玉米/花生间作行比和施磷对玉米光合特性的影响

试验于2014—2015年设玉米/花生间作2∶2(R₁)、2∶4(R₂)和2∶8(R₃)三种间作模式,研究了间作行比和施磷对玉米冠层光照日变化、功能叶的SPAD值、光合-光强响应曲线和光合-CO₂响应曲线的影响,以探究间作玉米适应强光的光合机理.结果表明: 间作玉米冠层日均光照表现为R₃>R₂>R₁;大口期至灌浆期,间作玉米穗位叶的SPAD值、表观量子效率(AQY)、光补偿点(LCP)、光饱和点(LSP)、光饱和时的最大净光合速率(LSP_n)、羧化效率(CE)、最大电子传递速率(J_max)、磷酸丙糖利用率(TPU)、气孔导度(g_s)、蒸腾速率(T_r)和净光合速率(P_n)均表现为R₃>R₂>R₁,胞间CO₂浓度(C_i) 则为R₁>R₂>R₃;蜡熟期R₃间作玉米的AQY、LSP_n、g_s、CE、J_max和TPU均低于R₂间作玉米;施磷能提高AQY、LSP_n、CE、V_{c max}、J_max和TPU等光合参数.这说明间作玉米g_s、AQY、CE、V_{c max}、J_max和TPU随着光强增加逐渐提高是其增强利用强光能力的关键,但超过一定光强易早衰,施磷肥有助于增强玉米对强光的利用和延缓叶片衰老.     

行距和播种量对冬小麦冠层光合有效辐射垂直分布、生物量和籽粒产量的影响

为明确行距和播种量对冬小麦冠层光合有效辐射(PAR)垂直分布、生物量和籽粒产量的影响,在不增加水肥等投入的基础上,设置等行距(R₁,20 cm+20 cm)、宽窄行(R₂,12 cm+12 cm+12 cm+24 cm)两种行距方式和低(D₁,120 kg·hm^-2)、中(D₂,157.5 kg·hm^-2)、高(D₃,195 kg·hm^-2)3个播种量水平,分析不同处理组合下冬小麦主要生育时期冠层PAR的截获率及利用率、群体光合能力、生物量和产量差异。结果表明: 冬小麦冠层总PAR截获率、上层PAR截获率均表现为R₁行距显著大于R₂,而中层和下层PAR截获率则表现为R₂大于R₁,且在中层差异显著;从小麦开花至成熟期,相同播种量下R₂行距光合势(LAD)、群体光合速率(CAP)、PAR转化率和利用率都显著高于R₁,并以R₂D₂处理最大;冬小麦的群体生物量(BA)和不同层次叶片生物量(BL)均表现为随播种量增加而增加,但单株生物量(BP)则相反。在同一播种量下,BA、BL和BP均在开花期之后表现为R₂行距高于R₁,其中,BA、BP在成熟期行距间差异显著,中层和下层BL在D₂、D₃播种量下行距间差异显著;不同处理组合间冬小麦的穗数、穗粒数、千粒重、籽粒产量分别以R₂D₃、R₂D₁、R₂D₁、R₂D₂最大,其中,R₂行距下千粒重、穗粒数和籽粒产量显著大于R₁。综上,改变行距可以改善小麦冠层中下层PAR的截获量,增强冬小麦单株和群体光合能力、光合有效辐射的利用及转化效率,提高生物量和籽粒产量。在冬小麦高产栽培中,应重视通过优化田间结构,塑造麦田理想的群体光合结构,以充分利用单位土地面积上光照资源,挖掘作物自身的光合生产潜力,达到高产高效的目的。在本试验条件下,以R₂D₂配置群体光合能力、光合有效辐射利用率和产量最佳。     

Direct nitration of aryl groups σ-bound to ruthenium(II)

A new method has been developed for the preparation of nitroaryl transition metal complexes using copper(II) nitrate in the presence of acetic anhydride (Menke conditions) to directly nitrate an aryl group which is already σ-bound to a transition metal centre. Under these conditions ruthenium(II) aryl complexes of the type: (where R₁=R₂=H; R₁=H, R₂=CH₃; R₁=CH₃, R₂=H) react to yield three distinct types of nitroaryl-containing products (I–III).

