配合物形成的三维超分子体系—[Ni(C_6H_4O_2N)_2(H_2O)_4]的水热法合成、晶体结构及热分析

采用水热法用Ni(NO3)26H2O和异烟酸制备出了一种新的由配合物形成的三维超分子体系—[Ni(C6H4O2N)2(H2O)4],并通过X射线衍射对其晶体结构进行了测定。 该晶体属三斜晶系,空间群为Pī, 所得晶胞参数为: a = 6.9228(4), b = 9.6664(19),c = 6.322(1) , a = 96.86(3), b = 113.33(3), g = 110.35(3)°, V = 347.6(1) 3, Z = 1, Mr = 374.98, Dc = 1.791 g/cm3, F(000) = 194, m = 1.443 mm-1。用1362个可观察的 (I > 2s(I))衍射点,修正123个结构参数, 最终偏离因子R = 0.0444,wR = 0.1271。在组成该化合物的基本结构单元[Ni(C6H4O2N)2(H2O)4]中,Ni处于1个稍微拉长的八面体的中心; 各个结构单元之间通过氢键OH…O相互连接,形成了无限伸展的具有层状结构的三维超分子体系。 另外,从差热及热重曲线可以看出,该化合物加热到154 ℃时开始分解, 首先失去4个H2O,再失去2个异烟酸根,最后残余物为NiO。     

新型三维开放骨架稀土硫酸盐[Ln4(H2O)4(SO4)10](C4N2H12)4(H2O)4(Ln=Gd,Eu)的合成、结构及荧光性质

以哌嗪为模板剂,在水-乙醇混合溶剂体系中溶剂热合成了两个具有三维开放骨架结构的稀土硫酸盐[Ln4(H2O)4(SO4)10](C4N2H12)4(H2O)4（Ln = Gd,化合物1和Eu,化合物2）,并对其进行了结构表征、热重以及荧光光谱分析. 单晶结构解析表明,化合物1和2属于同构异质,均结晶于单斜晶系,P21/c空间群,化合物1,a = 19.691(3) ?,b = 19.249(3) ?,c = 13.186(2) ?,β = 92.33(0)o,V = 4993.5(1) ?3, Z =4. 化合物2,a = 19.7233(8) ?,b = 19.2791(8) ?,c = 13.2095(5) ?,β = 92.329(1)o,V = 5018.7(3) ?3, Z =4. 两个化合物在ab平面上由SO4,GdO8和GdO9多面体共边或共角交错连接形成含有八元环和十六元环的二维层状结构,该二维层沿c方向平行排列,相邻层通过SO4四面体相连形成具有孔道的三维开放骨架结构,其孔道之中包含平衡骨架负电荷的质子化哌嗪分子. 化合物2的固体荧光光谱分析显示其在397nm激发波长下,表现出典型的Eu3+发光性质.       

含有两个簇阴离子[As_8V_(14)O_(42)(SO_4)]~(6-)的金属-氧簇合物(H_2en)_6[As_8V_(14)O_(42)(SO_4)]_28H_2O的水热合成与晶体结构

合成了一种新的砷-钒-氧簇合物(H2en)6[As8V14O42(SO4)]28H2O(en为乙二胺),用元素分析、IR和TG-DTA等手段进行了表征,并用X射线衍射法测定了晶体结构。结果表明, 该晶体属单斜晶系,P21/c空间群,晶胞参数a = 20.9235(4),b = 11.9382(2),c = 43.5783(6) 牛琤 = 102.13,V = 10642.1(3) ?,Z = 4,Mr = 4678.01,Dc = 2.920 g/cm3,F(000) = 8944,m = 7.437 mm-1,R = 0.0735,wR = 0.1361。结构测定表明,结构中2个簇阴离子{[As8V14O42(SO4)]6-}与有机铵阳离子[H2en]2+之间靠静电作用相结合,同时与H2O通过氢键构成无限的三维骨架结构。     

