木榄幼苗对淹水胁迫的生长和生理反应

在搭建于广西英罗湾红树林外裸滩的试验平台上设置8个海面高程组,研究全日潮海区潮汐淹水胁迫对木榄(Bruguiera gymnorrhiza)幼苗的生长和生理影响.幼苗立地基质平面的海面高程为320～390 cm,相邻高程组相差10 cm,幼苗培养时间为1 a.结果表明:小高程和大高程处理均促进木榄幼苗茎高度的增长,中等高程则起抑制作用;中等高程组幼苗茎节数稍少;叶数、叶面积与叶保存率均随淹水程度加大而急剧下降;小高程生境对叶片叶绿素含量的促进作用较微弱,而大高程生境更有利于叶绿素含量上升;但较长时间的淹水胁迫使叶绿素a/b比值反而较高;小高程处理均促使叶片和根系中超氧物歧化酶(SOD)和过氧化物酶(POD)酶活性增强,同一高程组的木榄幼苗根系中超氧物歧化酶和过氧化物酶酶活性均高于叶片的数倍;较大高程生境更有利于木榄幼苗生物量累积,尤其是叶生物量,同时随着淹水程度的加大,新生器官中生物量分配比例由叶向茎转移;所有高程组均有一些幼苗死亡,海面高程越小幼苗存活率越低,由73.6%下降到35.0%.综合考虑,建议北部湾海区木榄胚轴造林的宜林临界线高程不低于当地平均海面以上21 cm.     

广西沿海红海榄造林的宜林临界线

2004年8月—2005年8月,在广西英罗湾滩涂上建造8个高程梯度(320~390cm,相邻梯级间高度差10cm)的试验平台,研究全日潮海区潮汐淹水胁迫对红海榄幼苗生长和生理指标的影响.结果表明:小高程(320~330cm)生境对红海榄幼苗茎高生长有微弱促进作用,340cm以上高程组幼苗茎高随滩涂高程增加而增大.中等高程(350~370cm)有利于幼苗茎节数的增长.滩涂高程越低,幼苗叶数、叶面积和叶保存率越低.小高程组幼苗叶片叶绿素a受损明显,叶绿素b则受损相对较轻;叶绿素a/b值随滩涂高程降低而减少.长时间淹水诱导使根系中SOD活性上升,叶片中则表现为中等高程组酶活性较低.叶片和根系中POD活性均随高程降低而增加.淹水胁迫使红海榄幼苗各器官及全株的生物量降低;随着淹水程度加大,新生器官生物量分配比例由叶向茎转移.随着高程降低,幼苗存活率从88.9%降至40.0%,但370cm以上高程组存活率均在80%以上.建议将当地平均海面线作为广西沿海红海榄胚轴造林的宜林临界线.     

重金属镉对红树植物白骨壤和桐花树幼苗生理特性的影响

通过砂泥栽培实验研究了红树植物桐花树和白骨壤幼苗在含Cd 0.6～30 mmol·L~(-1)系列海水培养液中某些生理特性的变化。当培养液中Cd浓度为0.6 mmol·L~(-1)时桐花树和白骨壤幼苗生长正常,叶绿素含量和光合速率变化不大。当高于12 mmol·L~(-1)时,除桐花树和白骨壤幼苗除POD酶活性越来越高之外,叶绿素含量、光合速率、SOD、CAT酶活性均不断减弱,而且浓度愈高,这些指标下降愈大。结果表明Cd对红树植物桐花树和白骨壤幼苗具有毒害作用,Cd浓度愈高对其毒害愈严重,两种红树植物比较,桐花树抗重金属镉毒害的能力大于白骨壤。     

