STUDIES ON OLEFIN-COORDINATING TRANSITION-METAL CARBENE COMPLEXES .20. SYNTHESIS OF 1,3-CYCLOHEXADIENE(DICARBONYL) [ETHOXY(ARYL)-CARBENE]IRON COMPLEXES AND THEIR PHOSPHINE ADDUCTS - CRYSTAL-STRUCTURE OF C6H8(CO)2FEC(OC2H5)C6H4CH3-O

Reaction of 1,3-cyclohexadiene(tricarbonyl)iron (1) with ortho-substituted aryllithium reagents ArLi (Ar=o-CH3C6H4, o-CH3OC6H4, o-CF3C6H4) in ether at low temperature, and subsequent alkylation of the acylmetalates formed with Et3OBF4 in aqueous solution at 0-degrees-C or in CH2Cl2 at -60-degrees-C gave the 1,3-cyclohexadiene(dicarbonyl)[ethoxy(aryl)carbene]iron complexes (eta4-C6H8)(CO)2FeC(OC2H5)Ar (3, Ar = o-CH3C6H4; 4, Ar = o-CH3OC6H4), and the isomerized product (eta3-C6H8)(CO)2FeC(OC2H5)C6H4CF3-o (5), respectively, among which the structure of 3 has been established by an X-ray diffraction study. Complex 3 is monoclinic, space group P2(1) with a = 8.118(4), b = 7.367(4), c = 14.002(6) angstrom, beta = 104.09(3)-degrees, V = 812.2(6) angstrom3, Z = 2, D(c) = 1.39 g cm-3, R = 0.056, and R(w) = 0.062 for 976 observed reflections. Complexes 3 and 5 were converted into the chelated allyliron phosphine adducts(eta3-C6H8)(CO)2(PR31)FeC(OC2H5)Ar (6, Ar = o-CH3C6H4, R1 = Ph; 7, Ar = o-CH3C6H4, R1 = OPh; 9, Ar = o-CF3C6H4, R1 = Ph), by reaction with phosphines in petroleum ether at low temperatures.

Phosphine in various matrixes

Matrix-bound phosphine was determined in the Jiaozhou Bay coastal sediment, in prawn-pond bottom soil, in the eutrophic lake Wulonglan, in the sewage sludge and in paddy soil as well. Results showed that matrix-bound phosphine levels in freshwater and coastal sediment, as well as in sewage sludge, are significantly higher than that in paddy soil. The correlation between matrix bound phosphine concentrations and organic phosphorus contents in sediment samples is discussed.

Matrix-bound phosphine: A new form of phosphorus found in sediment of Jiaozhou Bay

Matrix-bound phosphine (PH3), a new form of phosphorus, was found in sediment of Jiaozhou Bay in December 2001. Concentration and distribution of PH3 in different layers of sediment with different stations were analyzed. The results show that PH3 concentrations are various with different layers and different stations. PH3 concentrations in the bottom layer of sediment (20-30 cm) are usually higher than those in the surface layer (0-4 cm). The highest PH3 concentration in our investigation reaches 685 ng/kg (dry), which is much higher than those in terrestrial paddy soil, marsh and landfill that have been reported up to now. The correlation analysis indicates that there is no apparent correlation between the concentrations of PH3 and inorganic phosphorus in sediment. However, the correlation between the concentrations of phosphine and organic phosphorus in the bottom layer of sediment is remarkable (R-2=0.83). It is mainly considered that PH3 in sediment of Jiaozhou Bay is produced from the decomposition of organic phosphorus in the anaerobic condition, and so PH3 concentrations are related to organic phosphorus concentration and anaerobic environment in sediment. The discovery of PH3 in sediment will give people some new ideas on the mechanisms of phosphorus supplement and biogeochemical cycle in Jiaozhou Bay.

Distribution characteristics of matrix-bound phosphine along the coast of China and possible environmental controls

