Novel Oxidovanadium Complexes with Redox-Active R-Mian and R-Bian Ligands: Synthesis, Structure, Redox and Catalytic Properties.

A new monoiminoacenaphthenone 3,5-(CF3)2C6H3-mian (complex 2) was synthesized and further exploited, along with the already known monoiminoacenaphthenone dpp-mian, to obtain oxidovanadium(IV) complexes [VOCl2(dpp-mian)(CH3CN)] (3) and [VOCl(3,5-(CF3)2C6H3-bian)(H2O)][VOCl3(3,5-(CF3)2C6H3-bian)]·2.85DME (4) from [VOCl2(CH3CN)2(H2O)] (1) or [VCl3(THF)3]. The structure of all compounds was determined using X-ray structural analysis. The vanadium atom in these structures has an octahedral coordination environment. Complex 4 has an unexpected structure. Firstly, it contains 3,5-(CF3)2C6H3-bian instead of 3,5-(CF3)2C6H3-mian. Secondly, it has a binuclear structure, in contrast to 3, in which two oxovanadium parts are linked to each other through V=O···V interaction. This interaction is non-covalent in origin, according to DFT calculations. In structures 2 and 3, non-covalent π-π staking interactions between acenaphthene moieties of the neighboring molecules (distances are 3.36-3.40 Å) with an estimated energy of 3 kcal/mol were also found. The redox properties of the obtained compounds were studied using cyclic voltammetry in solution. In all cases, the reduction processes initiated by the redox-active nature of the mian or bian ligand were identified. The paramagnetic nature of complexes 3 and 4 has been proven by EPR spectroscopy. Complexes 3 and 4 exhibited high catalytic activity in the oxidation of alkanes and alcohols with peroxides. The yields of products of cyclohexane oxidation were 43% (complex 3) and 27% (complex 4). Based on the data regarding the study of regio- and bond-selectivity, it was concluded that hydroxyl radicals play the most crucial role in the reaction. The initial products in the reactions with alkanes are alkyl hydroperoxides, which are easily reduced to their corresponding alcohols by the action of triphenylphosphine (PPh3). According to the DFT calculations, the difference in the catalytic activity of 3 and 4 is most likely associated with a different mechanism for the generation of ●OH radicals. For complex 4 with electron-withdrawing CF3 substituents at the diimine ligand, an alternative mechanism, different from Fenton's and involving a redox-active ligand, is assumed.

Water-Soluble Bismuth(III) Polynuclear Tyrosinehydroximate Metallamacrocyclic Complex: Structural Parallels to Lanthanide Metallacrowns.

Recently there has been a great deal of interest and associated research into aspects of the coordination chemistry of lanthanides and bismuth-elements that show intriguing common features. This work focuses on the synthesis and characterization of a novel bismuth(III) polynuclear metallamacrocyclic complex derived from aminohydroxamic acid, in order to compare the coordination ability of Bi3+ with the similarly sized La3+ ions. A polynuclear tyrosinehydroximate Bi(OH)[15-MCCu(II)Tyrha-5](NO3)2 (1) was obtained according to the synthetic routes previously described for water-soluble Ln(III)-Cu(II) 15-MC-5 metallacrowns. Correlations between structural parameters of Bi(III) and Ln(III) complexes were analyzed. DFT calculations confirmed the similarity between molecular structures of the model bismuth(III) and lanthanum(III) tyrosinehydroximate 15-metallacrowns-5. Analysis of the electronic structures revealed, however, stronger donor-acceptor interactions between the central ion and the metallamacrocycle in the case of the lanthanum analogue. Thermochromic properties of 1 were studied.

One-Electron Reduction of 2-Mono(2,6-diisopropylphenylimino)acenaphthene-1-one (dpp-mian).

The electrochemical characteristics of 2-mono(2,6-diisopropylphenylimino)acenaphthene-1-one (dpp-mian) have been investigated. One-electron reduction of dpp-mian involves the iminoketone fragment, which is revealed by the EPR spectrum obtained after the electrolysis of the dpp-mian solution in tetrahydrofuran (THF). The reduction of dpp-mian with one equivalent of metallic potassium leads to a similar EPR spectrum. The sodium complex [(dpp-mian)Na(dme)]2 (1) produces an EPR signal with hyperfine coupling on the nitrogen atom of the iminoketone fragment of the dpp-mian ligand. Dpp-mian can also be reduced in a one-electron process by SnCl2 ×(dioxane). In this case, complex (dpp-mian)2 SnCl2 (2) is formed, with the tin atom displaying an oxidation state of +4. Tin(II) chloride dihydrate, SnCl2 ×2(H2 O), also reduces dpp-mian, but the two ligands bound to tin in the product form a new carbon-carbon bond between the ketone moieties of the dpp-mian monoanions to form complex (bis-dpp-mian)HSnCl3 (3). Metallic tin reduces dpp-mian to form the (bis-dpp-mian)2 Sn (4) species. Compounds 1-4 were characterized by X-ray diffraction.