多氯联苯对桐花树幼苗生长及膜保护酶系统的影响

通过盆栽实验,研究了不同浓度(180、900、1 800和2 700 μg·kg^-1)多氯联苯(PCBs)对红树植物桐花树幼苗生长、叶绿素含量、膜质过氧化产物丙二醛（MDA）以及膜保护酶系统的影响.结果表明：PCBs对桐花树幼苗的生长有一定的促进作用,随着PCBs浓度的提高,桐花树幼苗的茎高、茎径和茎体积均呈升高趋势;在试验PCBs浓度范围内,桐花树幼苗叶片能保持相对正常的叶绿素水平和相对稳定的叶绿素a/b值,叶绿素a、叶绿素b和叶绿素a+b含量虽然有所降低,但均未低于对照的75%;叶绿素a/b值有所升高,但均未超过对照的10％.随着PCBs浓度的提高,桐花树幼苗叶片SOD活性呈单峰曲线变化,而POD活性和MDA含量呈单谷曲线变化.红树植物桐花树可通过生理生化机制适应一定浓度的PCBs污染,对PCBs有较强的耐受性和适应性,可用于PCBs污染的植物修复.     

大亚湾红树林研究Ⅱ,澳头港部分红树植物的生态生理

对大亚湾澳头港的３种红树植物的光合速率、呼吸速率和蒸腾速率进行测定,结果表明：桐花树、白骨壤和木榄的光合速率日进程呈双峰曲线,日平均光合速率的大小为桐花树＞木榄＞白骨壤,而日均呼吸速率的大小为桐花树＞白骨壤＞木榄,呼吸速率的变化幅度小于光合速率,提示白骨壤的生产力最低,可能与其所处的生境含盐量更高有关。蒸腾速率日进程呈单峰曲线,且泌盐植物桐花树和白骨壤的日均值很接近,都高于拒盐种木榄,表明蒸腾速率与它们的泌盐或拒盐生理特性密切相关。总体上,这些红树植物具有较高的光合速率、较低的呼吸速率和蒸腾速率,有利于生长在盐渍淹水的特殊海滩环境。     

秋茄(Kandelia candel)幼苗对多氯联苯污染的生理生态响应

通过盆栽实验,研究了4种不同浓度(180 、900 、1800 和2700μg kg^-1)的多氯联苯（PCBs）对红树植物秋茄幼苗的茎高、茎径、生物量、相对生长速率以及叶片的叶绿素含量、水势、丙二醛含量和游离脯氨酸含量等生理生态指标的影响,结果表明:（1）在所设PCBs浓度范围内,PCBs对秋茄幼苗的茎高、茎径、生物量和相对生长速率等生长指标的生长没有产生不利的影响,相反具有促进作用,红树植物秋茄在PCBs污染情况下能旺盛生长;（2）在所设PCBs浓度范围内,秋茄幼苗叶片能保持相对正常的叶绿素水平和相对稳定的叶绿素a/b值,叶绿素a、叶绿素b和叶绿素a+b的含量虽然有所降低,但均为对照的70%以上;叶绿素a/b值有所升高,但均未超过对照的15％。（3）随着PCBs浓度的升高,秋茄幼苗叶片水势呈上升趋势,而游离脯氨酸含量和膜质过氧化产物MDA含量均有一定的增加,说明PCBs对秋茄幼苗产生了一定的影响。总体来看,秋茄幼苗能在所设浓度的PCBs范围内正常生长,对PCBs有较强的耐受性和适应性,对PCBs污染的沉积物进行修复是可行的。     

三种泌盐红树植物对盐胁迫的耐受性比较

在盐度 0、5、15、2 5和 35 (% )下种植泌盐红树植物老鼠 (Acanthus ilicifolius)、桐花树 (Aegiceras corniculatum)和白骨壤(Avicennia marina)的繁殖体 ,以繁殖体萌发、幼苗生长、叶片泌盐量、叶片组织液盐含量和蒸腾蒸发量为指标 ,比较其对盐胁迫的耐受性。盐度提高对胎生种类桐花树和白骨壤的萌根速率无显著影响 ,但高盐度明显抑制非胎生种类老鼠的萌根。白骨壤的萌苗率不受盐度影响 ,但 2 5以上的盐度导致桐花树和老鼠的萌苗率下降。在盐度范围 5～ 35内 ,白骨壤幼苗的茎高生长随盐度的增加而减少 ,但减少量比桐花树小 ,而老鼠的减少量最大。老鼠因盐度提高而导致的叶片长度的减少量最大。在盐度提高的情况下 3种植物均具有泌盐量增加的效应 ,在任一盐度下泌盐能力的顺序均为白骨壤 >桐花树 >老鼠。淡水培养时 ,3种红树植物的叶片组织液盐含量 (约 2 % )均高于环境盐度 0。在盐度范围 5～ 35内 ,白骨壤的叶片组织液盐含量维持在较稳定的水平 (4 .3%～ 5 .0 % ) ,桐花树的变化范围为 2 .4 %～ 4 .5 % ,老鼠 2 .3%～ 5 .3%。淡水培养时 ,3种植物的蒸腾蒸发量类似 ,但盐性条件下白骨壤的蒸腾蒸发量显著高于桐花树和老鼠。随着盐度的增加 ,老鼠的蒸腾蒸发量下降最多。这些结果均表     

