Gelatin Type A from Porcine Skin Used as Co-Initiator in a Radical Photo-Initiating System

In the present study, a different approach for the preparation of poly(ethylene glycol) diacrylate-gelatin (PEGDA-gelatin) hydrogels was investigated. Gelatin type A from porcine skin was used as the co-initiator of a radical photo-initiating system instead of the traditional aliphatic or aromatic amines. This became possible because, upon visible-light irradiation, the amine sequences within gelatin generate initiating free-radicals through the intermolecular proton transfer in a Norrish type II reaction with camphorquinone (CQ). PEGDA-gelatin hydrogels were prepared by visible-light-induced photopolymerization. The gelatin content in the precursor formulations was varied. The influence of gelatin on the kinetics of the photocuring reaction was investigated, and it was found that gelatin fastened the rate of polymerization at all concentrations. The covalent attachment of gelatin segments within the cross-linked hydrogels was evaluated by means of attenuated total reflectance-infrared spectroscopy (ATR-FTIR) spectroscopy after solvent extraction. The thermo-mechanical properties, as well as the swelling behavior and gel content, were also investigated

Synthesis of γ-cyclodextrin substituted bis(acyl)phosphane oxide derivative (BAPO-γ-CyD) serving as multiple photoinitiator and crosslinking agent

Cyclodextrin with up to 10 bis(acyl)phosphanoxide functions serves as an initiator for highly cross-linked swellable hydrogels from mono-acrylates

Kinetic Stabilization of Heavier Bis(m-terphenyl)pnictogen Phosphaethynolates

Kinetic stabilization using bulky m-terphenyl substituents is the key to the isolation of the diarylantimony and diarylbismuth phosphaethynolates (2,6-Mes2C6H3)2EPCO and the related N-heterocyclic carbene complexes (2,6-Mes2C6H3)2EP(O)C(IMe4) (E=Sb, Bi; IMe4=1,3,4,5-tetramethylimidazol-2-ylidene), which have been fully characterized crystallographically and spectroscopically. The experimental characterization was augmented by a DFT based real space bond indicator analysis of the electron density, including AIM, NCI, and ELI-D methods

The Chemistry of the Cyaphide Ion

We review the known chemistry of the cyaphide ion, (C≡P)−. This remarkable diatomic anion has been the subject of study since the late nineteenth century, however its isolation and characterization eluded chemists for almost a hundred years. In this mini-review, we explore the pioneering and synthetic experiments that first allowed for its isolation, as well as more recent developments demonstrating that cyaphide transfer is viable in well-established salt-metathesis protocols. The physical properties of the cyaphide ion are also explored in depth, allowing us to compare and contrast the chemistry of this ion with that of its lighter congener cyanide (an archetypal strong field ligand and important organic functional group). Recent studies show that the cyaphide ion has the potential to be used as a versatile chemical regent for the synthesis of novel molecules and materials hinting at many interesting future avenues of investigation

Anionic 1-Aza-3,4-diphospholides as redox active ligands

ISSN:0020-1693ISSN:1873-325

Spectroscopic Characterization, Computational Investigation, and Comparisons of ECX

Three newly synthesized [Na+(221-Kryptofix)] salts containing AsCO–, PCO–, and PCS– anions were successfully electrosprayed into a vacuum, and these three ECX– anions were investigated by negative ion photoelectron spectroscopy (NIPES) along with high-resolution photoelectron imaging spectroscopy. For each ECX– anion, a well-resolved NIPE spectrum was obtained, in which every major peak is split into a doublet. The splittings are attributed to spin–orbit coupling (SOC) in the ECX• radicals. Vibrational progressions in the NIPE spectra of ECX– were assigned to the symmetric and the antisymmetric stretching modes in ECX• radicals. The electron affinities (EAs) and SO splittings of ECX• are determined from the NIPE spectra to be AsCO•: EA = 2.414 ± 0.002 eV, SO splitting = 988 cm–1; PCO•: EA = 2.670 ± 0.005 eV, SO splitting = 175 cm–1; PCS•: EA = 2.850 ± 0.005 eV, SO splitting = 300 cm–1. Calculations using the B3LYP, CASPT2, and CCSD(T) methods all predict linear geometries for both the anions and the neutral radicals. The calculated EAs and SO splittings for ECX• are in excellent agreement with the experimentally measured values. The simulated NIPE spectra, which are based on the calculated Franck–Condon factors, and the SO splittings nicely reproduce all of the observed spectral peaks, thus allowing unambiguous spectral assignments. The finding that PCS• has the greatest EA of the three triatomic molecules considered here is counterintuitive based upon simple electronegativity considerations, but this finding is understandable in terms of the movement of electron density from phosphorus in the HOMO of PCO– to sulfur in the HOMO of PCS–. Comparisons of the EAs of PCO• and PCS• with the previously measured EA values for NCO• and NCS• are made and discussed.National Science Foundation (U.S.) (Grant CHE-1362118

