Liquid Injection Field Desorption Ionization Research Articles

Aluminiumalkylinduzierte Isomerisierung von Gruppe IV meso Metallocen Komplexen

AbstractBei der Synthese von Gruppe IV Metallocen‐Präkatalysatoren für die Polymerisation von Propylen werden im Allgemeinen zwei verschiedene Isomere gebildet: Das racemische Isomer, das isotaktisches Polypropylen (iPP) produziert und das meso‐Isomer, das ataktisches Polypropylen (aPP) produziert. Aufgrund seiner vergleichbar schlechten physikalischen Eigenschaften ist die Anwendung von aPP sehr begrenzt. Um Mischungen beider Polymere zu vermeiden, was die mechanischen und thermischen Eigenschaften von iPP zu verschlechtern würde, müssen die meso Metallocenkomplexe mühsam von den racemischen Komplexen getrennt werden, was die Metallocen‐basierte Polymerisation von Propylen industriell weit weniger attraktiv macht als das Ziegler/Natta‐Verfahren. Um dieses Problem zu umgehen, haben wir ein Isomerisierungsprotokoll zur Umwandlung von meso Metallocenkomplexen in ihre racemischen Analoga entwickelt. Dieses Protokoll steigerte die Ausbeute an iPP um 400 %, wobei die hervorragenden physikalischen Eigenschaften des Polymers beibehalten wurden; es war sowohl auf Hafnocen‐, als auch auf Zirkonocenkomplexe, sowie auf verschiedene Methoden zur Aktivierung des Präkatalysators anwendbar. Durch gezielte Variation der Liganden wurden Methoxygruppen an den Indenylsubstituenten als die für eine Isomerisierung verantwortlichen Strukturmotive gefunden ‐ dieser experimentelle Nachweis wurde durch Dichtefunktionaltheorieberechnungen bestätigt. Flüssig‐Injektion‐Feld‐Desorption‐Ionisierung‐Massenspektrometrie, sowie 1H‐ und 29Si‐Kernresonanzstudien ermöglichten den Vorschlag eines Isomerisierungsmechanismus.

Aluminum Alkyl Induced Isomerization of Group IV meso Metallocene Complexes.

The synthesis of group IV metallocene precatalysts for the polymerization of propylene generally yields two different isomers: The racemic isomer that produces isotactic polypropylene (iPP) and the meso isomer that produces atactic polypropylene (aPP). Due to its poor physical properties, aPP has very limited applications. To avoid obtaining blends of both polymers and thus diminish the mechanical and thermal properties of iPP, the meso metallocene complexes need to be separated from the racemic ones tediously-rendering the metallocene-based polymerization of propylene industrially far less attractive than the Ziegler/Natta process. To overcome this issue, we established an isomerization protocol to convert meso metallocene complexes into their racemic counterparts. This protocol increased the yield of iPP by 400 % while maintaining the polymer's excellent physical properties and was applicable to both hafnocene and zirconocene complexes, as well as different precatalyst activation methods. Through targeted variation of the ligand frameworks, methoxy groups at the indenyl moieties were found to be the structural motifs responsible for an isomerization to take place-this experimental evidence was confirmed by density functional theory calculations. Liquid injection field desorption ionization mass spectrometry, as well as 1H and 29Si nuclear magnetic resonance studies, allowed the proposal of an isomerization mechanism.

Synthesis, characterization, and liquid injection field desorption ionization mass spectrometry analysis of pincer ligated group 6 (Cr, Mo, W) carbonyl complexes.

We report the synthesis of molybdenum and tungsten bromo dicarbonyl complexes (POCOPtBu)MIIBr(CO)2 (M = Mo or W; POCOPtBu = κ3-C6H3-1,3-[OP(tBu)2]2) supported by an anionic PCP pincer ligand, and the chromium complex (PNPtBu)Cr0(CO)3 (PNPtBu = 2,6-bis(di-tert-butyl-phosphinomethyl)pyridine) bearing a neutral PNP pincer scaffold. The three group six complexes described in this study have been characterized by Liquid Injection Field Desorption Ionization Mass Spectrometry (LIFDI-MS), NMR, and IR spectroscopy. Single crystal X-ray diffraction studies show the MoII and WII complexes adopt a six-coordinate distorted trigonal prismatic geometry, whereas the Cr0 complex exhibits a distorted octahedral geometry.