广西西端海岸四种红树植物天然种群生境高程

在广西防城港市东湾渔洲坪、石角、交东3个样地平行海面方向共设置18条剖面对4种红树植物白骨壤(Avicenniamarina)、桐花树(Aegiceras corniculatum)、秋茄(Kandelia obovata)、木榄(Bruguiera gymnorhiza)在沿海滩涂生长带高程测量和群落调查。调查结果表明:由于人类活动造成东湾渔洲坪和交东两个样地的坡度变化较大,分别从-0.37变化为-0.05和-0.72变化为-0.10,而地处北仑河口保护区内的石角样地受到保护,没有人为因素的影响,坡度从-0.23变化为-0.10变化不大。石角和交东两个样地中的桐花树集中出现在高程15至40 cm和33至36 cm范围内;秋茄集中出现在高程43至60 cm和37至51cm范围内;木榄集中出现在高程94至106 cm和111至119 cm范围内。所有样地中的白骨壤在高程60至80 cm范围内,树高最高达到220 cm,且分布密集;桐花树在高程20至40 cm范围内,树高最高达到200 cm,且分布密集;秋茄在高程40至80 cm范围内,树高最高达到200 cm,且分布密集;木榄在高程60至100 cm范围内,且分布密集,树高最高达280 cm。通过对各样地剖面上红树植物种类出现频度的分析和林木高度的测量,4种红树植物天然林临界滩涂高程分别为:桐花树为-7 cm;秋茄为+33 cm;白骨壤为+23和+26 cm;木榄为+44 cm。对应的浸淹时间分别为8.5、7.0、7.0、6.0h。在石角和交东分别有30.0%和56.7%的桐花树分布于平均海平面以下,秋茄也能分布在此高程下,平均株高也达1.75 m。根据现场实际调查结果,桐花树、秋茄可以大量生存在平均海平面以下的滩涂上。     

五种红树植物通气组织对人工非潮汐生境的响应

红树植物自然条件下生长于河口、海岸潮间带。受潮汐作用影响,红树植物在生理、形态、结构上对渍水环境产生了相应的适应机制。其中红树植物通气组织的发达程度与其耐淹水的能力具有很高的相关性,是衡量红树植物耐淹浸能力的重要依据。利用测定孔隙率和石蜡切片面积比两种方法揭示了华南地区5种红树植物优势种：白骨壤 (Avicennia marina)、红海榄 (Rhizophora stylosa)、木榄 (Bruguiera gymnorrhiza)、秋茄 (Kandelia candel)和桐花树 (Aegiceras corniculatum)在自然条件和人工生境下根通气组织的发育规律,并用石蜡切片研究了茎和叶的通气组织发育状况。结果表明：两种方法测得根的通气组织发育程度的结果相关性显著（P<0.05）。5种红树植物通气组织主要产生于根部,茎和叶发育较少,除了潮汐生境中白骨壤根的通气组织为根、茎、叶总和的48.16%、非潮汐生境中桐花树根为43.81%,其余树种根部通气组织占总体的50%以上。自然潮间带生境中,桐花树、木榄、白骨壤、秋茄、红海榄,通气组织分别为(14.98±3.34)%、(27.83±2.3)%、(29.64±3.17)%、(3009±4.12)%、(42.12±3.14)%,通气组织比例与其在潮间带上的分带性和演替序列较为吻合。非潮汐人工生境下,红海榄、木榄、秋茄、桐花树和白骨壤根部通气组织较自然生境下均有所增加,说明各树种对非潮汐淹浸条件具备一定的适应力。根据非潮汐生境下通气组织的比例可判定它们对恒定水位的适应能力依次为：桐花树>白骨壤>秋茄>木榄>红海榄。红树植物对非潮汐淹浸条件的适应有利于在沿海地区开展人工生境下红树林的栽培与推广应用,研究结果对提高栽培成活率,更大限度地发挥红树林的生态服务价值,具有重大的实践意义。     