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The preparation and characterisation of these compounds are described. X-ray crystallographic data for one example of each of the three types of compound, are also reported. The compounds that have been studied crystallographically are Ru(C₆H₄NO₂-4)(η²-O₂CCH₃)(CO)(PPh₃)₂ (1a), C₄₅H₃₇NO₅P₂Ru·(CH₂Cl₂)_0.5, a = 20.254(5), b=19.437(8), c=22.629(3) Å, β=115.390(10)°, monoclinic, space group C2/c, Z=8; Ru(C6H4N[O]O-2)- Cl(CO)(PPh₃)₂ (4a), C₄₃H₃₄ClNO₃P₂Ru, a=9.331(3), b=12.443(2), c=16.346(3) Å, =82.81(2), β=85.03(2), γ=74.76(2)°, triclinic, space group P , Z=2; Ru(C₆H₂CH₃-2,NO₂-4,N[O]O-6)Cl(CO)(PPh₃)₂ (5b), C₄₄H₃₅Cl- N₂O₅P₂Ru·(CH₂Cl₂)₂, a=19.497(3), b=14.502(3), c=19.340(5) Å, β=122.79(1)°, monoclinic, space group Cc, Z=4.     

Quantitative structure-activity relationships of nicotine analogues as neuronal nicotinic acetylcholine receptor ligands

Quantitative structure-activity relationships of 34 pyrrolidine-modified nicotine agonists are investigated for their binding affinity toward neuronal nicotinic acetylcholine receptor. The results indicate that a large substituent at the R₁, R₂, and R₃ position is detrimental to the binding affinity. Likewise, a large substituent at the R₂ or R₃ position as well as a hydrogen bond accepting substituent at the R_2β position are not beneficial to the binding.     

黄河口不同恢复阶段湿地土壤N2O产生过程对氮输入的响应

以黄河口生态恢复前后未恢复区(R₀)、2007年恢复区(R₂₀₀₇)和2002年恢复区(R₂₀₀₂)的芦苇湿地为研究对象,研究了不同形态氮输入对湿地土壤N₂O产生过程的影响与贡献.结果表明: 硝态氮(NO₃^--N)输入对恢复区湿地土壤N₂O总产生量的影响远远大于铵态氮(NH₄⁺-N),但两者均抑制了R₀土壤的N₂O总产生量.尽管NO₃^--N输入对R₂₀₀₂表层土壤N₂O总产生量的影响明显大于R₂₀₀₇,但二者的N₂O产生量均随氮输入量的增加而增加.恢复区湿地土壤的反硝化作用和硝化细菌反硝化作用受NO₃^--N输入的影响明显,而R₀土壤产生N₂O的生物过程受其影响并不显著.尽管NH₄⁺-N输入对湿地土壤N₂O的总产生量影响不大,但其输入整体促进了R₀ 土壤的硝化细菌反硝化作用、R₂₀₀₇土壤的硝化作用和R₂₀₀₂土壤的非生物作用.比较而言,NO₃^--N输入对R₀、R₂₀₀₇和R₂₀₀₂湿地土壤N₂O产生的非生物作用主要表现为抑制,NH₄⁺-N输入则整体提高了R₀和R₂₀₀₂湿地土壤非生物作用的N₂O产生量,这与不同形态氮输入对土壤pH的调节作用密切相关.研究发现,NO₃^--N输入大大增加了湿地土壤的N₂O总产生量,改变了原有湿地土壤生物作用和非生物作用的贡献模式,故生态恢复工程导致的营养盐输入(NO₃^--N)应受到特别关注.     

黄河口不同恢复阶段湿地土壤N2O产生过程对氮输入的响应

以黄河口生态恢复前后未恢复区(R₀)、2007年恢复区(R₂₀₀₇)和2002年恢复区(R₂₀₀₂)的芦苇湿地为研究对象,研究了不同形态氮输入对湿地土壤N₂O产生过程的影响与贡献.结果表明: 硝态氮(NO₃^--N)输入对恢复区湿地土壤N₂O总产生量的影响远远大于铵态氮(NH₄⁺-N),但两者均抑制了R₀土壤的N₂O总产生量.尽管NO₃^--N输入对R₂₀₀₂表层土壤N₂O总产生量的影响明显大于R₂₀₀₇,但二者的N₂O产生量均随氮输入量的增加而增加.恢复区湿地土壤的反硝化作用和硝化细菌反硝化作用受NO₃^--N输入的影响明显,而R₀土壤产生N₂O的生物过程受其影响并不显著.尽管NH₄⁺-N输入对湿地土壤N₂O的总产生量影响不大,但其输入整体促进了R₀ 土壤的硝化细菌反硝化作用、R₂₀₀₇土壤的硝化作用和R₂₀₀₂土壤的非生物作用.比较而言,NO₃^--N输入对R₀、R₂₀₀₇和R₂₀₀₂湿地土壤N₂O产生的非生物作用主要表现为抑制,NH₄⁺-N输入则整体提高了R₀和R₂₀₀₂湿地土壤非生物作用的N₂O产生量,这与不同形态氮输入对土壤pH的调节作用密切相关.研究发现,NO₃^--N输入大大增加了湿地土壤的N₂O总产生量,改变了原有湿地土壤生物作用和非生物作用的贡献模式,故生态恢复工程导致的营养盐输入(NO₃^--N)应受到特别关注.     

