Diphenyl(dipyrazolyl)methane complexes of Ni: synthesis, structural characterization, and chromotropism of NiBr2 derivatives

The reaction of NiBr2 with the bidentate ligand diphenyl(dipyrazolyl)methane (dpdpm) gives the pentacoordinated complexes [(dpdpm)Ni(mu-Br)Br]2 (1), [(dpdpm)NiBr2(H2O)] (2a), and [(dpdpm)NiBr(H2O)2]Br (2b), or the octahedral complexes [(dpdpm)NiBr(H2O)2(CH3CN)]Br (3), [(dpdpm)2NiBr2] (4), and [(dpdpm)2NiBr(H2O)]Br (5). All of these complexes are paramagnetic, both in the solid state and in solution, and have been characterized by spectroscopic (IR, NMR, and UV-vis-NIR) and X-ray diffraction studies. The unoccupied coordination site in the pentacoordinated compounds allows long-range interactions, in the solid state, between the Ni center and a Ph substituent of the dpdpm ligand. These weak interactions are replaced by Ni-solvent interactions, both in the solid state and in solution, facilitating the interconversion of these compounds under various reaction conditions and leading to interesting solvato-, vapo-, and thermochromic properties. UV-vis-NIR spectroscopy has been used to study these phenomena. Absorption spectra for the room-temperature methanol or acetonitrile solutions of the pentacoordinate or octahedral compounds show three main bands in the region of 350-1000 nm that represent spin-allowed (d-d) transitions from the ground state 3A2g to the excited states 3T2g, 3T1g(3F), and 3T1g(3P). A weak shoulder was also detected on the middle peak in most spectra (700-800 nm), representing the spin-forbidden 3A2g-->1Eg transition. On the other hand, the spectra of high-temperature CH2Cl2 or acetone solutions of all complexes show four main bands at ca. 490, 650-660, 860, and 1000 nm, in addition to a shoulder on the first or second band.     

[2‐(1H‐Inden‐3‐yl)­ethyl]­di­phenyl­phos­phine–borane

The title compound, C₂₃H₂₄BP, crystallizes in the centrosymmetric space group P2₁/c, with one mol­ecule in the asymmetric unit. The indene moiety is essentially planar. The P—B bond length is 1.923 (3) Å, which is within the expected range.     

New palladium(II)-(eta(3/5)- or eta1-indenyl) and dipalladium(I)-(mu,eta3-indenyl) complexes

Reaction of the dimeric species [(eta3-Ind)Pd(mu-Cl)]2 (1) (Ind = indenyl) with NEt3 gives the complex (eta(3-5)-Ind)Pd(NEt3)Cl (3), whereas the analogous reactions with BnNH2 (Bn = PhCH2) or pyridine (py) afford the complexes trans-L2Pd(eta1-Ind)Cl (L = BnNH2 (4), py (5)). Similarly, the one-pot reaction of 1 with a mixture of BnNH2 and the phosphine ligands PR3 gives the mixed-ligand, amino and phosphine species (PR3)(BnNH2)Pd(eta1-Ind)Cl (R = Cy (6a), Ph (6b)); the latter complexes can also be prepared by addition of BnNH2 to (eta(3-5)-Ind)Pd(PR3)Cl (R = Cy (2a), Ph (2b)). Complexes 6 undergo a gradual decomposition in solution to generate the dinuclear Pd(I) compounds (mu,eta3-Ind)(mu-Cl)Pd2(PR3)2 (R = Cy (7a), Ph (7b)) and the Pd(II) compounds (BnNH2)(PR3)PdCl2 (R = Cy (8a), Ph (8b)), along with 1,1'-biindene. The formation of 7 is proposed to proceed by a comproportionation reaction between in situ-generated Pd(II) and Pd0 intermediates. Interestingly, the reverse of this reaction, disproportionation, also occurs spontaneously to give 2. All new compounds have been characterized by NMR spectroscopy and, in the case of 3, 4, 5, 6a, 7a, 7b, and 8a, by X-ray crystallography.     

Ni(II) complexes featuring non-metallated pincer-type ligands

Attempts to prepare pincer-type Ni complexes from the ligands (i-Pr(2)POCH(2))(2)CH(2) and (pz*CH(2))(2)CH(2) (pz* = 3,5-dimethylpyrazol-1-yl) gave instead the complexes cis-{kappa(P),kappa(P')-(i-Pr(2)POCH(2))(2)CH(2)}NiCl(2) and {kappa(N),kappa(N')-(pz*CH(2))(2)CH(2)}NiBr(2). X-Ray diffraction studies confirmed that these potentially pincer-type ligands have not undergone metallation, serving instead as chelating ligands in essentially square-planar or tetrahedral complexes. Heating of these compounds failed to induce metallation of the coordinated ligands.     

Estimating local bonding/antibonding character of canonical molecular orbitals from their energy derivatives. The case of coordinating lone pair orbitals

According to Koopmans theorem, the derivative of the energy of a canonical molecular orbital (MO) with respect to nuclear coordinates quantifies its bonding/antibonding character. This quantity allows predictions of bond length variation on ionisation in a panel of 19 diatomic species. In polyatomic molecules, the derivative of a MO energy with respect to a given bond length reveals the nature and the degree of the bonding/antibonding contribution of this MO with respect to this bond. Accordingly, the HOMO “lone pairs” of CO and CN^? and the HOMO‐2 of CH₃CN are found to be antibonding with respect to the C? X bond (X = N, O), whereas the HOMO of N₂ is found to be bonding. With the same approach, the variation of the bonding character in the MOs of CO and CH₃CN on interaction with an electron acceptor (modeled through the approach of a proton) or by applying an electric field was studied. © 2016 Wiley Periodicals, Inc.     