Unprecedented intact radical anions, closed shell anions, cluster ions, and traditional cations and radical cations by LIFDI-MS.

Liquid injection field desorption ionization (LIFDI) proves the extraordinary softness of the ionization process combined with a convenient sample supply under the exclusion of moisture and air. LIFDI-mass spectrometry (MS) is used for organometallic and other seriously air-sensitive compounds forming intact ions without substantial fragmentation. Unprecedented molecular radical anions M-• are presented along with well-known intact M+• radical cations. Furthermore closed shell cations [C]+ and adduct ions like [M + H]+ or [M + Alkali]+ are gently transferred from the solid emitter surface into the gas phase. Anions [A]- or [M - H]- are accessible by LIFDI-MS at medium field strengths. Ion pairs [C]+[A]- are separately detected by positive and negative mode LIFDI-MS, respectively. Here we give an overview of the different ion types accessible by LIFDI-MS. For the first time the field ionization/desorption of solar cell electron acceptor compounds is shown to deliver M-• and M2-• radical ions.

Group 6 germylidyne complexes in the gas phase by LIFDI and APCI mass spectrometry.

Although showing fascinating chemical properties and reactivity in solution, heavier tetrelylidyne complexes with M≡E triple bonds have not been studied in the gas phase before due to their high sensitivity towards air and moisture. We selected four group 6 germylidyne complexes, [Cp(PMe3)2M≡GeArMes] (M = Mo (1-Mo), W (1-W), ArMes = 2,6-dimesitylphenyl) and [Tp'(CO)2M≡GeArMes] (M = Mo (2-Mo), W (2-W), Tp' = κ3-N,N',N''-hydridotris(3,5-dimethylpyrazolyl) borate), for a mass-spectrometric study. Liquid Injection Field Desorption Ionization (LIFDI) proved to be a well-suited technique to ionize these sensitive compounds as the spectra show the molecular ions as radical cations and only minor traces of fragmentation or degradation products. In addition, Atmospheric Pressure Chemical Ionization (APCI) connected to a high-resolving tandem mass spectrometer allowed us to study the gas-phase fragmentation behaviour of these compounds. The fragmentation patterns not only comprise the expected losses of phosphane or carbonyl ligands, respectively, but also indicate C-H bond activation by the electron-deficient metal centre. An enhanced reactivity of the tungsten species is visible in a preferred methyl abstraction in the phosphane complex 1-W compared to 1-Mo. Although degradation in solution before ionization obviously can destroy the M≡Ge triple bond, the cleavage of the M≡Ge bond upon gas-phase activation is not observed for the Mo species and only as a minor pathway for the W compounds, highlighting the high bonding energy between metal and tetrel.

Identification and characterization of selected silyl substituted silyl anions by liquid injection field desorption ionization mass spectrometry.

Silyl anions are crucial building blocks in silicon chemistry and are frequently used in organosilicon chemistry. These so-called silanides are negatively charged three-coordinate species, isoelectronic to carbanions. In this contribution, we synthesized already literature known and unknown anionic silicon species. Here we focused on silyl substituted silyl anions with different substituted silicon atoms like hydrogen, methyl, and methoxy groups. Furthermore, we investigated these species with liquid injection field desorption ionization mass spectrometry.

Negative-ion field desorption revitalized by using liquid injection field desorption/ionization-mass spectrometry on recent instrumentation

