavier gallagermylene [LPhGe-Ga(Cl)LBDI] was also investigated. All the isolated complexes represent rare examples of mixed group 13/14 iron polypnictogenides, which could only be synthesized by taking advantage of the cooperativity of the gallatetrylenes featuring low-valent Si(ii) or Ge(ii) and Lewis acidic Ga(iii) units/entities.

Divalent metallocenes of the lanthanides - a guideline to properties and reactivity.

Since the discovery in the early 1980s, the soluble divalent metallocenes of lanthanides have become a steadily growing field in organometallic chemistry. The predominant part of the investigation has been performed with samarium, europium, and ytterbium, whereas only a few reports dealing with other rare earth elements were disclosed. Reactions of these metallocenes can be divided into two major categories: (1) formation of Lewis acid-base complexes, in which the oxidation state remains +II; and (2) single electron transfer (SET) reductions with the ultimate formation of Ln(III) complexes. Due to the increasing reducing character from Eu(II) over Yb(II) to Sm(II), the plethora of literature concerning redox reactions revolves around the metallocenes of Sm and Yb. In addition, a few reactivity studies on Nd(II), Dy(II) and mainly Tm(II) metallocenes were published. These compounds are even stronger reducing agents but significantly more difficult to handle. In most cases, the metals are ligated by the versatile pentamethylcyclopentadienyl ligand: (C5Me5). Other cyclopentadienyl ligands are fully covered but only discussed in detail, if the ligand causes differences in synthesis or reactivity. Thus, the focus lays on three compounds: [(C5Me5)2Sm], [(C5Me5)2Eu] and [(C5Me5)2Yb] and their solvates. We discuss the synthesis and physical properties of divalent lanthanide metallocenes first, followed by an overview of the reactivity rendering the full potential of these versatile reactants.