Matrix-bound phosphine (MBP) concentrations in surface sediments collected from 37 stations along the coast of China in 2006 are reported. MBP was found in all samples and the average concentration was 6.30 ng kg(-1) dry weight (dw). The distribution of MBP showed certain spatial variation characteristics with high MBP concentrations at stations near to the coast. The average concentrations of MBP in the northern Yellow Sea (NYS), the southern Yellow Sea (SYS), the northern area of East China Sea (NECS), the southern area of East China Sea (SECS), and South China Sea (SCS) were 5.57 +/- 3.78, 3.78 +/- 2.81, 5.27 +/- 3.07, 5.48 +/- 4.05 and 13.52 +/- 7.86 ng kg(-1) dw. respectively. The correlations between MBP and influencing factors, such as the sedimentary environmental characteristics (sediment type, the grain size, contents of phosphorous, organic matters and redox potential) and the aquatic environmental characteristics (temperature, salinity, depth and hydrodynamics) were studied. The results indicated that MBP was strongly influenced by various factors, such as total phosphorus (TP), organic phosphorus (OP), organic carbon (OC), the grain size and hydrodynamics, all of which not only offered reasonable interpretations for the distribution characteristics of MBP but also provided evidence to support the viewpoint that phosphine originated from OP decomposition. This work is the first comprehensive study of the distribution of MBP along the coast of China and its relationships with environmental factors which will lead to a better understanding of the phosphorus (P) biogeochemical cycle in the sea. (C) 2008 Elsevier Ltd. All rights reserved.

Seasonal and spatial distribution of matrix-bound phosphine and its relationship with the environment in the Changjiang River Estuary, China

Sediment is commonly considered as a source of phosphine, which is a highly toxic and reactive atmospheric trace gas. This study aims to investigate the seasonal and spatial distribution of matrix-bound phosphine (MBP) and its relationship with the environment in the Changjiang River Estuary. A total of 43 surface sediments were collected in four seasons of 2006, and concentrations of MBP and relative environmental factors were analyzed. MBP ranged from 1.93 to 94.86 ng kg(-1) dry weight (dw) with an average concentration of 17.14 ng kg(-1) dw. The concentrations of MBP in the tipper estuary were, higher than those in the lower estuary, which could be attributed to greater pollutant inputs in the upper estuary. The concentrations of MBP also varied with season, with November > August > May > February. Significant correlations existed between MBP and total phosphorus (TP), organic phosphorus (OP), inorganic phosphorus (W), organic carbon (OC), total nitrogen (TN), the grain size, and redox potential (Eh), suggesting that these sedimentary environmental characteristics played an important role in controlling the MBP levels in the sediments. Notably, there were positive linear relationships between the concentrations of soluble reactive phosphorus (SRP), TP, and chlorophyll a (Chl a) in bottom water and MBP in sediments. These relationships might be very complicated and need further exploration. This work is the first comprehensive study of the seasonal and spatial distribution of MBP in sediments and its relationships with environmental factors in a typical estuary, and will lead to deeper understanding of the phosphorus (P) biogeochemical cycle. (C) 2008 Elsevier Ltd. All rights reserved.

Mild and efficient copper-catalyzed N-arylation of alkylamines and N-H heterocycles using an oxime-phosphine oxide ligand

A mild and efficient copper-catalyzed system for N-arylation of alkylamines and N-H heterocycles with aryl iodides using a novel, readily prepared and highly stable oxime-functionalized phosphine oxide ligand was developed. The coupling reactions could even be performed in solvent-free conditions with moderate to good yields. (c) 2005 Elsevier Ltd. All rights reserved.

Effect of syngas addition on lower alkene production by the oxidative cracking of hexane

The lower alkene production by the gas-phase oxidative cracking (GOC) or catalytic oxidative cracking (COC) of hexane (C6) with added syngas was investigated. The addition of syngas to the COC process could effectively enhance the selectivity to lower alkenes and decrease the selectivity to COx, because of the preferential reaction between O-2 with H-2 contained in the syngas, whereas it has little effect on the conversion of C6 and product distribution in the GOC process. The high selectivity to lower alkenes of 70% and low selectivity to CO, of 6% at C6 conversion of 66% were achieved over 0.1% Pt/MgAl2O4 catalyst. The COC process of C6 combined with the syngas in the feed could directly produce a gas mixture of lower alkenes, H-2, and CO, which usually is a suitable feedstock for the hydroformylation process.

反式和顺式-1，2-二氰-（4-乙基苯）乙烯结构的谱学分析

合成了2种新型的可溶性四氮杂卟啉中间体：反式-1，2二氰-（4-乙基苯）乙烯和顺式-1，2-二氰（4-乙基苯）乙烯。通过UV-Vis，FFIR，GC／MS，^1H NMR等方法对这2种化合物的结构进行了表征，给出了它们完整的结构信息。分析比较了顺、反异构体结构上的差异，分析两者的紫外-可见光谱（UV-Vis）、红外光谱（FTIR）和核磁共振光谱（^1H NMR）谱图的差异及其产生原因。

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.