Ligand-Induced Intramolecular Redox Diversity in Titanium Complexes with Acenaphthene-1,2-diimine.

A series of the chlorido and alkoxychlorido titanium complexes of the general formula (dpp-Bian)Ti(OiPr)nCl3-n, where dpp-Bian = 1,2-bis[(2,6-iPr2C6H3)imino]acenaphthene n = 0 (2), 1 (3), 2 (4), as well as (dpp-Bian)Ti(OiPr)2 (5) and (dpp-Bian)Ti(OiPr)Cl3 (3-Cl), were isolated and characterized using single-crystal X-ray diffraction analysis and spectroscopic studies combined with density functional theory (DFT) calculations. In the solid state, compounds 2-4 reveal a square-pyramidal geometry at the metal center supported with monoanionic dpp-Bian, whereas 3-Cl with a neutral diimine ligand and 5 bearing a dianionic enebisamide dpp-Bian show, respectively, an octahedral and tetrahedral coordination surrounding the metal ion. Paramagnetic complexes 2-4 exhibit electron paramagnetic resonance spectra in both toluene solution and solid state, confirming the transfer of spin density from the metal ion to the dpp-Bian ligand as the number of alkoxy groups increases. The increase in polarity of the Ti-N bonds in the row 2 < 3 < 4 contributes to enhanced stability of the metal complexes with respect to O-donor molecules. Thus, in tetrahydrofuran (THF), compounds 2 and 3 undergo reversible solvolysis, whereas complex 4 is stable. The charge and spin density distributions as well as molecular orbital energies in 2-4 were analyzed on the basis of DFT calculations which also provided information on the electronic transition energies, absorption band assignments, and thermodynamic parameters of the reactions between the complexes and THF.

Effect of a single methyl substituent on the electronic structure of cobaltocene studied by computationally assisted MATI spectroscopy.

Metallocenes represent archetypical organometallic compounds playing key roles in various fields of fundamental and applied chemistry. Many of their unique properties arise from low ionization energies (IE) which can be tuned by introducing substituents into the rings. Here we report the first mass-analyzed threshold ionization (MATI) spectrum of a methylmetallocene, (Cp')(Cp)Co (Cp' = η5-C5H4Me, Cp = η5-C5H5). The presence of a single Me group allows us to study the "pure" effect of methylation without the mutual influence of substituents. The MATI technique provides an extremely high accuracy in determining the adiabatic IE of (Cp')(Cp)Co which equals 5.2097(6) eV. The effect of a Me group on the IE of cobaltocene appears to be 36% stronger than that in bis(η6-benzene)chromium. The MATI spectrum of (Cp')(Cp)Co shows a rich vibronic structure from which vibrational frequencies of the free ion are determined. This information provides a solid basis for testing the quality of quantum chemical calculations. Various levels of the DFT and coupled cluster computations are used to describe the structural and electronic transformations accompanying the detachment of an elctron from (Cp')(Cp)Co. New aspects of the methyl substituent influence on the potential energy surfaces, as well as on the inhomogeneous changes in charge density and electrostatic potential caused by ionization, are discussed.

X/Y platinum(II) complexes: some features of supramolecular assembly via halogen bonding.