Synthesis and structural characterization of two cis-dioxorhenium(V) ReO2[SN][P] mixed-ligand complexes

Two novel five-coordinate cis-dioxorhenium(V) complexes of the general formula ReO₂[R₂NCH₂CH₂S][PPh₃] (R₂N=Et₂N, complex 1 and R₂N=(o-CH₃O---C₆H₄N(CH₂CH₂)₂N, complex 2) have been synthesized by reacting ReOCl₃(PPh₃)₂ with the respective bidentate ligands R₂NCH₂CH₂SH. The complexes have been characterized by elemental analysis, IR, NMR spectroscopies and X-ray crystallography. X-ray crystallographic studies showed that the coordination geometry around rhenium is distorted trigonal bipyramidal. The basal plane is defined by the two doubly bonded oxygen atoms and the sulfur of the bidentate ligand, while the nitrogen of the ligand and the phosphorus occupy the apical positions.     

The versatile coordination chemistry of tricyanoethenolate, [(NC)2C=C(CN)O]

The reaction of meso-tetrakis (4-dimethoxyphenyl) porphinatomanganese(II), MnTP_OMeP, with TCNE (TCNE = tetracyanoethylene) leads to the formation of [MnTP_OMeP]⁺ [TCNE]⁻ and [MnTP_OMeP]⁺[OC(CN)C(CN)₂]⁻. The single-crystal X-ray structures of the latter as well as [Cu(bipy)₂Cl]⁺ [OC(CN)C(CN)₂]⁻ were determined. The former has a disordered [OC(CN)C(CN)₂]⁻ bridging via C and O between a pair of Mn^III sites, whereas the latter has an isolated [OC(CN)C(CN)₂]⁻ unbound to Cu^II. The IR characterization for μ₂-C,O bound [OC(CN)C(CN)₂]⁻ is at 2219m and 2196s (νCN) cm⁻¹ and at 1558s (νCO) cm⁻¹ while for unbound [OC(CN)C(CN)₂]⁻ it is at 2210m, 2203m, 2181m (νCN) cm⁻¹ and at 1583s (νCO) cm⁻¹.     

自组装短肽R2I4R2对皮肤创伤快速修复过程的研究

研究探索自组装短肽R₂I₄R₂在人皮肤成纤维细胞体外三维培养的应用效果与对创伤修复过程的作用。通过圆二色谱仪分析不同时间、温度和离子条件对其二级结构的影响;刚果红染色宏观检测短肽自组装情况;体外培养人皮肤成纤维细胞探索细胞在R₂I₄R₂形成的纳米纤维网络中的生长状态及凋亡情况;建立SD大鼠皮肤创伤模型,HE染色与免疫组织化学检测其对皮肤创伤修复的病理变化。结果表明,R₂I₄R₂在不同条件下均可形成较为稳定的二级结构;自组装24h后可形成均一稳定的膜片状结构,为细胞三维培养提供支架;人皮肤成纤维细胞可在R₂I₄R₂形成的纳米纤维网络三维环境中生长且状态良好;动物实验表明,短肽R₂I₄R₂可减少炎症、促进新生血管生成、加速皮肤创伤修复过程。自组装短肽R₂I₄R₂作为新的纳米支架材料,可用于细胞三维培养与皮肤创伤修复。     

估测水稻叶层氮浓度的新型蓝光氮指数

基于不同氮素水平与品种类型的多个田间试验,综合分析了水稻冠层高光谱植被指数与叶层氮浓度的定量关系.结果表明：对氮反应最敏感的波段为红光665～675 nm、蓝光490～500 nm和红边区域波段680～760 nm.400～2500 nm波段范围内两波段植被指数与水稻叶层氮浓度相关性最好的是550～600 nm与500～550 nm,属绿光波段组合,决定系数（R²）最高的是比值指数SR(533,565).以3个蓝光波段构建的光谱参数R₄₃₄/(R₄₉₆+R₄₀₁)（蓝光氮指数）与水稻叶层氮浓度呈极显著的直线相关关系,与SR(533,565)相比,该参数显著提高了对叶层氮浓度的预测性.独立资料检验结果显示,R₄₃₄/(R₄₉₆+R₄₀₁)对水稻叶层氮浓度具有较好的预测性,检验根均方差（RMSE）和相对误差（RE）值分别为9.67%和8%,是一种适合于水稻叶层氮浓度估测的良好高光谱植被指数.     

