Design, Synthesis, and Study of Novel Platforms for Iron-N2 Chemistry and Photoinduced, Copper-mediated C-N Bond Formation

Several new ligand platforms designed to support iron dinitrogen chemistry have been developed. First, we report Fe complexes of a tris(phosphino)alkyl (CP^iPr₃) ligand featuring an axial carbon donor intended to conceptually model the interstitial carbide atom of the nitrogenase iron-molybdenum cofactor (FeMoco). It is established that in this scaffold, the iron center binds dinitrogen trans to the C_alkyl anchor in three structurally characterized oxidation states. Fe-C_alkyl lengthening is observed upon reduction, reflective of significant ionic character in the Fe-C_alkyl interaction. The anionic (CP^iPr₃)FeN₂^- species can be functionalized by a silyl electrophile to generate (CP^iPr₃)Fe-N₂SiR₃. This species also functions as a modest catalyst for the reduction of N₂ to NH₃. Next, we introduce a new binucleating ligand scaffold that supports an Fe(μ-SAr)Fe diiron subunit that coordinates dinitrogen (N₂-Fe(μ-SAr)Fe-N₂) across at least three oxidation states (Fe^IIFe^II, Fe^IIFe^I, and Fe^IFe^I). Despite the sulfur-rich coordination environment of iron in FeMoco, synthetic examples of transition metal model complexes that bind N₂ and also feature sulfur donor ligands remain scarce; these complexes thus represent an unusual series of low-valent diiron complexes featuring thiolate and dinitrogen ligands. The (N₂-Fe(μ-SAr)Fe-N₂) system undergoes reduction of the bound N₂ to produce NH₃ (~50% yield) and can efficiently catalyze the disproportionation of N₂H₄ to NH₃ and N₂. The present scaffold also supports dinitrogen binding concomitant with hydride as a co-ligand. Next, inspired by the importance of secondary-sphere interactions in many metalloenzymes, we present complexes of iron in two new ligand scaffolds ([SiP^NMe₃] and [SiP^iPr₂P^NMe]) that incorporate hydrogen-bond acceptors (tertiary amines) which engage in interactions with nitrogenous substrates bound to the iron center (NH₃ and N₂H₄). Cation binding is also facilitated in anionic Fe(0)-N₂ complexes. While Fe-N₂ complexes of a related ligand ([SiP^iPr₃]) lacking hydrogen-bond acceptors produce a substantial amount of ammonia when treated with acid and reductant, the presence of the pendant amines instead facilitates the formation of metal hydride species.

Additionally, we present the development and mechanistic study of copper-mediated and copper-catalyzed photoinduced C-N bond forming reactions. Irradiation of a copper-amido complex, ((m-tol)₃P)₂Cu(carbazolide), in the presence of aryl halides furnishes N-phenylcarbazole under mild conditions. The mechanism likely proceeds via single-electron transfer from an excited state of the copper complex to the aryl halide, generating an aryl radical. An array of experimental data are consistent with a radical intermediate, including a cyclization/stereochemical investigation and a reactivity study, providing the first substantial experimental support for the viability of a radical pathway for Ullmann C-N bond formation. The copper complex can also be used as a precatalyst for Ullmann C-N couplings. We also disclose further study of catalytic C_alkyl-N couplings using a CuI precatalyst, and discuss the likely role of [Cu(carbazolide)₂]^- and [Cu(carbazolide)₃]^- species as intermediates in these reactions.

Finally, we report a series of four-coordinate, pseudotetrahedral P₃Fe^II-X complexes supported by tris(phosphine)borate ([PhBP₃Fe^R]^-) and phosphiniminato X-type ligands (-N=PR'₃) that in combination tune the spin-crossover behavior of the system. Low-coordinate transition metal complexes such as these that undergo reversible spin-crossover remain rare, and the spin equilibria of these systems have been studied in detail by a suite of spectroscopic techniques.