Charge Effects in PCP Pincer Complexes of NiII bearing Phosphinite and Imidazol(i)ophosphine Coordinating Jaws: From Synthesis to Catalysis through Bonding Analysis

This contribution reports on a new family of Ni^II pincer complexes featuring phosphinite and functional imidazolyl arms. The proligands ^RPIMC^HOP^R′ react at room temperature with Ni^II precursors to give the corresponding complexes [(^RPIMCOP^R′)NiBr], where ^RPIMCOP^R=κ^P,κ^C,κ^P‐{2‐(R′₂PO),6‐(R₂PC₃H₂N₂)C₆H₃}, R=iPr, R′=iPr ( 3 b , 84 %) or Ph ( 3 c , 45 %). Selective N‐methylation of the imidazole imine moiety in 3 b by MeOTf (OTf=OSO₂CF₃) gave the corresponding imidazoliophosphine [(^iPrPIMIOCOP^iPr)NiBr][OTf], 4 b , in 89 % yield (^iPrPIMIOCOP^iPr=κ^P,κ^C,κ^P‐{2‐(iPr₂PO),6‐(iPr₂PC₄H₅N₂)C₆H₃}). Treating 4 b with NaOEt led to the NHC derivative [(NHCCOP^iPr)NiBr], 5 b , in 47 % yield (NHCCOP^iPr=κ^P,κ^C,κ^C‐{2‐(iPr₂PO),6‐(C₄H₅N₂)C₆H₃)}). The bromo derivatives 3–5 were then treated with AgOTf in acetonitrile to give the corresponding cationic species [(^RPIMCOP^R)Ni(MeCN)][OTf] [R=Ph, 6 a (89 %) or iPr, 6 b (90 %)], [(^RPIMIOCOP^R)Ni(MeCN)][OTf]₂ [R=Ph, 7 a (79 %) or iPr, 7 b (88 %)], and [(NHCCOP^R)Ni(MeCN)][OTf] [R=Ph, 8 a (85 %) or iPr, 8 b (84 %)]. All new complexes have been characterized by NMR and IR spectroscopy, whereas 3 b , 3 c , 5 b , 6 b , and 8 a were also subjected to X‐ray diffraction studies. The acetonitrile adducts 6 – 8 were further studied by using various theoretical analysis tools. In the presence of excess nitrile and amine, the cationic acetonitrile adducts 6 – 8 catalyze hydroamination of nitriles to give unsymmetrical amidines with catalytic turnover numbers of up to 95.     

A structural study of model peptides derived from HIV-1 integrase central domain

The HIV-1 integrase (IN) catalyzes the integration of viral DNA in the human genome. In vitro the enzyme displays an equilibrium of monomers, dimers, tetramers and larger oligomers. However, its functional oligomeric form in vivo is not known. We report a study of the auto-associative properties of three peptides denoted K156, E156 and E159. These derive from the alpha4 helix of the IN catalytic core. The alpha4 helix is an amphipatic helix exposed at the surface of the protein and could be involved in the oligomerization process through its hydrophobic face. The peptides were obtained from the replacement of several amino acid residues by more helicogenic ones in the alpha4 helix peptide. K156 carries the basic residues Lys156 and Lys159, which have been shown important for the binding of IN to viral DNA. In E156 and E159 they are replaced with the acidic residue Glu. A fourth peptide K(E)156 obtained from the replacement of hydrophobic residues with Glu in K156 in order to abolish the auto-associative properties is used as a negative control. The capacity shown by peptides for alpha-helical formation is demonstrated by circular dichroism (CD) analysis performed in aqueous solution and in aqueous trifluoroethanol (TFE) mixtures. Both electrospray ionization mass spectrometry (ESI-MS) and glutaraldehyde chemical cross-linking show that peptides adopt different solvent-dependent equilibriums of monomers, dimers, trimers and tetramers. Oligomerization of peptides in aqueous solution is related to their ability to form helical structures. Addition of a small amount of TFE (<10%) stimulates helix stabilization and the interhelical hydrophobic contacts. Higher amounts of TFE alter the hydrophobic contacts and disrupt the oligomeric species. In addition to hydrophobic interactions, the patterns indicate that the biologically important Lys156 and Lys159 residues also participate in helix association. K(E)156 despite its ability to adopt a helical structure is unable to associate into oligomers, demonstrating the importance of hydrophobic contacts for oligomerization. Thus, the designed peptides provide us information on the functional properties of the alpha4 IN that seems to hold a dual role in DNA recognition and protein oligomerization.     

Facile fabrication of novel polycaprolactone-based electrospun fibers using in-process water exposure

To overcome the problems related to the low surface enrichment of blended fibers from hydrophilic polymer, routine blend electrospinning setup was modified by exposing the polycaprolactone (PCL)–Pluronic P123 solution to water in order to attract the hydrophilic chains toward the fiber surface. Analysis of the modified fibers revealed a drastic surge of hydrophilic polymer surface enrichment value in comparison with that of the routine method which suggested homogenously positioned Pluronic on the surface and the subsequent reduction of its accumulations within fibers. The thermogram of the proposed method showed induced crystallization in the Pluronic section. Furthermore, the intensity of PCL characteristic peaks decreased for this method.