山西历山千金榆群落物种多样性研究

在野外调查的基础上,应用Patric丰富度指数（R₀）、Simpson指数（λ）和Shannon-Wiener多样性指数（H'）、Pielou均匀度指数（E₁）和Alatalo均匀度指数（E₅）等对山西历山千金榆群落物种多样性进行了分析研究。结果表明：（1）千金榆群落R₀、H'、E₁和E₅等多样性指数变化趋势基本一致,λ与H'等指数变化趋势相反;综合考虑：千金榆群落的物种多样性顺序为群丛Ⅰ（千金榆-山胡椒-糙苏群丛） > 群丛Ⅲ（千金榆-连翘-糙苏群丛） > 群丛Ⅳ（千金榆-土庄绣线菊+连翘-鹿药群丛） > 群丛Ⅶ（千金榆-接骨木-贝加尔唐松草+淫羊藿群丛） > 群丛Ⅱ（千金榆-小花溲疏-糙苏群丛） > 群丛Ⅵ（千金榆-小花溲疏-香根芹群丛） > 群丛Ⅴ（千金榆-小花溲疏-鹿药群丛）;（2）乔木层多样性与灌木层多样性、草本层多样性呈负相关（P<0.05）,而灌木层多样性与草本层的多样性相关不显著（P>0.05）;（3）千金榆各群丛间多样性指数差异不显著。     

Chronopharmacology of Albuterol in Hospitalized Asthmatic Children

Eleven children (8-16 years old) hospitalized for acute bronchospasm were included in this investigation. Throughout the study, the children received the standardized course of therapy for hospitalized asthmatics with corticosteroids and albuterol nebulizations. Children receiving ipratropium were excluded from the study. Spirometric measurements, including forced expiratory volume in 1s (FEV₁), were made immediately before and 30 min after each albuterol nebuliza-tion over a 24-h period. The well-known temporal changes in FEV₁, were observed in patients suffering from nocturnal asthma (NA): basal values were maximal at midday (10 a.m. to 2 p.m.) and lowest in the evening or at night (10 p.m. to 6 a.m.). This 24-h variation in lung function was not found in children without nocturnal exacerbations of their asthma. A 24-h variation was also observed in albuterol-induced bronchodilation in patients with NA: maximal effectiveness occurred at night, and lower effect was obtained with the midday administration. The albuterol-induced increases in FEV₁, were not clinically significant in children without nocturnal asthma except when the β₂-agonist was inhaled between 10 p.m. and 2 a.m. The data suggest that patients with nonnocturnal asthma might have different drug requirements than those with nocturnal symptoms. Key Words: Albuterol—Asthma—Circadian rhythms—-Children—FEV₁.     

Inhibition of human gastric and pancreatic lipases by chiral alkylphosphonates. A kinetic study with 1,2-didecanoyl-sn-glycerol monolayer

Enantiomerically pure alkylphosphonate compounds RR′P(O)PNP (R=C_nH_2n+1, R′=OY with Y=C_n′H_2n′+1 with n=n′ or n≠n′; PNP=p-nitrophenoxy) noted (RY), mimicking the transition state occurring during the carboxyester hydrolysis were synthesized and investigated as potential inhibitors of human gastric lipase (HGL) and human pancreatic lipase (HPL). The inhibitory properties of each enantiomer have been tested with the monomolecular films technique in addition to an enyzme linked immunosorbent assay (ELISA) in order to estimate simultaneously the residual enzymatic activity as well as the interfacial lipase binding. With both lipases, no obvious correlation between the inhibitor molar fraction (₅₀) leading to half inhibition, and the chain length, R or Y was observed. (R₁₁Y₁₆)s were the best inhibitor of HPL and (R₁₀Y₁₁)s were the best inhibitors of HGL. We observed a highly enantioselective discrimination, both with the pure enantiomeric alkylphosphonate inhibitors as well as a scalemic mixture. We also showed, for the first time, that this enantioselective recognition can occur either during the catalytic step or during the initial interfacial adsorption step of the lipases. These experimental results were analyzed with two kinetic models of covalent as well as pseudo-competitive inhibition of lipolytic enzymes by two enantiomeric inhibitors.     