Microwave power effects on the properties of phosphorus-doped SiC:H films prepared using ECR-CVD

There has been a growing interest in hydrogenated silicon carbide films (SiC:H) prepared using the electron cyclotron resonance-chemical vapour deposition (ECR-CVD) technique. Using the ECR-CVD technique, SiC:H films have been prepared from a mixture of methane, silane and hydrogen, with phosphine as the doping gas. The effects of changes in the microwave power (from 150 to 900 W) on the film properties were investigated in a series of phosphorus-doped SiC:H films. In particular, the changes in the deposition rate, optical bandgap, activation energy and conductivity were investigated in conjunction with results from Raman scattering and Fourier transform infra-red (FTIR) analysis. It was found that increase in the microwave power has the effect of enhancing the formation of the silicon microcrystalline phase in the amorphous matrix of the SiC:H films. This occurs in correspondence to a rapid increase in the conductivity and a reduction in the activation energy, both of which exhibit small variations in samples deposited at microwave powers exceeding 500 W. Analysis of IR absorption results suggests that hydrogen is bonded to silicon in the Si-H stretching mode and to carbon in the sp3 CHn rocking/wagging and bending mode in films deposited at higher microwave powers.

In situ doping control for growth of n-p-n Si/SiGe/Si heterojunction bipolar transistor by gas source molecular beam epitaxy

N-p-n Si/SiGe/Si heterostructures have been grown by a disilane (Si2H6) gas and Ge solid sources molecular beam epitaxy system using phosphine (PH3) and diborane (B2H6) as n- and p-type in situ doping sources, respectively. Adopting an in situ doping control technology, the influence of background B dopant on the growth of n-Si emitter layer was reduced, and an abrupt B dopant distribution from SiGe base to Si emitter layer was obtained. Besides, higher n-type doping in the surface region of emitter to reduce the emitter resist can be realized, and it did not result in the drop of growth rate of Si emitter layer in this technology. (C) 2004 Elsevier B.V. All rights reserved.

Abatement of waste gases and water during the processes of semiconductor fabrication

The purpose of this article is to examine the methods and equipment for abating waste gases and water produced during the manufacture of semiconductor materials and devices. Three separating methods and equipment are used to control three different groups of electronic wastes. The first group includes arsine and phosphine emitted during the processes of semiconductor materials manufacture. The abatement procedure for this group of pollutants consists of adding iodates, cupric and manganese salts to a multiple shower tower (MST) structure. The second group includes pollutants containing arsenic, phosphorus, HF, HCl, NO2, and SO3 emitted during the manufacture of semiconductor materials and devices. The abatement procedure involves mixing oxidants and bases in an oval column with a separator in the middle. The third group consists of the ions of As, P and heavy metals contained in the waste water. The abatement procedure includes adding CaCO3 and ferric salts in a flocculation-sedimentation compact device equipment. Test results showed that all waste gases and water after the abatement procedures presented in this article passed the discharge standards set by the State Environmental Protection Administration of China.

Growth of SiGe heterojunction bipolar transistor using Si2H6 gas and Ge solid sources molecular beam epitaxy

N-p-n Si/SiGe/Si heterostructure has been grown by a disilane (Si2H6) gas and Ge solid sources molecular beam epitaxy system using phosphine (PH3) and diborane (B2H6) as n- and p-type in situ doping sources, respectively. X-ray diffraction (XRD) and secondary ion mass spectroscopy (SIMS) measurements show that the grown heterostructure has a good quality, the boron doping is confined to the SiGe base layer, and the Ge has a trapezoidal profile. Postgrowth P implantation was performed to prepare a good ohmic contact to the emitter. Heterojunction bipolar transistor (HBT) has been fabricated using the grown heterostructure and a common-emitter current gain of 75 and a cut-off frequency of 20 GHz at 300 K have been obtained. (C) 2001 Elsevier Science B.V. All rights reserved.