Field ionization (FI), field desorption (FD), and liquid injection field desorption/ionization (LIFDI) provide soft positive ionization of gaseous (FI) or condensed phase analytes (FD and LIFDI). In contrast to the well-established positive-ion mode, negative-ion FI or FD have remained rare exceptions. LIFDI provides sample deposition under inert conditions, i.e., the exclusion of atmospheric oxygen and water. Thus, negative-ion LIFDI could potentially be applied to highly sensitive anionic compounds like catalytically active transition metal complexes. This work explores the potential of negative-ion mode using modern mass spectrometers in combination with an LIFDI source and presents first results of the application of negative-ion LIFDI-MS. Experiments were performed on two orthogonal-acceleration time-of-flight (oaTOF) instruments, a JEOL AccuTOF GCx and a Waters Micromass Q-TOF Premier equipped with LIFDI sources from Linden CMS. The examples presented include four ionic liquids (ILs), i.e., N-butyl-3-methylpyridinium dicyanamide, 1-butyl-3-methylimidazolium tricyanomethide, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, and trihexyl(tetradecyl)phosphonium tris(pentafluoroethyl)trifluorophosphate), 3-(trifluoromethyl)-phenol, dichloromethane, iodine, polyethylene glycol diacid, perfluorononanoic acid, anionic surfactants, a tetraphosphazene silanol-silanolate, and two bis(catecholato)silanes. Volatile samples were delivered as vapors via the sample transfer capillary of the LIFDI probe or via a reservoir inlet. Condensed phase samples were applied to the emitter as dilute solutions via the sample transfer capillary. The compounds either yielded ions corresponding to their intact anions, A−, or the [M–H]− species formed upon deprotonation. This study describes the instrumental setups and the operational parameters for robust operation along with a discussion of the negative-ion LIFDI spectra of a variety of compounds.

Enabling LIFDI-MS measurements of highly air sensitive organometallic compounds: a combined MS/glovebox technique.

A new setup combining a ThermoFisher Exactive Plus Orbitrap Mass Spectrometer with a liquid injection field desorption ionization (LIFDI) source directly connected to an inert atmosphere glovebox is presented. The described setup allows for the analysis of very air- and moisture sensitive samples. Furthermore, the soft nature of LIFDI ionization gives access to the molecular ions of fragile molecules. This new setup is therefore especially useful for sensitive organometallic complexes. The functionality of the new setup is tested against [(Cp)2TiCl]˙, which is known for its notorious sensitivity to air and moisture. Its drastic colour change from green to orange upon exposure to air further supports the easy detection of traces of oxygen during the experiment. In addition, we applied this setup to the mass spectrometric analysis of the qualitative composition of a Cu/Al cluster mixture, which is not accessible by other analytical methods.

Nanometallurgy in solution: organometallic synthesis of intermetallic Pd-Ga colloids and their activity in semi-hydrogenation catalysis.

Nanoparticles (NPs) of Pd1--xGax (x = 0.67, 0.5, 0.33), stabilized in non-aqueous colloidal solution, were obtained via an organometallic approach under mild conditions using [Pd2(dvds)3] and GaCp* as all-hydrocarbon ligated metal-precursor compounds (dvds = 1,1,3,3-tetramethyl-1,3-divinyl-disiloxane; Cp* = η5-C5Me5; Me = CH3). The reaction of the two precursors involves the formation of a library of molecular clusters [PdnGamCp*y(dvds)z], as shown by liquid injection field desorption ionization mass spectrometry (LIFDI-MS). Full characterization of the catalytic system (HR-TEM, EDX, DLS, PXRD, XPS, NMR, IR, Raman) confirmed the formation of ultra-small, spherical NPs with narrow size distributions ranging from 1.2 ± 0.2 nm to 2.1 ± 0.4 nm (depending on the Pd : Ga ratio). The catalytic performance of the Pd1--xGax NPs in the semi-hydrogenation of terminal and internal alkynes and the influence of the gallium content on product selectivity were investigated. The highest activities (65%) and selectivities (81%) are achieved using colloids with a "stoichiometric" Pd/Ga ratio of 1 : 1 at 0 °C and 2.0 bar H2 pressure. While lower Ga ratios lead to an increase in activity, higher Ga contents increase the olefin selectivity but are detrimental to the activity.

From the discovery of field ionization to field desorption and liquid injection field desorption/ionization-mass spectrometry-A journey from principles and applications to a glimpse into the future.