Four series of new luminescent cyclometalated complexes [Pt(C^N)(IPy)Y] (HC^N = 2-phenylpyridine (Hppy), 2-(1-benzofuran-3-yl)pyridine (Hbfpy), methyl-2-phenylquinoline-4-carboxylate (Hmpqc), 2-(1-benzothiophen-3-yl)pyridine (Hbtpy), IPy = 4-iodopyridine, and Y = Cl, Br, I) have been investigated as X/Y 'building blocks' for the construction of a supramolecular network utilizing the I atom in IPy as a halogen bond (XB) donor (the X atom). The σ-hole of the X atom was found to provide non-covalent X⋯Y, X⋯Pt and X⋯π (π system of the metalated chelate ring) interactions for the complexes in the crystal state. NBO analysis confirms donation of the platinum electron density to iodine upon the X⋯Pt interaction. The nature of the X counterpart in XB depends on the nature of the Y atom and the cyclometalating ligand of the Pt(II) complex. DFT calculations show that the HOMO of [Pt(C^N)(IPy)Y] in the S0 state is delocalized over Pt, Y and a C-coordinating fragment of C^N, while the LUMO in most complexes is formed by the Py orbitals of IPy. However, the α-HOMO in the lowest triplet state of [Pt(C^N)(IPy)Y] contains no contribution of the IPy wavefunctions. All Pt(II) complexes exhibited triplet luminescence in solution and in the solid state (Φ up to 0.129), which is determined by the nature of the C^N ligand. The emission profile is independent of the nature of the ligand Y, while the quantum yield decreases from Cl to I. Accordingly, on the basis of DFT calculation, this emission is interpreted as a C^N intraligand charge transfer predominantly. The XB formation did not show an effect on the luminescence of the complexes in the solid phase, however grinding of crystals results in an increase of brightness.

The reactivity of antimony and bismuth N,C,N-pincer compounds toward K[BEt3H] - the formation of heterocyclic compounds vs. element-element bonds vs. stable terminal Sb-H bonds.

The oxidative addition of CF3SO3CH2Si(CH3)3 (NpSiOTf) toward organopnictogen(I) N,C,N-pincer compounds, i.e. [2,6-(DippNCH)2C6H3]E (1-E, where E = Sb, Bi; Dipp = 2,6-iPr2C6H3) produced compounds [2,6-(DippNCH)2C6H3]E(NpSi)(OTf) (2-E, where E = Sb, Bi). By analogy, the in situ reduction of [2,6-(Me2NCH2)2C6H3]ECl2 (3-E, where E = Sb, Bi) followed by treatment with NpSiOTf or MeI gave compounds [2,6-(Me2NCH2)2C6H3]E(R)(X) (R/X = NpSi/OTf 4-E, where E = Sb, Bi; R/X = Me/I 5-Sb). The reactivity of these compounds toward 1 eq. of K[BEt3H] was examined showing remarkable differences depending both on the ligand backbone and the pnictogen used. Thus in the case of 2-E, the addition of the hydride across the imino-function was achieved thereby yielding azapnicta-heterocyclic compounds [2-(DippNCH2)-6-(DippNCH)C6H3]E(NpSi) (6-E, where E = Sb, Bi). The same reaction of 4-Bi produced dibismuthine {[2,6-(Me2NCH2)2C6H3]Bi(NpSi)}2 (7-Bi), but in the case of 4/5-Sb the analogous distibines {[2,6-(Me2NCH2)2C6H3]Sb(R)}2 (R = NpSi7-Sb, Me 8-Sb) were not formed directly and hydrides [2,6-(Me2NCH2)2C6H3]Sb(R)H (R = NpSi9-Sb, Me 10-Sb) could be isolated instead. Nevertheless, heating of both 9-Sb and 10-Sb led to an activation of a labile Sb-H bond and the formation of distibines 7/8-Sb.

Ionization of Decamethylmanganocene: Insights from the DFT-Assisted Laser Spectroscopy.

Metallocenes represent one of the most important classes of organometallics with wide prospects for practical use in various fields of chemistry, materials science, molecular electronics, and biomedicine. Many applications of these metal complexes are based on their ability to form molecular ions. We report the first results concerning the changes in the molecular and electronic structure of decamethylmanganocene, Cp*2Mn, upon ionization provided by the high-resolution mass-analyzed threshold ionization (MATI) spectroscopy supported by DFT calculations. The precise ionization energy of Cp*2Mn is determined as 5.349 ± 0.001 eV. The DFT modeling of the MATI spectrum shows that the main structural deformations accompanying the detachment of an electron consist in the elongation of the Mn-C bonds and a change in the Me out-of-plane bending angles. Surprisingly, the DFT calculations predict that most of the reduction in electron density (ED) upon ionization is associated with the hydrogen atoms of the substituents, despite the metal character of the ionized orbital. However, the ED difference isosurfaces reveal a complex mechanism of the charge redistribution involving also the carbon atoms of the molecule.