The growth of Si/SiGe/Si structures for heterojunction bipolar transistor by gas source molecular beam epitaxy

Three n-p-n Si/SiGe/Si heterostructures with different layer thickness and doping concentration have been grown by a home-made gas source molecular-beam epitaxy (GSMBE) system using phosphine (PH3) and diborane (B2H6) as n-and p-type in situ doping sources, respectively. Heterojunction bipolar transistors (HBTs) have been fabricated using these structures and a current gain of 40 at 300 K and 62 at 77 K have been obtained. The influence of thickness and doping concentration of the deposited layers on the current gain of the HBTs is discussed. (C) 2000 Elsevier Science B.V. All rights reserved.

Doping during low-temperature growth of materials for n-p-n Si/SiGe/Si heterojuction bipolar transistor by gas source molecular beam epitaxy

In situ doping for growth of n-p-n Si/SiGe/Si heterojuction bipolar transistor (HBT) structural materials in Si gas source molecular beam epitaxy is investigated. We studied high n-type doping kinetics in Si growth using disilane and phosphine, and p-type doping in SiGe growth using disilane, soild-Ge, and diborane with an emphasis on the effect of Ge on B incorporation. Based on these results, in situ growth of n-p-n Si/SiGe/Si HBT device structure is demonstrated with designed structural and carrier profiles, as verified from characterizations by X-ray diffraction, and spreading resistance profiling analysis. (C) 2000 Elsevier Science B.V. All rights reserved.

High phosphorous doping and morphological evolution during Si growth by gas source molecular beam epitaxy (GSMBE)

Uniform and high phosphorous doping has been demonstrated during Si growth by GSMBE using disilane and phosphine. The p-n diodes, which consist of a n-Si layer and a p-SiGe layer grown on Si substrate, show a normal I-V characteristic. A roughening transition during P-doped Si growth is found. Ex situ SEM results show that thinner film is specular. When the film becomes thicker, there are small pits of different sizes randomly distributed on the flat surface. The average pit size increases, the pit density decreases, and the size distribution is narrower for even thicker film. No extended defects are found at the substrate interface or in the epilayer. Possible causes for the morphological evolution are discussed. (C) 1999 Elsevier Science B.V. All rights reserved.

Recyclable heterogeneous Rh/SiO2 catalyst enhanced by organic PPh3 ligand

Heterogeneous PPh3-Rh/SiO2 catalysts for hydroformylation of olefins, prepared by direct doping of phosphine onto the heterogeneous Rh/SiO2 precursor, exhibited high activity and selectivity towards aldehydes, which originated from chemical coordination bond between the phosphine and Rh metal nantoparticles on the SiO2 support.

The optical properties and the natural lifetime calculation of a Sm(III) complex

The photophysical properties of the complex Sm(PM)(3)(TP)(2) [PM = 1-phenyl-3-methyl-4-isobutyryl-5-pyrazolone, TP = triphenyl phosphine oxide] are determined in crystal state, and energy transfer process is modeled for ligands to center Sm(III) ion. The characteristic luminescence of Sm(III) is sensitized by PM and TP, and most of transitions from excited state (4)G(5/2) of Sm3+ are detected.

1.54 mu m near-infrared photoluminescent and electroluminescent properties of a new Erbium (111) organic complex

The crystal structure of Er(PM)(3)(TP)(2) [PM = 1-Phenyl-3-methyl-4-isobutyryl-5-pyrazoloiie, TP = triphenyl phosphine oxide] was reported and its photoluminescence properties were studied by UV-vis absorption, excited, and emission spectra. The Judd-ofelt theory was introduced to calculate the radiative transition rate and the radiative decay time of 3.65 ms for the I-4(13/2) -> I-4(15/2) transition of Er3+ ion in this complex.