土壤水分含量对菖蒲(Acorus calamus) 萌发及幼苗生长发育的影响

应用盆栽试验方法,采用完全随机试验设计,研究了菖蒲在不同土壤水分含量下的萌发和幼苗生长。试验共设6个处理,处理时间为60d。结果表明：（1）水分亏缺对菖蒲萌发和幼苗有不同程度的影响,在持续干旱60d条件下,菖蒲幼苗的萌发率仅为32．5％,为正常水分条件下的1／3,幼苗的平均高度为19．0cm,是正常水分条件下的1／3左右;（2）菖蒲幼苗叶片长度、宽度和基茎随土壤水分含量降低而减小,叶片数量与叶片面积也随土壤水分含量降低而减小,叶片含水率各试验组无明显差异;（3）在试验的20、40、60d,各试验组的根、茎、叶及总生物量都比对照组（CK）有不同程度的降低,并随试验时间的延长,各水分含量条件下的生物量差别增大,在不同土壤水分条件下,根、茎和叶生物量增量均表现为茎的最多,叶的次之,根的最少,叶、茎、根生物量比例平均为1：1．59：0．82;（4）菖蒲幼苗叶片的叶绿素a、b随土壤水分含量减少而下降,叶绿素a／b随土壤水分含量减少而下降而升高,类胡萝卜素（Car）含量随土壤水分含量减少而下降;（5）Fv/Fm、qP随土壤水分含量降低而下降,重度干旱对菖蒲幼苗光合系统PSⅡ的最大量子产量影响显著,菖蒲幼苗在重度干旱条件下30、45、60d的Fv／Fm分别为0．800、0．796、0．787,分别比对照降低5．0％、4．7％和6．2％;菖蒲幼苗在重度干旱条件下30、45、60d的qN分别为0．270、0．259和0．200,分别是对照的6．75、3．92、2．78倍,可见干旱条件会导致菖蒲幼苗以热的形式耗散掉的光能部分增加,有效保护了菖蒲叶片PSⅡ系统,但持续干旱（60d）导致qN降低,菖蒲叶片PSⅡ系统受到不同程度的破坏;干旱胁迫还对菖蒲植株的光响应曲线具有较大的影响,使最大ETR降低。     

Solution-mediated syntheses and characterizations of two new zincophosphites [C6H14N2]0.5[Zn(H2PO3)2] and [C4H12N2]0.5[(CH3)2NH2][Zn2(HPO3)3]

Two new zincophosphites [C₆H₁₄N₂]_0.5[Zn(H₂PO₃)₂] 1 and [C₄H₁₂N₂]_0.5[(CH₃)₂NH₂][Zn₂(HPO₃)₃] 2 have been solvothermally synthesized in mixed solvents of N,N-dimethylformamide (DMF) and 1,4-dioxane (DOA), respectively. Single-crystal X-ray diffraction analysis reveals that compound 1 exhibits a neutral inorganic chain formed by ZnO₄ and HPO₂(OH) units. Interestingly, the left- and right-handed hydrogen-bonded helical chains are alternately formed via the hydrogen-bonds between two adjacent chains. Compound 2 exhibits a layer structure with 4- and 12-MRs formed by ZnO₄ and HPO₃ units, in which two kinds of organic amine molecules both act as countercations to compensate the overall negative electrostatic charge of the anionic network.     

p-Quinquephenyl diamine, C6H5-p-C6H4-p-C6H2(2,3-NH2)-p-C6H4-C6H5, and its corresponding diimine-Ru(II) complex: Crystal structure and electrochemical and optical properties