Beyond simple hetero Diels-Alder cycloadditions. A new type of element-ligand cooperativity at N,C,N-coordinated arsinidene and stibinidene centres in the reaction with an electron-deficient alkyne.

The reactivity of two types of organopnictogen(I) N,C,N-pincer ligand coordinated compound, i.e. [2,6-(DippNCH)2C6H3]E (1-E, where E = As, Sb, Bi; Dipp = 2,6-iPrC6H3) and [2-(DippNCH)-6-(DippNHCH2)C6H3]E (6-E, where E = As or Sb), toward an electron-deficient alkyne, i.e. dimethyl acetylenedicarboxylate (DMAD), is reported. All reactions represent remarkable examples of element-ligand cooperation (ELC). In the first step, all compounds react via dearomatization of a latent heteropnictole ring producing rare examples of hetero Diels-Alder (DA) adducts. These compounds then smoothly convert to 1-arsanaphthalenes via hydrogen migration, thereby recovering the aromatic 10π-electron system. Furthermore, in the case of bis(imino) derivatives of 1-E, heating of DA adducts in pyridine led to a hydrogenation of the triple bond of DMAD with the concomitant recovery of the univalent pnictinidene centre, which is in turn able to activate the second molecule of DMAD. In contrast, the non-symmetric derivative of 6-As upon heating in pyridine produced bicyclic trivalent arsenic compounds as a result of an attack of the pendant secondary NH group into the arsa-heterocyclic system. For 6-Sb, a remarkable stoichiometric hydrogenation of the DMAD molecule was observed by NMR spectroscopy involving the reductive elimination of dimethylfumarate in the final step of the reaction sequence. The whole study is accompanied by a theoretical survey that describes the main thermodynamic parameters of the reported reactions and explains the reaction pathways observed in the experiments.

Perfluorinated Trialkoxysilanol with Dramatically Increased Brønsted Acidity.

The Brønsted acidity of the perfluorinated trialkoxysilanol {(F3 C)3 CO}3 SiOH is more than 13 orders of magnitude higher than that of orthosilicic acid, Si(OH)4 , and even more for most previously known silanols. It is easily deprotonated by simple amines and pyridines to give the conjugate silanolates [OSi{OC(CF3 )3 }3 ]- , which possess extremely short Si-O bonds, comparable to those of silanones.

Laser spectroscopic and computational insights into unexpected structural behaviours of sandwich complexes upon ionization.

Transition-metal sandwich complexes play key roles in various fields such as fundamental and applied chemistry; many of their unique properties arise from their ability to form stable or reactive ions. The first mass-analyzed threshold ionization (MATI) spectra of mixed sandwich compounds, (Ch)(Cp)Cr and (Cot)(Cp)Ti (Ch = η7-C7H7, Cp = η5-C5H5, Cot = η8-C8H8), presented in this work provide an extremely accurate description of the electron detachment. The ionization energies of the neutrals and stabilization energies of the metal-ligand interactions upon ionization are derived from the MATI data with an accuracy of 0.0006 eV. In combination with DFT calculations, laser threshold ionization spectroscopy reveals surprisingly different structural variations accompanying the detachment of the non-bonding dz2 electron from the sandwich molecules. The geometry of (Ch)(Cp)Cr remains practically unchanged while the ionization of (Cot)(Cp)Ti causes a noticeable shortening of the inter-ring distance, similar to that resulting from the ionization of a typical antibonding orbital. Electron density analysis throws light on the nature of these amazing effects.

Reversible Addition of Carbon Dioxide to Main Group Metal Complexes at Temperatures about 0 °C.

