Probing the C-H Activation of Linear and Cyclic Ethers at (PNP)Ir

Interaction of the amido/bis(phosphine)-supported (PNP)Ir fragment with a series of linear and cyclic ethers is shown to afford, depending on substrate, products of α,α-dehydrogenation (carbenes), α,β-dehydrogenation (vinyl ethers), or decarbonylation. While carbenes are exclusively obtained from tert-amyl methyl ether, sec-butyl methyl ether (SBME), n-butyl methyl ether (NBME), and tetrahydrofuran (THF), vinyl ethers or their adducts are observed upon reaction with diethyl ether and 1,4-dioxane. Decarbonylation occurs upon interaction of (PNP)Ir with benzyl methyl ether, and a mechanism is proposed for this unusual transformation, which occurs via a series of C−H, C−O, and C−C bond cleavage events. The intermediates characterized for several of these reactions as well as the α,α-dehydrogenation of tert-butyl methyl ether (MTBE) are used to outline a reaction pathway for the generation of PNP-supported iridium(I) carbene complexes, and it is shown that the long-lived, observable intermediates are substrate-dependent and differ for the related cases of MTBE and THF. Taken together, these findings highlight the variety of pathways utilized by the electron-rich, unsaturated (PNP)Ir fragment to stabilize itself by transferring electron density to ethereal substrates through oxidative addition and/or the formation of π-acidic ligands

syn,syn-15,17-Di-2-naphthyl­hexa­cyclo­[10.2.1.13,10.15,8.02,11.04,9]hepta­decane deuterochloro­form monosolvate

The main molecule of the title compound, C37H36·CDCl3, is a hydro­carbon with two naphthalene segments attached to opposite ends of a rigid norbornylogous spacer with an overall structure that is approximately C-shaped. The dihedral angle between the naphthalene ring planes is 9.27 (7)°. The cleft that exists between the naphthalene rings is large enough that the compound crystallizes with a solvent mol­ecule (CDCl3) in the cleft. The CDCl3 solvent mol­ecule is present in two disordered orientations in a 3:2 ratio, each involving C—D⋯π to C 6 ring centers

Electronic Structure of Dinuclear Gold(I) Complexes

Cyclic voltammetry (CV) experiments on LL(AuSR∗)2 complexes [LL = diphenylphosphinomethane (dppm), diphenylphosphinopentane (dpppn); R* = p-SC6H4CH3] show anodic sweeps that broaden by about 25 mV on going from the longer (dpppn) to the shorter (dppm) bidentate phosphine ligand. Changing concentrations had no effect on the shape of the waveform. The result suggests a weak intramolecular metal-metal interaction in dppm(AuSR∗)2 that correlates well with rate acceleration occurring in the reaction of dppm(AuSR∗)2 with organic disulfides. Quantum yields for cis-dppee(AuX)2 [dppee = 1,2-bis(diphenylphosphino)ethylene; X = Cl, Br, I] complexes, (disappearance) Φ , are significantly higher in complexes with a softer X ligand, a trend that correlates well with aurophilicity. This result also suggests that electronic perturbation caused by Au(I)-Au(I) interactions is important in explaining the reactivity of some dinuclear gold(I) complexes. The crystal structure for cis-dppee(Aul)2 shows short intramolecular Au(I)-Au(I) interactions of 2.9526 (6) A°, while the structure of trans-dppee(AuI)2 , shows intermolecular Au(I)-Au(I) interactions of 3.2292 (9) A°. The substitution of .As for P results in a ligand, cis-diphenylarsinoethylene (cis-dpaee), that is photochemically active, in contrast to the cis-dppee ligand. The complexes, cis-dpaee(AuX)2, are also photochemically active but with lower quantum yields than the cis-dppee(AuX)2 complexes

Penerapan Model Pembelajaran Atraktif Berbasis Multiple Intelligences Tentang Pemantulan Cahaya pada Cermin