The molecular structure of an o-phenylenediamine unit-containing oligophenylene (1), Ph-Ph′-Ph′(2,3-NH₂)-Ph′-Ph (Ph = phenyl; Ph′ = p-phenylene; Ph′(2,3-NH₂) = 2,3-diamino-p-phenylene), was determined by X-ray crystallography. 1 has a twisted structure, and forms an intermolecular C-H?π interaction network. The -NH₂ group of 1 was air-oxidized to an imine, NH, group in the presence of [RuCl₂(bpy)₂] (bpy = 2,2′-bipyridyl) and gave a ruthenium(II)-benzoquinone diimine complex [Ru(2)(bpy)₂](PF₆)₂ (2: Ph-Ph′-Ph′(2,3-imine)-Ph′-Ph). The molecular structure of [Ru(2)(bpy)₂](PF₆)₂ was confirmed by X-ray crystallography. [Ru(2)(bpy)₂](PF₆)₂ underwent two-step electrochemical reduction with E^1/2 = −0.889 V and −1.531 V versus Fc⁺/Fc. The E^1/2’s were located at higher potentials by 91 mV and 117 mV, respectively, than those of reported [Ru(bqdi)(bpy)₂](PF₆)₂ (bqdi = benzoquinone diimine). Electrochemical oxidation of [Ru(2)(bpy)₂](PF₆)₂ occurred at a lower potential by 180 mV than that of [Ru(bqdi)(bpy)₂](PF₆)₂. Occurrence of the easier reduction and oxidation of [Ru(2)(bpy)₂](PF₆)₂ than those of [Ru(bqdi)(bpy)₂](PF₆)₂ is ascribed to the presence of a large π-conjugation system in 2.     

New preparations and molecular structures of cis-MCl2(Ph2PCH2PPh2)2, M = Ru,Os and trans-RuCl2(Ph2PCH2PPh2)2

The title compounds were made by reacting bis(diphenylphosphino)methane (dppm) with reduced solutions of OsCl₆^4? and Ru₂OCl₁₀^4?. The crystal and molecular structures of these compounds have been determined form three-dimensional X-ray study. The cis-isomers crystallize with one CHCl₃ per molecule of the complex. All three compounds crystallize in the monoclinic space group P2₁/n with unit cell dimensions as follows: Cis-OsCl₂(dppm)₂·CHCl₃: a = 13.415(4) Å, b = 22.859(4) Å, c = 16.693(3) Å, β = 105.77(3)°, V = 4926(3) ų, Z = 4. cis-RuCl₂(dppm)₂·CHCl₃: a = 13.442(3) Å, b = 22.833(7) Å, c = 16.750(4) Å, β = 105.53(2)°, V = 4953(3) ų, Z = 4. trans-RuCl₂(dppm)₂: a = 11.368(7) Å, b = 10.656(6) Å, c = 18.832(12) Å; β = 103.90(6)°, V = 2213(7) ų; Z = 2. The structures were refined to R = 0.044 (R_w = 0.055) for cis-OsCl₂(dppm)₂·CHCl₃; R = 0.065 (R_w = 0.079) for cis-RuCl₂(dppm)₂·CHCl₃ and R = 0.028 (R_w = 0.038) for trans-RuCl₂(dppm)₂. The complexes are six coordinate with stable four-membered chelate rings. The PMP angle in the chelate rings is ca. 71° in each case.     

Selective synthesis of triangular cluster oxido-sulfidocomplexes of Mo and W: High yield preparations of [Mo3O2S2(H2O)9], [W3O2S2(H2O)9], [W2MoO2S2(H2O)9] and their derivatization