The discovery of the ionizing effect of strong electric fields in the order of volts per Ångstrom in the early 1950s eventually led to the development of field ionization-mass spectrometry (FI-MS). Due to the very low ion currents, and thus, limited by the instrumentation of the 1960s, it took some time for the, by then, new technique to become adopted for analytical applications. In FI-MS, volatile or at least vaporizable samples mainly deliver molecular ions, and consequently, mass spectra showing no or at least minor numbers of fragment ion signals. The next major breakthrough was achieved by overcoming the need to evaporate the analyte prior to ionization. This was accomplished in the early 1970s by simply depositing the samples onto the field emitter and led to field desorption-mass spectrometry (FD-MS). With FD-MS, a desorption ionization method had become available that paved the road to the mass spectral analysis of larger molecules of low to high polarity and even of organic salts. In FD-MS, all of these analytes deliver spectra with no or at least few fragment ion peaks. The last milestone was the development of liquid injection field desorption/ionization (LIFDI) in the early 2000s that allows for sample deposition under the exclusion of atmospheric oxygen and water. In addition to sampling under inert conditions, LIFDI also enables more robust and quicker operation than classical FI-MS and FD-MS procedures. The development and applications of FI, FD, and LIFDI had mutual interference with the mass analyzers that were used in combination with these methods. Vice versa, the demand for using these techniques on other than magnetic sector instruments has effectuated their adaptation to different types of modern mass analyzers. The journey started with magnetic sector instruments, almost skipped quadrupole analyzers, encompassed Fourier transform ion cyclotron resonance (FT-ICR) and orthogonal acceleration time-of-flight (oaTOF) analyzers, and finally arrived at Orbitraps. Even interfaces for continuous-flow LIFDI have been realized. Even though being niche techniques to some degree, one may be confident that FI, FD, and LIFDI have a promising future ahead of them. This Account takes you on the journey from principles and applications of the title methods to a glimpse into the future.

Structural investigation of perfluorocarboxylic acid derivatives formed in the reaction with N,N-dimethylformamide dialkylacetals.

A structural investigation of perfluorocarboxylic acid derivatives formed in the reaction with N,N-dimethylformamide dialkylacetals employing several techniques of mass spectrometry (MS) is described. Two derivatizing reagents, dimethylformamide dimethyl acetal (DMF-DMA) and dimethylformamide diethylacetal (DMF-DEA) were used. In contrast to carboxylic acids, perfluorocarboxylic acids are not able to form alkyl esters as the main product in this reaction. We found that perfluorooctanoic acid (PFOA) forms a salt with N,N-dimethylformamide dialkylacetals. This salt undergoes a further reaction inside the injection block of a gas chromatograph (GC) by loss of CO2 and then forms 1,1-perfluorooctane-(N,N,N,N-tetramethyl)-diamine. The GC-MS experiments using both electron ionization (EI) and positive-ion chemical ionization (PCI) revealed that the same reaction products are formed with either derivatizing reagent. Subjecting the perfluorocarboxylic acid derivative to electrospray ionization (ESI) and direct analysis in real time (DART), both positive- and negative-ion modes indicated that cluster ions are formed. In the positive-ion mode, this cluster ion consists of two iminium cations and one PFOA anion, while in the negative-ion mode, it comprises two PFOA anions and one cation. The salt structure was further confirmed by liquid injection field desorption/ionization (LIFDI) as well as infrared (IR) spectroscopy. We propose a simple mechanism of N,N,N',N'-tetramethylformamidinium cation formation. The structure elucidation is supported by specific fragment ions as obtained by GC-EI-MS and GC-PCI-MS analyses.

Self-Supplied Liquid Injection Field Desorption/Ionization Ion Source for an Orthogonal Time-of-Flight Instrument.