Characteristics and use as spin trapping agent of a beta-phosphorylated nitroso compound, DEPNP

2-(Diethylphosphonate)-nitrosopropane (DEPNP), prepared by oxidation of the corresponding aminophosphonate, was found to essentially exist as monomer in both water and organic solvents. The mechanisms of its degradation under 80°C heating or visible light exposure were studied by EPR spectroscopy: its decomposition gave rise to paramagnetic by-products, which have been identified as DEPNP / ·C(CH₃)₂[P(O)(OC₂H₅)₂] and DEPNP / ·P(O)(OC₂H₅)₂ spin adducts. Despite this drawback, DEPNP was successfully used as spin trapping agents to scavenge various carbon — and phosphorus-centred free radicals both in aqueous and organic media, giving rise to intense EPR spectra characteristic of the species trapped.     

滨海盐土土壤水分的高光谱参数及估测模型

基于滨海盐土5个试验点的土壤含水量和室内土壤表面高光谱反射率,综合分析了350～2500 nm波段范围内土壤含水量与土壤光谱之间的关系,并基于比值光谱指数(RSI)、归一化光谱指数(NDSI)和差值光谱指数(DI)确定了光谱参数,进而构建土壤含水量估测定量模型.结果表明： 滨海盐土原始光谱反射率与土壤含水量呈显著负相关关系,且最大负相关出现在1930 nm(r=0.86)附近.对RSI、NDSI和DI的直线回归方程、幂函数回归方程进行对比,以RSI(R₁₄₀₇,R₁₄₅₉)为自变量构建的土壤含水量指数函数线性回归方程决定系数最大(0.780),标准误较小(0.016),拟合方程为y=0.00001e^9.72053x.估测模型能够更好地监测滨海盐土土壤水分状况.基于RSI(R₁₄₀₇,R₁₄₅₉)构建的模型可实现对江苏省滨海盐土土壤水分的精确监测.     

叶片和群落尺度净光合速率关系的探讨

叶片净光合速率(P_n)是研究光合作用机理的基本尺度; 而群落净光合速率(P_c)是研究群落光合能力及其与外部环境因子间关系的更好尺度, 特别是区域乃至全球尺度碳循环的研究, 需要将叶片尺度的生理生态模型扩展到冠层尺度。理论上, 群落内所有叶片的累积P_n与实测群落净气体交换速率(NCE)是相等的, 但在野外实际观测中, 两者之间的相互关系目前尚未见报道。该文选取敖汉苜蓿(Medicago sativa ‘Aohan’)人工草地, 采用美国LI-COR公司生产的便携式光合测定系统LI-6400测定P_n, 结合叶面积指数等参数推算P_c, 利用LI-8100连接同化箱测定生态系统净气体交换速率(NEE), 加上土壤呼吸速率, 得到NCE。结果表明: P_c为3.52 μmol CO₂·m^-2·s^-1, 与实测NCE (3.56 μmol CO₂·m^-2·s^-1)基本相等。这表明: 可利用P_n, 结合叶面积指数、群落叶片数目、健康叶片比例和群落可接收有效光照的平均比例等4个关键参数, 准确地换算P_c。然而, 利用同化箱式法测定群落呼吸速率时, 不可避免地会包含土壤呼吸, 所以在观测NCE时, 需要同时测定土壤呼吸。此外, 在冠层模型中, 群落垂直结构和光量子的非线性响应不可忽视。     