[Co(enMe)_3]_2[As_8V_(14)O_(42)(H_2O)]·10H_2O的水热合成、性质和晶体结构

合成了一种新的砷-钒-氧簇合物[Co(enMe)3]2[As8V14O42(H2O)]10H2O(enMe为1,2-丙二胺),用元素分析、IR和TGA-DTA等进行了表征,并用X射线衍射法测定了晶体结构。结果表明,该晶体属单斜晶系,C2/c空间群,晶胞参数a=28.990(7),b=15.540(6),c=22.77(1),b=131.24(4),Mr=2744.68,V=7714(7)3,Z=4,F(000)=5232,m(MoKa)=7.239mm-1,Dc=2.363g/cm3,R=0.069,Rw=0.073。结构测定表明,结构中簇阴离子[As8V14O42(H2O)]4-与配位阳离子[Co(enMe)3]2+之间靠静电作用相结合,同时通过氢键构成无限的三维骨架结构。     

聚金属氧酸盐[(C_4H_9)_4N]_6[PMo_(12)O_(40)]_2·0.5H_2O的晶体结构

在乙腈-水混合溶剂中培养得到了聚金属氧酸盐[(C4H9)4N]6[PMo12O40]2.0.5H2O的单晶.X射线衍射结构分析表明,该晶体属于单斜晶系,C2/c空间群,晶胞参数:a=4.996(10)nm,b=1.411(3)nm,c=2.633(5)nm,β=114.804(4)°,V=16.844 nm3,Z=1,R1=0.0843,wR2=0.2546.化合物分子由两个多阴离子[PMo12O40]3-,6个四丁基胺阳离子[n-Bu4N]+和0.5个结晶水组成.     

SYNTHESIS AND CRYSTAL STRUCTURE OF AZACROWN (2, 2) DINITRATE [C_(12)H_(28)O_4N_2] (NO_3)_2

<正> [C12H28O4N2](NO3)2, Mr = 388. 45, monoclinic space group P21/ n,a = 7. 811(2), b = 10.626(4), c= 11. 823(6) A , β=106.51(3)°, Z = 2, Dc = 1.37 gem-3, V = 940. 8(7) (?)3 F(000) = 416, μ(MoKα) =1. 3 cm-1, R =0. 044 for 1373 reflections. The structure contains prdtonated azacrown [H2(2,2)]2+ and two (NO3-) which are bridged by four hydrogen bonds O(nitrate) ...H-N(crown). The ion [H2(2,2)]2+ in the title crystal lies on the crystallographic center of symmetry. There is half a [H2(2,2)]2+ and one NO3- in an asymmetric unit.     

2D氢键网络镉配合物Cd(pyridine-2-sulfonato)_2(H_2O)_2和锌配合物Zn(pyridine-2-sulfonato)_2(H_2O)_2的合成和晶体结构

合成了镉的吡啶-2-磺酸配合物Cd(C5H4NSO3)2(H2O)2 1和锌的吡啶-2-磺酸配合物Zn(C5H4NSO3)2(H2O)2 2。 研究表明, 2个化合物属异质同晶, 均属单斜晶系, 空间群为C2/c. 化合物1晶胞参数为:a = 13.7671(5), b = 7.2778(3), c = 16.1559(9) ? b = 106.656(3)? V = 1550.8(1) 3, Z = 4, Dc = 1.990 g/cm3, m =1.719 mm-1, F(000) = 920, R = 0.0225, wR = 0.0584, 共收集到1759个独立衍射点, 其中I≥2(I)的可观测点为1681个;化合物2晶胞参数为:a = 13.711(1), b = 7.1451(9), c = 15.972(1) , b =107.079(5)? V = 1495.7(3) 3, Z = 4, Dc = 1.855 g/cm3, m = 1.964 mm-1, F(000) = 848, R = 0.0310, wR = 0.0831, 共收集到1707个独立衍射点, 其中I≥2(I)的可观测点为1592个。在2个标题配合物中, Cd2+离子(或Zn2+离子)由2个吡啶-2-磺酸中的2个氮和2个氧以及2个水分子中的2个氧配位形成畸变的N2O4八面体配位构型。每个配合物分子具有晶体学2次旋转轴对称性。配合物分子之间通过许多OH(配位水分子)LO(未配位磺酸根)氢键联结成二维结构网络。     