A new implementation of a dedicated ion source for field ionization (FI), field desorption (FD), and liquid injection field desorption/ionization (LIFDI) for the JEOL AccuTOF GC series of orthogonal-acceleration time-of-flight instruments is presented. In contrast to existing implementations, this third-party LIFDI probe and source combination does not require the exchange of the entire ion source comprising ion source block and lens stack to switch from electron ionization (EI) to LIFDI. Rather, the methods may be swapped conveniently by only exchanging the ion source block for a mechanical probe guide and inserting the LIFDI probe in place of the standard direct insertion probe (DIP) via the vacuum lock. Further, this LIFDI setup does not require any changes of the electronics or software of the AccuTOF mass spectrometer because it is self-supplied in terms of power supply, observation optics, and computer control. The setup offers advanced FI/FD/LIFDI control features such as emission-controlled emitter heating current and emitter flash baking during elongated runs as required for gas chromatography-FI-mass spectrometry (MS). The LIFDI source and probe and its operation are reported in detail. FI spectra of the volatile analytes toluene, heptane, and pentafluoroiodobenzene are presented. LIFDI operation is demonstrated for the analysis of the saturated hydrocarbon dotriacontane and the low-mass hydrocarbon polymers polystyrene 484 and polystyrene 1050. Further, the air-sensitive 2nd-generation Hoveyda-Grubbs catalyst is analyzed by LIFDI-MS. For comparison with long-established LIFDI instrumentation, some of the spectra obtained with the new setup are also compared with those from a double-focusing magnetic sector instrument.

Activation of the dimers and tetramers of metal amidinate atomic layer deposition precursors upon adsorption on silicon oxide surfaces

The gas-phase structure of three copper amidinate compounds, copper(I)-N,N′-di-sec-butyl-acetamidinate (1), copper(I)-N-sec-butyl-2-iminopyrrolidinate (2), and copper(I)-N-tert-butyl-5,5-dimethyl-2-iminopyrrolidinate (3), and their initial adsorption on silicon oxide surfaces, were characterized by a combination of experimental measurements and density-functional theory (DFT) calculations. These compounds have previously been shown to crystallize in dimeric or tetrameric form, and liquid-injection field desorption ionization mass spectrometry data proved that such structures are retained upon vaporization into the gas phase (dimers for the first and third compounds, a tetramer for the second). Results from DFT calculations of the relative energies of formation of the monomers, dimers, and tetramers confirmed the experimental results. Adsorption on the surface of silicon oxide films was determined, based on additional DFT calculations, to lead to the binding of the copper amidinates preferentially as dimers; although the monomers form stronger bonds to the silicon surface because they bind directly through their copper atom, this cannot fully compensate for the large energy required to break the dimers apart. N 1s x-ray photoelectron spectroscopy data were used to corroborate both the presence of the dimers on the surface with the second (2) precursor and the threshold for their surface decomposition around room temperature. The behavior of the third compound is somewhat more complex, with some decomposition possibly happening immediately upon adsorption at 100 K.

On the mechanism of imine elimination from Fischer tungsten carbene complexes.

(Aminoferrocenyl)(ferrocenyl)carbene(pentacarbonyl)tungsten(0) (CO)5W=C(NHFc)Fc (W(CO)5(E-2)) is synthesized by nucleophilic substitution of the ethoxy group of (CO)5W=C(OEt)Fc (M(CO)5(1Et)) by ferrocenyl amide Fc-NH– (Fc = ferrocenyl). W(CO)5(E-2) thermally and photochemically eliminates bulky E-1,2-diferrocenylimine (E-3) via a formal 1,2-H shift from the N to the carbene C atom. Kinetic and mechanistic studies to the formation of imine E-3 are performed by NMR, IR and UV–vis spectroscopy and liquid injection field desorption ionization (LIFDI) mass spectrometry as well as by trapping experiments for low-coordinate tungsten complexes with triphenylphosphane. W(CO)5(E-2) decays thermally in a first-order rate-law with a Gibbs free energy of activation of ΔG‡298K = 112 kJ mol−1. Three proposed mechanistic pathways are taken into account and supported by detailed (time-dependent) densitiy functional theory [(TD)-DFT] calculations. The preferred pathway is initiated by an irreversible CO dissociation, followed by an oxidative addition/pseudorotation/reductive elimination pathway with short-lived, elusive seven-coordinate hydrido tungsten(II) intermediates cis(N,H)-W(CO)4(H)(Z-15) and cis(C,H)-W(CO)4(H)(Z-15).

Hume-Rothery phase-inspired metal-rich molecules: cluster expansion of [Ni(ZnMe)₆(ZnCp*)₂] by face capping with Ni⁰(η⁶-toluene) and Ni(I)(η⁵-Cp*).