Reaction of [Mo₂O₂(μ-S)₂(H₂O)₆]²⁺ with Mo(CO)₆ or metallic Mo under hydrothermal conditions (140 °C, 4 M HCl) gives oxido-sulfido cluster aqua complex [Mo₃(μ₃-S)(μ-O)₂(μ-S)(H₂O)₉]⁴⁺ (1). Similarly, [W₃(μ₃-S)(μ-O)₂(μ-S)(H₂O)₉]⁴⁺ (2) is obtained from [W₂O₂(μ-S)₂(H₂O)₆]²⁺ and W(CO)₆. While reaction of [Mo₂O₂(μ-S)₂(H₂O)₆]²⁺ with W(CO)₆ mainly proceeds as simple reduction to give 1, [W₂O₂(μ-S)₂(H₂O)₆]²⁺ with Mo(CO)₆ produces new mixed-metal cluster [W₂Mo(μ₃-S)(μ-O)₂(μ-S)(H₂O)₉]⁴⁺ (3) as main product. From solutions of 1 in HCl supramolecular adduct with cucurbit[6]uril (CB[6]) {[Mo₃O₂S₂(H₂O)₆Cl₃]₂CB[6]}Cl₂⋅18H₂O (4) was isolated and structurally characterized. The aqua complexes were converted into acetylacetonates [M₃O₂S₂(acac)₃(py)₃]PF₆ (M₃ = Mo₃, W₃, W₂Mo; 5a-c), which were characterized by X-ray single crystal analysis, electrospray ionization mass spectrometry and ¹H NMR spectroscopy. Crystal structure of (H₅O₂)(Me₄N)₄[W₃(μ₃-S)(μ₂-S)(μ₂-O)₂(NCS)₉] (6), obtained from 2, is also reported.     

Synthesis and crystal structure of the MgCl2(CH3COOC2H5)2· (CH3COOC2H5) adduct

The reaction of α-MgCl₂ with boiling ethyl acetate affords MgCI₂(CH₃COOC₂H₅)₂· (CH₃COOC₂H₅), which is obtained as crystals suitable for X-ray analysis only from the mother liquor. M=315.5, orthorhombic, space group P2₁22₁ (No. 18), a=25.077(3), b=8.616(1), c=7.345(1) Å, V=1587.0(3) ų, Z=4, D_x=1.32 g cm⁻³,λ A(Mo Kα)=0.71069 Å, μ=4.17 cm⁻¹, F(000)=664, T=298 K, observed reflections: 1667, R=0.059 and R_w=0.069. The structure is composed of polymeric chains of MgCl₂(CH₃COOC₂H₅₎₂ and the ethyl acetate molecules occupy a mutually trans position.     

Synthesis of tantalum and niobium complexes that contain the diamidoamine ligand, [(3,4,5-F3C6H2NCH2CH2)2NMe], and the triamidoamine ligand, [(3,5-Cl2C6H3NCH2CH2)3N]

Several niobium and tantalum compounds were prepared that contain either the diamidoamine ligand, [(3,4,5-F₃C₆H₂NCH₂CH₂)₂NMe]²⁻ ([F₃N₂NMe]²⁻), or the triamidoamine ligand, [(3,5-Cl₂C₆H₃NCH₂CH₂)₃N]³⁻ ([Cl₂N₂NMe]³⁻). The former include [F₃N₂NMe]TaCl₃, [F₃N₂NMe]NbCl₃, [F₃N₂NMe]TaMe₃, [F₃N₂NMe]NbMe₃, [(F₃N₂NMe)TaMe₂][MeB(C₆F₅)₃], [F₃N₂NMe]Ta(CHSiMe₃)(CH₂SiMe₃), [F₃N₂NMe]Ta(CH₂-t-Bu)Cl₂, [F₃N₂NMe]Ta(CH-t-Bu)(CH₃), and [F₃N₂NMe]Ta(η²-C₂H₄)(CH₂CH₃). The latter include [Cl₂N₂NMe]TaCl₂, [Cl₂N₂NMe]TaMe₂, [Cl₂N₂NMe]Ta(η²-C₂H₄), and [Cl₂N₂NMe]Ta(η²-C₂H₂).X-ray diffraction studies were carried out on [F₃N₂NMe]Ta(CHSiMe₃)(CH₂SiMe₃), [F₃N₂NMe]Ta(η²-C₂H₄)(CH₂CH₃), and [Cl₂N₂NMe]TaMe_2..     