三核铁簇硫酸盐K_2(H_3O)_3[Fe_3(H_2O)_3O(SO_4)_6]·6H_2O的合成与晶体结构

在室温条件下合成了含三核铁簇的硫酸盐配合物K2(H3O)3[Fe3(H2O)3O(SO4)6].6 H2O,借助IR光谱、紫外-可见吸收光谱、X射线光电子能谱(XPS)和X射线单晶衍射等测试手段对其结构进行了表征.结果表明,标题化合物属于六方晶系,P6(3)/m空间群,晶胞参数为:a=b=0.963 7(2)nm,c=1.885 1(9)nm,V=1.516 3(9)nm3,Z=2,Dc=2.316 g/cm3,GOOF=1.089,R1=0.062 8,wR2=0.165 1.其分子由1个三核铁簇阴离子[Fe3(H2O)3O(SO4)6]5-、2个K+离子、3个水合质子H3O+和6个结晶水分子组成.     

SYNTHESIS AND STRUCTURE OF A COBALT DIMER COMPLEX (Bt_4N)_2 [Co(SOC_6H_4 )(HOSC_6H_4)]_2

<正> The title compound was obtained by reaction of CoCl2.6H2O and mp2- (σ-C6H4SO2-) in MeCN,crystallized as Et4N+ salt in monoclinic system with space group P21/c, Mr=877.040. The cell parameters are:a =16.606(2), b=15.575(1),c=17.725(2)A,β=111.07(1)°,V=4277.8A3,Z=4,Dx= 1.36g/cm3.It is a dimer of [Co(mp)(Hmp)]- connected by two strong hydrogen bonds with a twist angle of about 36.94 .     

无机-有机杂化硫属化合物[Mn(1,2-dap)_2(H_2O)]_2(μ-Sn_2Q_6)(Q=S、Se)和[Mn(tren)]_2(μ-Sn_2S_6)的合成、晶体结构与性能（英文）

采用溶剂热方法合成了3个多元硫属化合物[Mn(1,2-dap)2(H2O)]2(μ-Sn2Q6)(Q=S(1)和Se(2))和[Mn(tren)]2(μ-Sn2S6)(3),用X-射线单晶衍射测定了化合物的结构,并通过红外光谱、紫外-可见漫反射光谱对其进行了表征。单晶结构解析表明,化合物1和2都属于正交晶系,Pccn空间群(No.56),晶体结构是由[Mn(1,2-dap)2(H2O)]2+配合物阳离子和[Sn2Q6]4-二聚体通过Mn-Q键连接而成的[Mn(1,2-dap)2(H2O)]2(μ-Sn2Q6)低聚体,相邻的低聚体之间通过氢键相连形成三维结构。化合物3属于三斜晶系,晶体结构是由[Mn(tren)]2(μ-Sn2S6)单元通过氢键连接而成的二维结构。紫外-可见漫反射光谱结果显示化合物1,2和3的带隙分别为2.5,2.1,2.4 e V,属于半导体材料。     

Synthesis and Crystal Structure of [Cu2（DMF）（H2O）（C7H4NO4）2（C7H3NO4）]2·3.5DMF

A new copper（H） complex [Cu2（DMF）（H2O）（C7H4NO4）2（C7H3NO4）]2-3.5DMF has been synthesized and its structure was determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1^- with a = 10.722（3）, b = 18.170（4）, c = 20.923（7）A,α = 105.297（9）, β = 101.701（10）, γ = 105.74（1）°, V= 3615（1）A^3, Z = 2, C58.50H64.50Cu4N1l.50O3150, Mr = 1686.90, Dc = 1.550 g/cm^3,μ= 1.255 mm^-1, F（000） = 1728.00, T = 150（2） K, the final R = 0.0640 and wR = 0.173 for 11310 observed reflections with I 〉 2σ（I）. In the crystal, each formular unit consists of two dinuclear copper（H） compounds, between which the O-H…O hydrogen bonds exist. Each Cu^Ⅱ cation is six-coordinated in an octahedral geometry. The intermolecular hydrogenbonding interaction leads to a 3-D framework of the title compound.     