The novel all-hydrocarbon ligand-stabilized binuclear clusters of metal-core composition Ni2Zn7E, [(η(5)-Cp*)Ni2(ZnMe)6(ZnCp*)(ECp*)] (1-Zn, E = Zn; 1-Ga, E = Ga) and [(η(6)-toluene)Ni2(ZnCp*)2(ZnMe)6] (2; Cp* = pentamethylcyclopentadienyl), were obtained via Ga/Zn and Al/Zn exchange reactions using the starting compounds [Ni2(ECp*)3(η(2)-C2H4)2] (E = Al/Ga) and an excess of ZnMe2 (Me = CH3). Compounds 1-Zn and 1-Ga are very closely related and differ only by one Zn or Ga atom in the group 12/13 metal shell (Zn/Ga) around the two Ni centers. Accordingly, 1-Zn is EPR-active and 1-Ga is EPR-silent. The compounds were derived as a crystalline product mixture. All new compounds were characterized by (1)H and (13)C NMR and electron paramagnetic resonance (EPR) spectroscopy, mass spectrometric analysis using liquid-injection field desorption ionization, and elemental analysis, and their molecular structures were determined by single-crystal X-ray diffraction studies. In addition, the electronic structure has been investigated by DFT and QTAIM calculations, which suggest that there is a Ni1-Ni2 binding interaction. Similar to Zn-rich intermetallic phases of the Hume-Rothery type, the transition metals (here Ni) are distributed in a matrix of Zn atoms to yield highly Zn-coordinated environments. The organic residues, ancillary ligands (Me, Cp*, and toluene), can be viewed as the "protecting" shell of the 10-metal-atom core structures. The soft and flexible binding properties of Cp* and transferability of Me substituents between groups 12 and 13 are essential for the success of this precedence-less type of cluster formation reaction.

Organogallium- and organozinc-rich palladium and platinum clusters

The heteroleptic, binuclear compounds [M2(GaCp*)3(PMe3)2] (M = Pd: 1a, Pt: 1b, Cp* = pentamethylcyclopentadienyl) can be obtained if [Pd2(dvds)3] (dvds = 1,3-divinyl-1,1,3,3-tetramethyldisiloxane) or [Pt(COD)2] (COD = cyclooctadiene) were treated with a 3 : 2 ratio of GaCp* and PMe3. A trinuclear complex [Pd3(GaCp*)3(PMe3)3] (2) was isolated from in situ prepared [Pd(PMe3)2Me2] and treatment with GaCp*. The new complexes were used as starting compounds for selective Ga/Zn exchange reactions to afford the dinuclear palladium compound [Pd2(ZnCp*)(ZnMe)3(PMe3)5] (3a) and the mononuclear platinum compound [Pt(ZnCp*)2(ZnMe)2(PMe3)2] (3b). The effects of a final transition metal count in organozinc ligated compounds and stabilization of Lewis acidic fragments like [Pd(PPh3)3], [Ni(C2H4)3] or [Mo(CO)5] were presented and discussed. All compounds have been fully characterized by (1)H, (13)C, and (31)P NMR spectroscopy, mass spectrometry using a liquid injection field desorption ionization (LIFDI) method, elemental analysis, and single crystal X-ray diffraction studies and the coordination polyhedra were analysed by the method of continuous shape measure (CShM).

Clusters [Ma(GaCp*)b(CNR)c] (M = Ni, Pd, Pt): Synthesis, Structure, and Ga/Zn Exchange Reactions