Alternating Copolymerization of Cyclohexene Oxide and Carbon Dioxide Catalyzed by Noncyclopentadienyl Rare-Earth Metal Bis(alkyl) Complexes

The syntheses of several dialkyl complexes based on rare-earth metal were described. Three beta-diimine compounds with varying N-aryl substituents (HL1 = (2-CH3O(C6H4))N=C(CH3)CH=C(CH3)NH(2-CH3O(C6H4)), HL2 = (2,4,6-(CH3)(3) (C6H2))N=C(CH3)CH=C(CH3)NH(2,4,6-(CH3)(3)(C6H2)), HL3 = PhN=C(CH3)CH(CH3) NHPh) were treated with Ln(CH2SiMe3)(3)(THF)(2) to give dialkyl complexes L(1)Ln (CH2SiMe3)(2) (Ln = Y (1a), Lu (1b), Sc (1c)), L(2)Ln(CH2SiMe3)(2)(THF) (Ln = Y (2a), Lu (2b)), and (LLu)-Lu-3(CH2SiMe3)(2)(THF) (3). All these complexes were applied to the copolymerization of cyclohexene oxide (CHO) and carbon dioxide as single-component catalysts.

Thiophene-NPN Ligand Supported Rare-Earth Metal Bis(alkyl) Complexes. Synthesis and Catalysis toward Highly trans-1,4 Selective Polymerization of Butadiene

A series of new rare-earth metal bis(alkyl) complexes [L(1-3)Ln(CH2SiMe3)(2)(THF)(n)] (L-1 = MeC4H2SCH2NC6H4(Ph)(2)P=NC6H2Me3-2,4,6: Ln = Sc, n = 1 (1a); Ln = Lu, n = 1 (1b); L-2 = MeC4H2SCH2NC6H4(Ph)(2)P=NC6H3Et2-2,6: Ln = Sc, n = 1 (2a); Ln = Lu, n = 1 (2b); Ln = Y, n = 1 (2c); L-3 = MeC4H2SCH2NC6H4(Ph)(2)P=(NC6H3Pr2)-Pr-i-2,6: Ln = Sc, n = 0 (3a)) and (LSc)-Sc-4(CH2SiMe3)(2()THF) (4a) (L-4 = C6H5CH2NC6H4(Ph)(2)P=NC6H3Et2-2,6) have been prepared by reaction of rare-earth metal tris(alkyl)s with the corresponding HL1-4 ligands via alkane elimination.

Isoprene polymerization with indolide-imine supported rare-earth metal alkyl and amidinate complexes

Reaction of 7-{(N-2,6-R)iminomethyl)}lindole (HL1, R = dimethylphenyl; HL2, R = diisopropylphenyl) and rare-earth metal tris(alkyl)s, Ln(CH2SiMe3)(3)(THF)(2), generated new rare-earth metal bis(alkyl) complexes LLn(CH2SiMe3)(2)(THF) [L = L-1: Ln = Lu. (1a), Sc (1b); L = L-2 : Ln = Lu (3a), Se (3b)] and mono(alkyl) complexes L-2 Lu-2(CH2SiMe3) (4a). Treatment of alkyl complexes 1a and 4a with N,N'-diisopropylcarbodiimide afforded the corresponding amidinates (LLu)-Lu-1{iPr(2)NC(CH2SiMe3) NiPr2}(2) (2a) and L-2 Lu-2{iPr(2)NC(CH2SiMe3)NiPr2} (5a), respectively.

Near-infrared luminescent properties and natural lifetime calculation of a novel Er3+ complex

in this communication, a novel Er3+ complex Er(PT)(3)TPPO [PT = 1-phenyl-3-methyl-4-tert-butylbenzoyl-5-pyrazolone, TPPO = triphenyl phosphine oxide] is successfully synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. Its optical properties and the energy transfer process from the ligand PT to the Er3+ ion are investigated, the typical near-infrared (NIR) luminescence (centered at around 1530 nm) is attributed to the I-4(13/2) -> I-4(15/2) transition of Er3+ ion which results from the efficient energy transfer from PT to Er3+ ion (an antenna effect). The wider full width at half maximum (78 nm) peaked at 1530 nm in the emission spectrum and the Judd-Ofelt theory calculation on the radiative properties suggest that Er(PT)(3)TPPO should be a promising candidate for tunable lasers and planar optical amplifiers.