Synthesis and Crystal Structure of a Novel Three-dimensional Supramolecular Compound [（AgI3）（4-HBPFA）2（H2O）]

1 INTRODUCTION In recent years, the rational design and synthesisof metal-directed supramolecular frameworks throughintermolecular hydrogen bonds, π-π stacking interac-tion or other weak interactions have received muchattention because of their interesting molecular topo-logies and various potential applications in catalysis,superconductor, magnetism, nonlinear optics, sen-sors and molecular recognition[1～4]. On the otherhand, the attachment of mono- or polypyridyl frag-ments to a ferr…     

Synthesis and Crystal Structure of [Cu(phen)2(SO4)(H2O)]·0.5C4H4O4·7H2O

The title compound, [Cu(phen)2(SO4)(H2O)]·0.5C4H4O4·7H2O (phen = 1,10-phe-nanthroline and C4H4O4 = fumaric acid), has been synthesized and characterized by single-crystal X-ray diffraction. The crystal is of triclinic, space group P with a = 11.4827(2), b = 11.9086(2), c = 13.77350(10)(A), α = 80.6830(10), β = 66.6480(10), γ = 64.0480(10)o, V = 1554.63(4) (A)3, Mr = 722.17, Z = 2, Dc = 1.543 g/cm3, μ = 0.845 mm-1, F(000) = 750, R = 0.0349 and wR = 0.0837 for 4754 observed reflections (I > 2σ(I)). The compound contains a six-coordinated copper(II) center, which is surround by four N atoms of two phen ligands (Cu-N distances in the range of 1.997(2)～2.225(2)(A)), one sulfate O atom (Cu-O = 2.0037(17) (A)) and one water O atom (Cu-O(5w) = 2.719(2) (A)) in a distorted octahedral geometry. Extensive hydrogen-bonding interactions are involved in water molecules, ligated sulfate anions and fumaric acid molecules. In addition, π-π interactions via aromatic nitrogen-containing ligands are also discussed. The combination of non-covalent interactions leads to the formation of a 3-D network structure.     

Syntheses and Crystal Structures of Molybdenum-Sulfur Clusters Mo_3S_4 (dtp)_3(o-CH_3OC_6H_4COO)(Py) and Mo_3S_4 (dtp)_3(p-HOC_6H_4COO)(DMF)·EtOH

1 INTRODUCTION Recent years have seen a drastic increase of compounds containing the Mo3S4 core. A major synthetic route to these compounds is by the reaction of the aqua ion [Mo3S4(H2O)9]4+ with different kinds of ligands replacing some or all of the water molecules. In this way, Mo3S4(dtp)4(H2O), which was synthesized by the spontaneous- assembly method in 1986[1] and its structural characterization and chemical reactivity have been well recognized [2], can be rationally synthesize…     

Monomeric oxovanadium(IV) compounds of the general formula cis-[V(IV)(=O)(X)(L(NN))(2)](+/0) [X = OH(-), Cl(-), SO(4)(2)(-) and L(NN) = 2,2'-bipyridine (bipy) or 4,4'-disubstituted bipy