Reactions of homoleptic isonitrile ligated complexes or clusters of d(10)-metals with the potent carbenoid donor ligand GaCp* are presented (Cp* = pentamethylcyclopentadienyl). Treatment of [Ni4(CNt-Bu)7], [{M(CNR)2}3] (M = Pd, Pt) and [Pd(CNR)2Me2] (R = t-Bu, Ph) with suitable amounts of GaCp* lead to the formation of the heteroleptic, tri- and tetranuclear clusters [Ni4(CNt-Bu)7(GaCp*)3] (1), [{M(CNt-Bu)}3(GaCp*)4] (M = Pd: 2a, Pt: 2b), and [{Pd(CNR)}4(GaCp*)4] (R = t-Bu: 3a, Ph: 3b). The reactions involve isonitrile substitution reactions, GaCp* addition reactions, and cluster formation reactions. The new compounds were investigated for their ability to undergo Ga/Zn exchange reactions when treated with ZnMe2. The novel tetranuclear Zn-rich clusters [Ni4GaZn7(Cp*)2Me7(CNt-Bu)6] (4) and [{Pd(CNR)}4(ZnCp*)4(ZnMe)4] (R = t-Bu: 5a, Ph: 5b) were obtained and isolated. The electronic situation and geometrical arrangement of atoms of all compounds will be presented and discussed. All new compounds are characterized by solution (1)H, (13)C NMR and IR spectroscopy, elemental analysis (EA), liquid injection field desorption ionization mass spectrometry (LIFDI-MS) as well as single crystal X-ray crystallography.

Group-13 carbenoid ligands at tungsten: Coordination and C–H activation

Reactions of zero valent tungsten complexes with AlCp∗ and GaCp∗ (Cp∗ = pentamethylcyclopentadienyl) are presented. The treatment of [W(C2H4)2(PMe3)4] with 2 equiv of GaCp∗ or AlCp∗ leads to the formation of cis-[W(GaCp∗)2(PMe3)4] (1) or trans,cis,cis-[W(AlCp∗)2(C2H4)2(PMe3)2] (2) under cleavage of ethylene or PMe3 ligands, respectively. Treatment of either [W(C2H4)2(PMe3)4] or 2 with 4 or 6 equiv of AlCp∗ leads to the C–H activated species of over-all composition [W(AlCp∗)6(C2H4)2] (3), which features terminal W–H as well as bridging W–H–Al hydride ligands and C–H activated C2H4 resulting in Al–C bonds. All new compounds are characterized by solution NMR, IR, elemental analyses (EA), liquid injection field desorption ionization mass spectrometry (LIFDI-MS) as well as single crystal x-ray crystallography.

From AlCp*‐ and GaCp*‐Ligated Ruthenium Hydrides to Zinc‐Rich Heterometallic Complexes

AbstractThe reactivity of ZnMe2 towards heteroleptic (poly)hydride ruthenium complexes was investigated. The Ru centers were coligated with different ligands including reactive low‐valent ECp* (E = Ga, Al; Cp* = pentamethylcyclopentadienyl) ligands and nonreactive phosphane ligands (PCy3, PPh3, Cy = cyclohexyl, Ph = phenyl). The ECp* ligands undergo a redox reaction together with Cp*/Me group exchange when treated with ZnMe2 to form two equivalents of ZnR (R = Cp*, Me) units, and ER3 species are liberated. Similarly, Ru–H moieties react with ZnMe2 to form one equivalent of ZnMe and one equivalent of CH4. The 18‐electron rule proved valid for the rationalization of the obtained compositions; one ECp* or phosphane ligand is equivalent to two one‐electron ZnR or H ligands. The factors that control the exchange of phosphane or hydride ligands are discussed. All compounds were characterized by NMR and IR spectroscopy, liquid injection field desorption ionization (LIFDI) MS analysis, single‐crystal X‐ray diffraction, and elemental analysis.

Liquid Injection Field Desorption Ionization Mass Spectrometry of Cyclic Metal Carbonyl Complexes with Tetra-Antimony Ligands

Reactions of (norbornadiene)Cr(CO)(4) or cis-(piperidine)(2)Mo(CO)(4) with R(2)Sb-SbR(2), and cyclo-(R'Sb)(n) (R' = Et, n-Pr; n = 4, 5) give the complexes cyclo-[M(CO)(4)(R(2)Sb-SbR'- SbR'-SbR(2))] (1: M = Cr, R = Me, R'= Et; 2: M = Mo, R = Et, R' = Et; 3: M = Mo, R = Et, R' = n-Pr). Not accessible to established characterization methods, the oily, extremely reactive unpurified mixture of 3 with scrambled ligands was characterized by mass spectrometry using liquid injection field desorption ionization (LIFDI).