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.

The intramolecular rearrangement of phosphinohydrazides [R'2P-NR-NR-M] → [RN═PR'2-NR-M]: general rules and exceptions. transformations of bulky phosphinohydrazines (R-NH-N(PPh2)2, R = tBu, Ph2P).

Reactions of diphosphinohydrazines R-NH-N(PPh(2))(2) (R = tBu (1), Ph(2)P (3)) with some metalation reagents (Co[N(SiMe(3))(2)](2), LiN(SiMe(3))(2), La[N(SiMe(3))(2)](3), nBuLi, MeLi) were performed. Compound 1 was synthesized by the reaction of Ph(2)PCl with tert-butylhydrazine hydrochloride in 83% yield. This compound reveals temperature-dependent (31)P NMR spectra due to hindered rotation about the P-N bonds. Complicated redox reaction of 1 with Co[N(SiMe(3))(2)](2) proceeds with cleavage of the P-N and N-N bonds to form a binuclear cobalt complex [Co{HN(PPh(2))(2)-κ(2)P,P'}(2)(µ-PPh(2))](2) (2) demonstrating a short Co···Co distance of 2.3857(5) Å, which implies a formal double bond between the Co atoms. Strong nucleophiles (nBuLi, MeLi) cause fragmentation of the molecules 1 and 3, while reactions of 3 with lithium and lanthanum silylamides give products of the NNP → NPN rearrangement [Li{Ph(2)P(NPPh(2))(2)-κ(2)N,N'}(THF)(2)] (4) and [La{Ph(2)P(NPPh(2))(2)-κ(2)N,N'}{N(SiMe(3))(2)}(2)] (5), respectively. These complexes represent the first examples of a κ(2)N,N' bonding mode for the triphosphazenide ligand [(Ph(2)PN)(2)PPh(2)](-). DFT calculations showed large energy gain (52.1 kcal/mol) of the [NNP](-) to [NPN](-) anion rearrangement.

Chemistry of the phosphorus-nitrogen ligands. Multiple isomeric transformations of the diphosphinohydrazine bearing 8-quinolyl substituent: P→C, P→N, and P→P migrations caused by different factors.

The reaction of 8-quinolylhydrazine with 2 equiv of Ph(2)PCl in the presence of Et(3)N gives 8-[(Ph(2)P)(2)NNH]-Quin (1) (Quin = quinolyl) in 84% yield. The heating of 1 at 130 °C for 1 h in toluene results in migration of the [Ph(2)PNPPh(2)] group to a carbon atom of the quinolyl fragment to form an isomer, 7-(Ph(2)P-N═PPh(2))-8-NH(2)-Quin (2). The same migration is caused by the addition of LiN(SiMe(3))(2) to 1. On the contrary, lithiation of 1 with n-BuLi followed by the addition of ZnI(2) (1:1) affords the aminoquinolyl-phosphazenide dinuclear complex [ZnI(8-Quin-NPPh(2)═N-PPh(2))-κ(3)N,N,P](2) (4), which is a result of P→N migration. Compound 1 itself reacts with ZnI(2) in THF to form 4 and protonated molecule 1·HI, which rearranges to the more stable iminobiphosphine salt (Ph(2)P-PPh(2)═N-NH-Quin-8)·HI. Zinc iodide reacts with 2 equiv of the lithium salt of 1 without rearrangement, to form homoleptic aminoquinolyl zinc complex Zn[{(Ph(2)P)(2)NN-Quin-8}-κ(2)N,N](2) (6). Solutions of 4 and 2 in dichloromethane show luminescence at 510 and 460 nm (quantum yields are 45% and 7%, respectively). DFT calculations were provided for possible isomers and their complexes.