煤矿区复垦土壤中有机肥的分解动态及其驱动因素

基于煤矿区不同复垦年限土壤,研究有机肥的分解动态及其驱动因素,可为有机肥合理施用和矿区土壤培肥提供科学依据。本研究以山西煤矿复垦区为试验平台,采用尼龙网袋填埋法,在复垦年限为1年(复垦初期阶段,R₁)、10年(复垦中期阶段,R₁₀)和30年(复垦长期阶段,R₃₀)的土壤中进行有机肥分解试验(有机肥碳量与土壤重量比例为4∶100)。供试有机肥为牛粪和猪粪,以不添加有机肥为对照(CK),填埋深度为15 cm。在填埋后的第12、23、55、218、281和365 d采集尼龙网袋样品,测定有机肥残留量、土壤微生物生物量碳(MBC)和可溶性有机碳(DOC)含量,采用方差分解分析(VPA)量化土壤性质、有机肥性质和水热条件对有机肥分解的贡献率。结果表明: 猪粪的分解速率显著高于牛粪。猪粪的腐殖化系数(46.3%)显著低于牛粪(71.7%);猪粪在复垦30年的土壤中的腐殖化系数(44.5%)显著低于复垦1年和10年的土壤(47.2%);而牛粪在3种复垦年限土壤中的腐殖化系数无显著差异。猪粪和牛粪的易分解碳库占总碳库的比例分别为52%和26%,易分解碳库分解速率常数分别为0.00085和0.00074 ℃^-1,且差异显著。在0~218 d填埋时间段内,猪粪还田对复垦土壤MBC和DOC的提升作用显著高于牛粪,在281~365 d填埋时间段内,两者差异不显著。有机肥还田下,3种复垦年限土壤中MBC和DOC的增长幅度均表现为R₁ >R₁₀ ≈ R₃₀。在土壤性质、物料性质和水热条件中,有机肥性质是其分解的主要影响因子,对有机肥分解的单独贡献率最大,为17.9%。综上,猪粪的分解受到土壤复垦年限的影响,而牛粪的分解不受土壤复垦年限的影响。在不同复垦年限土壤中,牛粪的腐殖化系数显著高于猪粪,在煤矿复垦区建议选择腐熟的牛粪进行有机肥还田,以提高土壤肥力。     

Electrical skin resistance and rectal temperature changes in resting human subjects exposed to heat

1. 1.|Fourteen male volunteers were examined under passive heating.

2. 2.|Electrical skin resistance (ESR) and rectal temperature (T_re) were measured during the whole period of exposure.

3. 3.|It was found that:

• —|ESR decreases rapidly with increasing air temperature. Assuming an exponential curve yields a mean time constant of 14 min.

• —|There is a correlation between the individual ESR time constants and T_re increases (r = 0.695, P < 0.005).

• —|Additional changes of ESR were noted in 8 subjects at a constant air temperature of 42°C.

4. 4.|It is concluded that ESR may be a useful indicator of the sweating response of the human thermoregulatory system during exogenous heat load.

遮光和施氮对暗紫贝母生长和C-N平衡的影响

为了了解暗紫贝母对资源变化的适应策略,本研究通过田间控制试验,研究了遮光和施氮对暗紫贝母生物量、生物量分配,以及叶、根C、N状态的影响。结果表明：遮光和施氮处理后,暗紫贝母生物量均减少;遮光下叶片的生物量分配相对增加,叶根生物量比显著升高（P<0.05）,但施氮处理下叶根生物量比的变化不明显;遮光和施氮后,暗紫贝母叶、根N含量均显著升高（P<0.05）,叶片和根的C：N显著降低（P<0.05）;相关分析显示,叶片N、C：N与暗紫贝母总生物量、叶根生物量比有极显著的相关性（P<0.01）。本研究表明,与生物量分配相比,C-N平衡,尤其是叶片的C：N比能更好的解释暗紫贝母对资源变化的适应。     

Synthesis, characterization and reactivity of platinum-substituted ketenes [PtX{η-C(PPh3)CO}L2]BF4, (X=Me, Cl; L2=1,5-cyclooctadiene, 1,2-bis(diphenylphosphino)ethane, cis-1,2-bis(diphenylphosphino)ethene). Steric and electronic effects of the ancillary ligands

Ketenylidenetriphenylphosphorane, Ph₃PC=C=O, 1, has been used to synthesize platinum-substituted ketenes [PtMe{η¹-C(PPh₃)CO}L₂]BF₄, 2a, b (L₂=1,5-cyclooctadiene, cod (a), 1,2-bis(diphenylphosphino)ethane, diphos (b)). Parent compound [PtCl{η¹-C(PPh₃)CO}L₂]BF₄, 3, with L₂=cis-1,2-bis(diphenylphosphino)ethene, diphoe, was also synthesized, which is stable only at low temperature. The stability of 2 and 3 and the reactivity of the C=C=O moiety have been examined and discussed in terms of the electronic and steric characteristics of the ancillary ligands, also taking into account the reactivity of the ‘PtXL₂’ fragment with other carbonyl stabilized phosphorus ylides, Ph₃PCHCOR (R=Me, Ph, OMe, OEt).