The reaction of dialane [LAl-AlL] (1; L=dianion of 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene, dpp-bian) with carbon dioxide results in two different products depending on solvent. In toluene at temperatures of about 0 °C, the reaction gives cycloadduct [L(CO2 )Al-Al(O2 C)L] (2), whereas in diethyl ether, the reaction affords oxo-bridged carbamato derivative [L(CO2 )(Et2 O)Al(µ-O)AlL] (3). The DFT and QTAIM calculations provide reasonable explanations for the reversible formation of complex 2 in the course of two subsequent (2+4) cycloaddition reactions. Consecutive transition states with low activation barriers were revealed. Also, the DFT study demonstrated a crucial effect of diethyl ether coordination to aluminium on the reaction of dialane 1 with CO2 . The optimized structures of key intermediates were obtained for the reactions in the presence of Et2 O; calculated thermodynamic parameters unambiguously testify the irreversible formation of the product 3.

Taking a snapshot of the triplet excited state of an OLED organometallic luminophore using X-rays.

OLED technology beyond small or expensive devices requires light-emitters, luminophores, based on earth-abundant elements. Understanding and experimental verification of charge transfer in luminophores are needed for this development. An organometallic multicore Cu complex comprising Cu-C and Cu-P bonds represents an underexplored type of luminophore. To investigate the charge transfer and structural rearrangements in this material, we apply complementary pump-probe X-ray techniques: absorption, emission, and scattering including pump-probe measurements at the X-ray free-electron laser SwissFEL. We find that the excitation leads to charge movement from C- and P- coordinated Cu sites and from the phosphorus atoms to phenyl rings; the Cu core slightly rearranges with 0.05 Å increase of the shortest Cu-Cu distance. The use of a Cu cluster bonded to the ligands through C and P atoms is an efficient way to keep structural rigidity of luminophores. Obtained data can be used to verify computational methods for the development of luminophores.

A Small Cationic Organo-Copper Cluster as Thermally Robust Highly Photo- and Electroluminescent Material.

Organic light-emitting diodes (OLEDs) are revolutionizing display applications. In this aspect, luminescent complexes of precious metals such as iridium, platinum, or ruthenium still playing a significant role. Emissive compounds of earth-abundant copper with equivalent performance are desired for practical, large-scale applications such as solid-state lighting and displays. Copper(I)-based emitters are well-known to suffer from weak spin-orbit coupling and a high reorganization energy upon photoexcitation. Here we report a cationic organo-copper cluster [Cu4(PCP)3]+ (PCP = 2,6-(PPh2)2C6H3) that features suppressed nonradiative decays, giving rise to a robust narrow-band green luminophore with a photoluminescent (PL) efficiency up to 93%. PL decay kinetics corroborated by DFT calculations reveal a complex emission mechanism involving contributions of both thermally activated delayed fluorescence and phosphorescence. This robust compound was solution-processed into a thin film in prototype OLEDs with external quantum efficiency up to 11% and a narrow emission bandwidth (65 nm fwhm).

Reversible C=C Bond Activation by an Intramolecularly Coordinated Antimony(I) Compound.

The reaction of N,C,N-chelated stibinidene ArSb (1) (Ar=C6 H3 -2,6-(CH=NtBu)2 ) with selected N-alkyl/aryl-maleimides RN(C(O)CH)2 (R=Me, tBu, Ph) gave the addition products with bridged bicyclic [2.2.1] structure containing an antimony atom at the bridgehead position, fused with a 6-membered benzene and a 5-membered N-alkyl/aryl-pyrrolidine ring. These compounds were completely characterized. More importantly, additional studies showed that these reactions are reversible in solution, thereby representing an unprecedented reversible activation of a C=C bond by an antimony(I) compound.

Rydberg state mediated multiphoton ionization of (η7-C7H7)(η5-C5H5)Cr: DFT-supported experimental insights into the molecular and electronic structures of excited sandwich complexes.

The resonance-enhanced multiphoton ionization (REMPI) of a mixed sandwich complex has been achieved for the first time when exciting (η7-C7H7)(η5-C5H5)Cr via the Rydberg 4pz state. The REMPI spectrum is indicative of unexpectedly small changes of the sandwich geometry on excitation. Time-dependent DFT calculations reveal fine effects of the ligand nature on the molecular and electronic structure variations accompanying electronic excitation. Different trends are predicted for the sandwich geometry transformations in the mixed sandwich complex and its symmetric isomer, (η6-C6H6)2Cr, both on Rydberg excitation and ionization.