Low-valent homobimetallic Rh complexes: influence of ligands on the structure and the intramolecular reactivity of Rh–H intermediates

Supporting two metal binding sites by a tailored polydentate trop-based (trop - 5H-dibenzo[a,d] cyclohepten-5-yl) ligand yields highly unsymmetric homobimetallic rhodium(I) complexes. Their reaction with hydrogen rapidly forms Rh hydrides that undergo an intramolecular semihydrogenation of two C≡C bonds of the trop ligand. This reaction is chemoselective and converts C≡C bonds to a bridging carbene and an olefinic ligand in the first and the second semihydrogenation steps, respectively. Stabilization by a bridging diphosphine ligand allows characterization of a Rh hydride species by advanced NMR techniques and may provide insight into possible elementary steps of H₂ activation by interfacial sites of heterogeneous Rh/C catalysts

Isomerization and fragmentation reactions of gaseous dimethyl phenylarsane radical cations and methyl phenylarsenium cations. A study by tandem mass spectrometry and density functional theory calculations

Kirchhoff D, Grützmacher H-F, Grützmacher H. Isomerization and fragmentation reactions of gaseous dimethyl phenylarsane radical cations and methyl phenylarsenium cations. A study by tandem mass spectrometry and density functional theory calculations. EUROPEAN JOURNAL OF MASS SPECTROMETRY. 2006;12(1):171-180.The unimolecular reactions of the radical cation of dimethyl phenylarsane, C6H5As(CH3)(2), 1(.+), and of the methyl phenylarsenium cation, C6H5As+CH3, 2(+), in the gas phase were investigated using deuterium labeling and methods of tandem mass spectrometry. Additionally, the rearrangement and fragmentation processes were analyzed by density functional theory (DFT) calculations at the level UBHLYP/6-311+G(2d,p)//UBHLYP/5-31+G(d). The molecular ion 1(.+) decomposes by loss of a center dot CH3, radical from the As atom without any rearrangement, in contrast to the behavior of the phenylarsane radical cation. In particular, no positional exchange of the H atoms of the CH3 group and at the phenyl ring is observed. The results of DFT calculations show that a rearrangement of 1(.+) by reductive elimination of As and shift of the CH3 group is indeed obstructed by a large activation barrier. The mass-analyzed kinetic energy spectrum of 2(+) shows that this arsenium cation fragments by losses of H-2 and AsH. The fragmentation of the trideuteromethyl derivative 2-d(3)(+) proves that all H atoms of the neutral fragments originate specifically from the methyl ligand. Identical fragmentation behavior is observed for metastable m-tolyl arsenium cation, m-CH3-C6H4As+H, 2tol(+). The loss of AsH generates ions C7H7+ which requires rearrangement in 2(+) and bond formation between the phenyl and methyl ligands prior to fragmentation. The DFT calculations confirm that the precursor of this fragmentation is the benzyl methylarsenium cation, 2bzl(+), and that 2bzl(+) is also the precursor ion fo the elimination of H-2. The analysis of the pathways for rearrangements of 2(+) to the key intermediate, 2bzl(+), by DFT calculations show that the preferred route corresponds to a 1,2-H shift of a H atom from the CH3 ligand to the As atom and a shift of the phenyl group in the reverse direction. The expected rearrangement by a reductive elimination of the As atom, which is observed for the phenylarsenium cation and for halogeno phenyl arsenium cations, requires much more activation enthalpy