Zero kinetic energy spectroscopy: mass-analyzed threshold ionization spectra of chromium sandwich complexes with alkylbenzenes, (η(6)-RPh)(2)Cr (R = Me, Et, i-Pr, t-Bu).

For over 25 years zero kinetic energy (ZEKE) spectroscopy has yielded a rich foundation of high-resolution results of molecular ions. This was based on the discovery in the late 60's of long-lived ion states throughout the ionization continuum of molecular ions. Here, an example is chosen from another fundamental system pioneered at this university. The mass-analyzed threshold ionization (MATI) spectra of jet-cooled chromium bisarene complexes (η(6)-RPh)(2)Cr (R = Me (1), Et (2), i-Pr (3), and t-Bu (4)) have been measured and interpreted on the basis of DFT calculations. The MATI spectra of complexes 1 and 2 appear to reveal features arising from ionizations of the isomers formed by the rotation of one arene ring relative to the other. The 1 and 2 MATI spectra show two intense peaks corresponding to the 0(0)(0) ionizations with inverse intensity ratios. As indicated by the DFT calculations, the intensity ratio change on going from 1 to 2 results from different isomers contributing to each MATI peak. The ionization energies corresponding to the 0(0)(0) peaks are 42746 ± 5 and 42809 ± 5 cm(-1) for compound 1 and 42379 ± 5 and 42463 ± 5 cm(-1) for complex 2. The 1 and 2 spectra show also the weaker features representing transitions to the vibrationally excited cationic levels, the signals of individual rotamers being detected and assigned on the basis of calculated vibrational frequencies. The MATI spectra of compounds 3 and 4 reveal only one strong peak because of close ionization potentials of the isomers contributing to the MATI signal. The 3 and 4 ionization energies are 42104 ± 5 and 41917 ± 5 cm(-1), respectively. The precise values of ionization energies obtained from the MATI spectra reveal a nonlinear dependence of the IE on the number of Me groups in the alkyl substituents of (η(6)-RPh)(2)Cr. This can be explained by an increase in the molecular zero point energies on methylation of the substituents.

[(dpp-bian)Ga-Ga(dpp-bian)] and [(dpp-bian)Zn-Ga(dpp-bian)]: synthesis, molecular structures, and DFT studies of these novel bimetallic molecular compounds.

1,2-Bis[(2,6-diisopropylphenyl)imino]acenaphthene) (dpp-bian) stabilizes gallium-gallium and zinc-gallium bonds (compounds 1-3). The compound [(dpp-bian)Ga-Ga(dpp-bian)] (2) was prepared by the reaction of GaCl3 with K3[dpp-bian] and the heterometallic [(dpp-bian)Zn-Ga(dpp-bian)] (3) was prepared by a simple one-pot reaction of [{(dpp-bian)ZnI}(2)] with GaCl3 and K4[dpp-bian]. In contrast to [(dpp-bian)Zn-Zn(dpp-bian)] (1) and 3, compound 2 is ESR silent, thus proving the dianionic character of both dpp-bian ligands. The solution ESR spectrum of 3 reveals the coupling of an unpaired electron with the gallium nuclei (69)Ga and (71)Ga (A((69)Ga)=0.97, A((71)Ga)=1.23 mT), thus confirming the presence of Zn-Ga bonds in solution. According to the results of the X-ray crystal structure analyses the metal-metal bond lengths in 2 (2.3598(3) A) and 3 (2.3531(8) A) are close to that found in 1 (2.3321(2) A). The electronic structures of compounds 2 and 3 were studied by DFT (B3 LYP/6-31G* level). The metal-metal pi bond in 2 is mainly formed by overlap of the p orbitals of Ga in the HOMO and HOMO-1, the latter showing a stronger interaction. The s and p orbitals of Ga overlap in the deeper located HOMO-17 producing a Ga-Ga sigma bond. In contrast to the Zn-Zn bond in 1, which has 95 % s character, the NBO (natural bond order) analysis of 2 reveals 67.8 % s, 32.0 % p, and 0.2 % d character for the Ga-Ga bond. Compound 3 has a doublet electronic ground state. The unpaired electron occupies the alpha HOMO-1 localized at the Zn-containing fragment. The Ga-Zn bond is mainly formed by overlap of the metal orbitals in the alpha HOMO-6 and beta HOMO-5. According to the results of the NBO analysis, the Zn wave functions are responsible for 28.7 % of the Zn-Ga bond, with 96.7 % s, 1.0 % p, and 2.3 % d character.