From a 2,1-Benzazaarsole to Elusive 1-Arsanaphthalenes in One Step.

The 2,1-benzazaarsole (1) showed a diene-like reactivity towards selected alkynes RC≡CR (R=CO2 Me, C5 F4 N) thus forming 1-arsa-1,4-dihydro-iminonaphthalenes 2 a and 3 a as hardly isolable intermediates, that underwent facile CH→NH proton migration leading to before elusive substituted 1-arsanaphthalenes 2 b and 3 b that could be completely structurally characterized.

TD DFT insights into unusual properties of excited sandwich complexes: structural transformations and vibronic interactions in Rydberg-state bis(η6-benzene)chromium.

Sandwich compounds represent the only class of organometallics revealing vibronic structures of Rydberg transitions in their gas-phase absorption and ionization spectra. This provides rare possibilities of verifying computational results for Rydberg-state metal complexes by comparison with experimental spectroscopic data. In this work, the lowest Ryberg p state of bis(η6-benzene)chromium (1) corresponding to the 3dz2→ R4px,y transition has been modeled for the first time by TD DFT. The calculations were found to be able not only to estimate the energy of the Rydberg excitation in the 1 molecule but also to simulate its vibronic structure on the basis of the Rydberg-state optimized geometries and vibrational frequencies. The structural transformations caused by the Jahn-Teller effect in the excited 1 molecule appear to differ strongly from those in the degenerate-state benzene ion, cobaltocene or other metal-benzene complexes. The in-plane CH bending mode provides the main contribution to the JT distortion of the 1 excited-state D6h structure resulting in splitting of the R4px,y state into the R4px and R4py components belonging to the D2h point group. The calculations predict, however, a fluxional 1 behavior described by the D6h symmetry. Nevertheless, the JT effect leads to additional allowed vibronic components of the 3dz2→ R4px,y transition which is clearly revealed by the TD DFT simulation. The computational results correlate surprisingly well with the known experimental spectroscopic data and provide new insights into vibronic interactions in the Rydberg-state sandwich molecules.

Rare-earth metal-mediated PhC[triple bond, length as m-dash]N insertion into N,N-bis(trimethylsilyl)naphthalene-1,8-diamido dianion - a synthetic approach to complexes coordinated by ansa-bridged amido-amidinato ligand.

Lithium silylamides 1,8-C10H6[N(SiMe3)Li(L)]2 (L = Et2O (); L = TMEDA (1TMEDA)), when treated with PhC[triple bond, length as m-dash]N, formed the adducts 1,8-C10H6[N(SiMe3)Li(N[triple bond, length as m-dash]CPh)(OEt2)][N(SiMe3)Li(OEt2)] () and 1,8-C10H6[N(SiMe3)Li(N[triple bond, length as m-dash]CPh)][N(SiMe3)Li(TMEDA)] (2TMEDA) containing one benzonitrile molecule coordinated to Li ion while the second molecule retains a coordinated L ligand. The salt metathesis reactions of LnCl3 (Ln = Y, Sm) with equimolar amounts of and 2TMEDA (THF, 4 h, 40 °C) resulted in benzonitrile insertion and formation of new dianionic amido-amidinate ligands. The reactions of with LnCl3 afforded ionic chloro complexes [{1,8-C10H6[NSiMe3][NC(Ph)NSiMe3]}{1,8-C10H6[N(H)SiMe3][NC(Ph)NSiMe3]}LnCl][Li(L)n] (Ln = Y, L = THF, n = 4 (3Y), Ln = Sm, L = DME, n = 3 (3Sm)), while the reaction of 2TMEDA and YCl3 leds to the formation of the neutral salt-free yttrium chloro complex {1,8-C10H6[NSiMe3][NC(Ph)NSiMe3]}YCl(TMEDA) (4). The treatment of 3Y and 4 with tBuOK enabled the synthesis of tert-butoxides [{1,8-C10H6[NSiMe3][NC(Ph)NSiMe3]}{1,8-C10H6[N(H)SiMe3][NC(Ph)NSiMe3]}YOtBu][Li(THF)4] (7) and {1,8-C10H6[NSiMe3][NC(Ph)NSiMe3]}YOtBu(TMEDA) (8). Complexes 7 and 8 were evaluated as initiators for the ring opening polymerization of rac-lactide. Neutral tert-butoxide complex 8 demonstrated significantly higher activity compared to that of ionic 7.