Penelitian ini bertujuan untuk mengetahui efektivitas penerapan model pembelajaran atraktif berbasis multiple intelligences dalam meremediasi miskonsepsi siswa tentang pemantulan cahaya pada cermin. Pada penelitian ini digunakan bentuk pre-eksperimental design dengan rancangan one group pretest-post test design. Alat pengumpulan data berupa tes pilihan ganda dengan reasoning. Hasil validitas sebesar 4,08 dan reliabilitas 0,537. Siswa dibagi menjadi lima kelompok kecerdasan, yaitu kelompok linguistic intelligence, mathematical-logical intelligence, visual-spatial intelligence, bodily-khinestetic intelligence, dan musical intelligence. Siswa membahas konsep fisika sesuai kelompok kecerdasannya dalam bentuk pembuatan pantun-puisi, teka-teki silang, menggambar kreatif, drama, dan mengarang lirik lagu. Efektivitas penerapan model pembelajaran multiple intelligences menggunakan persamaan effect size. Ditemukan bahwa skor effect size masing-masing kelompok berkategori tinggi sebesar 5,76; 3,76; 4,60; 1,70; dan 1,34. Penerapan model pembelajaran atraktif berbasis multiple intelligences efektif dalam meremediasi miskonsepsi siswa. Penelitian ini diharapkan dapat digunakan pada materi fisika dan sekolah lainnya

Fitting the pieces of the puzzle: The δ bond

The development of our understanding of the δ bond and its role in quadruple metal-metal bonding is described in terms of the conceptual advances and experimental and theoretical results achieved through a 50-year period beginning with the seminal report by Cotton and co-workers in 1964. The work behind the original discovery is described, along with the qualitative orbital description of the components of the quadruple bond. The effect of torsion about the metal-metal axis on the metal-metal bond length is described, together with the conclusion that this accords with a progressive loss of the δ component of the metal-metal bond. The important role of photoelectron spectroscopy in characterizing the loss of electrons from the metal-metal bonding orbitals is reviewed, as are the electron paramagnetic resonance results that establish that unpaired electrons, when present, populate metal-based orbitals. Other important results are described: destabilization of the metal-metal bond to produce strong reducing agents, exceptions to the expected orbital ordering, and the use of chiroptical properties to reveal additional information about the electronic structure of the metal-metal bond.C.A.M. thanks Texas A&M University and the National Science Foundation (IR/D support). L.R.F. thanks the Ministerio de Ciencia e Innovación (Spain) for support under Grant MAT2011-27233-C02-01 with cofinancing from the European Union Regional Development Fund (FEDER), and B.M.F. acknowledges the National Science Foundation for support.Peer Reviewe

Single crystal x-ray structures of 2-pyridinecarboxaldehydeazine and biacetylazine: implications of the conjugation in systems with carbon-nitrogen double bonds

Crystal structures were determined for two compounds, 2-pyridinecarboxaldehydeazine, 1, and biacetylazine, 2. 2-Pyridinecarboxaldehydeazine crystallizes in space group P21/c with a = 10.0487(7) Å, b = 4.6452(7) Å, c = 11.6700(11) Å, β = 91.030(6)°, V = 544.65(10) Å3, Z = 2, R = 0.0345. Biacetylazine crystallizes in space group C2/c with a = 9.879(7) Å, b = 12.409(4) Å, c = 7.950(6) Å, β= 98.44(6)°, V = 964.0(11) Å3, Z = 4, R = 0.0496. Comparison of the imine bond lengths of these and other azine and diimine systems found in the literature suggests that conjugation of imines is better through the carbon-carbon bond than through the nitrogen-nitrogen bond. Semiempirical structural calculations demonstrate that the N-N bond in these azines is rotationally soft, thereby allowing significant twisting at little energy cost. This accounts for the observation that 1 is planar and 2 is not. © 1999 American Chemical Society