Synthesis and structure of a lead(II)-citrate: {Na(H2O)3}[Pb5(C6H5O7)3(C6H6O7)(H2O)3]·9.5H2O

The reaction of lead(II) nitrate with trisodium citrate Na₃(C₆H₅O₇) in a 1:22.5 ratio at pH 4.8 provides crystals of {Na(H₂O)₃}[Pb₅(H₂O)₃(C₆H₅O₇)₃(C₆H₆O₇)]·9.5H₂O (1). The structure of 1 is two-dimensional and exhibits five distinct Pb(II) sites and four different modes of citrate bonding. The five lead sites all display hemidirected coordination geometries, that is, irregular distribution of neighboring oxygen atoms resulting in obvious gaps in the coordination spheres. Consequently, the lead coordination geometries exhibit proximal bonding to a number of oxygen donors, as well as distal interactions with nearest neighbors. The coordination numbers vary from 8 to 10, with ‘5+3’, ‘5+4’, ‘6+4’ and ‘7+3’ coordination modes where the first number refers to the proximal ligands and the second to the distal set. The four crystallographically distinct citrate groups include three with deprotonated carboxylate groups (C₆H₅O₇)³⁻ and one with a single protonated carboxyl group (C₆H₆O₇)². The citrate ligands bridge 3, 5, 7 and 7 lead sites. Three of the citrate groups exhibit tridentate chelation coordination to a lead site through two carboxylate oxygen donors and the hydroxyl groups. One citrate group projects an uncoordinated -OH group and a pendant protonated carboxyl group into the interlamellar domain. This latter carboxyl group coordinates to a sodium cation, which exhibits five coordinate geometry defined by three aqua ligands and the carbonyl oxygen of the -CO₂H groups in the basal plane and a citrate -OH donor in the apical position.     

Crystal structures of MoCl2(O)(O2)(OPMePh2)2 and mixtures of MoCl2(O2)(OPPh3)2 and MoCl2(O)(O2)(OPPh3)2: allylic alcohol isomerization studies using MoCl2(O)(O2)(OPMePh2)2

Adding one equivalent of H₂O₂ to compounds of stoichiometry MoCl₂(O)₂(OPR₃)₂, OPR₃ = OPMePh₂ or OPPh₃, leads to the formation of oxo-peroxo compounds MoCl₂(O)(O₂)(OPR₃)₂. The compound MoCl₂(O)(O₂)(OPMePh₂)₂ crystallized with an unequal disorder, 63%:37%, between the oxo and peroxo ligands, as verified by single-crystal X-ray diffractometry, and can be isolated in reasonable yields. MoCl₂(O)(O₂)(OPPh₃)₂, was not isolated in pure form, co-crystallized with MoCl₂(O)₂(OPPh₃)₂ in two ratios, 18%:82% and 12%:88%, respectively, and did not contain any disorder in the arrangement of the oxo and peroxo groups. These complexes accomplish the isomerization of various allylic alcohols. A mechanism of this reaction has been constructed based on ¹⁸O isotopic studies and involves exchange between the alcohol and metal bonded O atoms.     

Metal-organophosphonates: hydrothermal synthesis and structures of [Cu(O3PC10H6CO2H)] and [Cu(bpy)(HO3PC10H6CO2)] (H2O3PC10H6CO2H = 2,6-carboxynaphthalene phosphonic acid)

Hydrothermal methods were used to prepare [Cu(O₃PC₁₀H₆CO₂H)] (1) and [Cu(bpy)(HO₃PC₁₀H₆CO₂)]·2H₂O (2·2H₂O), where H₂O₃PC₁₀H₆CO₂H is 2,6-carboxynaphthalene phosphonic acid (H₃cnp). The two-dimensional structure of 1 consists of layers of edge-sharing {CuO₆} octahedra, producing an AlCl₃- type structure of fused hexagonal rings of copper octahedra, enclosing voids of hexagonal profile. The layer composition is CuO₃ or CuO₆/₂ as each oxygen bridges two copper sites. The Hcnp ligands project from either face of the copper “oxide” layer. Adjacent layers interact through hydrogen bonding interactions between the pendant -CO₂H groups of the ligand. Coordination of the bipyridine ligand in [Cu(HO₃PC₁₀H₆CO₂)] (2) obstructs expansion in two-dimensions, and the material exhibits a chain structure. The chain is constructed of binuclear units of edge-sharing ‘4+1’ {CuO₃N₂} square pyramids linked through the dipodal {HO₃PC₁₀H₆CO₂}²⁻ ligands.