The Weakly Coordinating Tris(trichlorosilyl)silyl Anion.

Closely following the procedure for the preparation of the base-stabilized dichlorosilylene complex NHCDipp ⋅SiCl2 reported by Roesky, Stalke, and co-workers (Angew. Chem. Int. Ed. 2009, 48, 5683-5686), a few crystals of the salt [NHCDipp -H⋅⋅⋅Cl⋅⋅⋅H-NHCDipp ]Si(SiCl3 )3 were isolated, aside from the reported byproduct [NHCDipp -H+ ⋅⋅⋅Cl- ], and characterized by X-ray crystallography (NHCDipp =N,N-di(2,6-diisopropylphenyl)imidazo-2-ylidene). They contain the weakly coordinating anion Si(SiCl3 )3- , which was also obtained in high yields upon deprotonation of the conjugate Brønsted acid HSi(SiCl3 )3 with NHCDipp or PMP (PMP=1,2,2,6,6-pentamethylpiperidine). The acidity of HSi(SiCl3 )3 was estimated by DFT calculations to be substantially higher than those of other H-silanes. Further DFT studies on the electronic structure of Si(SiCl3 )3- , including the electrostatic potential and the electron localizability, confirmed its low basicity and nucleophilicity compared with other silyl anions.

Increasing the Brønsted acidity of Ph2PO2H by the Lewis acid B(C6F5)3. Formation of an eight-membered boraphosphinate ring [Ph2POB(C6F5)2O]2.

Autoprotolysis of the metastable acid (C6F5)3BOPPh2OH, prepared in situ by the reaction of the rather weak Brønsted acid Ph2PO2H with the strong Lewis acid B(C6F5)3, gave rise to the formation of the eight-membered ring [Ph2POB(C6F5)2O]2 and C6F5H. The conjugate base was isolated as stable sodium crown ether salt [Na(15-crown-5)][Ph2PO2B(C6F5)3].

Lewis-acid induced disaggregation of dimeric arylantimony oxides.

The previously known dimeric arylantimony oxides (Ph3SbO)2 and [2,6-(Me2NCH2)2C6H3SbO]2 were disaggregated by the Lewis acid B(C6F5)3 giving rise to the formation of the Lewis pair complexes Ph3SbOB(C6F5)3 and 2,6-(Me2NCH2)2C6H3SbOB(C6F5)3 having short bipolar single Sb-O bonds.

Electronic excited states of chromium and vanadium bisarene complexes revisited: interpretation of the absorption spectra on the basis of TD DFT calculations.

The nature and energies of the (arene)2Cr, (arene)2V and (arene)2Cr(+) (arene = η(6)-C6H6, η(6)-C6H5Me, η(6)-1,3-C6H4Me2, and η(6)-1,3,5-C6H3Me3) electronic excited states have been determined on the basis of the time-dependent density functional theory (TD DFT) approach and comparison with the gas-phase and condensed-phase absorption spectra. Both valence-shell and Rydberg electronic excitations were taken into account. The TD DFT results appear to describe correctly the influence of the metal atom and the ligand on the band positions and intensities in the UV-visible absorption spectra as well as the mixing of Rydberg and intravalency states. The TD DFT calculations suggest new assignments for long-wavelength valence-shell absorption bands in the spectra of (arene)2V and (arene)2Cr(+).