Reaction of [V(IV)OCl(2)(THF)(2)] in aqueous solution with 2 equiv of AgBF(4) or AgSbF(6) and then with 2 equiv of 2,2'-bipyridine (bipy), 4,4'-di-tert-butyl-2,2'-bipyridine (4,4'-dtbipy), or 4,4'-di-methyl-2,2'-bipyridine (4,4'-dmbipy) affords compounds of the general formula cis-[V(IV)O(OH)(L(NN))(2)]Y [where L(NN) = bipy, Y = BF(4)(-) (1), L(NN) = 4,4'-dtbipy, Y = BF(4)(-) (2.1.2H(2)O), L(NN) = 4,4'-dmbipy, Y = BF(4)(-) (3.2H(2)O), and L(NN) = 4,4'-dtbipy, Y = SbF(6)(-) (4)]. Sequential addition of 1 equiv of Ba(ClO(4))(2) and then of 2 equiv of bipy to an aqueous solution containing 1 equiv of V(IV)OSO(4).5H(2)O yields cis-[V(IV)O(OH)(bipy)(2)]ClO(4) (5). The monomeric compounds 1-5 contain the cis-[V(IV)O(OH)](+) structural unit. Reaction of 1 equiv of V(IV)OSO(4).5H(2)O in water and of 1 equiv of [V(IV)OCl(2)(THF)(2)] in ethanol with 2 equiv of bipy gives the compounds cis-[V(IV)O(OSO(3))(bipy)(2)].CH(3)OH.1.5H(2)O (6.CH(3)OH.1.5H(2)O) and cis-[V(IV)OCl(bipy)(2)]Cl (7), respectively, while reaction of 1 equiv of [V(IV)OCl(2)(THF)(2)] in CH(2)Cl(2) with 2 equiv of 4,4'-dtbipy gives the compound cis-[V(IV)OCl(4,4'-dtbipy)(2)]Cl.0.5CH(2)Cl(2) (8.0.5CH(2)Cl(2)). Compounds cis-[V(IV)O(BF(4))(4,4'-dtbipy)(2)]BF(4) (9), cis-[V(IV)O(BF(4))(4,4'-dmbipy)(2)]BF(4) (10), and cis-[V(IV)O(SbF(6))(4,4'-dtbipy)(2)]SbF(6) (11) were synthesized by sequential addition of 2 equiv of 4,4'-dtbipy or 4,4'-dmbipy and 2 equiv of AgBF(4) or AgSbF(6) to a dichloromethane solution containing 1 equiv of [V(IV)OCl(2)(THF)(2)]. The crystal structures of 2.1.2H(2)O, 6.CH(3)OH.1.5H(2)O, and 8.0.5CH(2)Cl(2) were demonstrated by X-ray diffraction analysis. Crystal data are as follows: Compound 2.1.2H(2)O crystallizes in the orthorhombic space group Pbca with (at 298 K) a = 21.62(1) A, b = 13.33(1) A, c = 27.25(2) A, V = 7851(2) A(3), Z = 8. Compound 6.CH(3)OH.1.5H(2)O crystallizes in the monoclinic space group P2(1)/a with (at 298 K) a = 12.581(4) A, b = 14.204(5) A, c = 14.613(6) A, beta = 114.88(1) degrees, V = 2369(1), Z = 4. Compound 8.0.5CH(2)Cl(2) crystallizes in the orthorhombic space group Pca2(1) with (at 298 K) a = 23.072(2) A, b = 24.176(2) A, c = 13.676(1) A, V = 7628(2) A(3), Z = 8 with two crystallographically independent molecules per asymmetric unit. In addition to the synthesis and crystallographic studies, we report the optical, infrared, magnetic, conductivity, and CW EPR properties of these oxovanadium(IV) compounds as well as theoretical studies on [V(IV)O(bipy)(2)](2+) and [V(IV)OX(bipy)(2)](+/0) species (X = OH(-), SO(4)(2)(-), Cl(-)).     

Synthesis and Crystal Structure of [Cu(phen)_2(SO_4)(H_2O)]·0.5C_4H_4O_4·7H_2O

1INTRODUCTION The construction of metal-organic coordination polymers based on covalent interactions[1]or supra-molecular contacts such as hydrogen-bonding and/orπ-πinteractions)[2]is now of great interest not only due to the enormous variety of intriguing structural topologies themselves,but also to their unexpected physical and chemical properties for potential prac-tical applications as functional materials.Many N-containing ligands,such as4,4?-bipyridine,2,2?-bi-pyridine and1,10-phen…     

Substitution and derivatization reactions of a water soluble iron(II) complex containing a self-assembled tetradentate phosphine ligand

Facile substitution reactions of the two water ligands in the hydrophilic tetradentate phosphine complex cis-[Fe{(HOCH2)P{CH2N(CH2P(CH2OH)2)CH2}2P(CH2OH)}(H2O)2](SO4) (abbreviated to [Fe(L1)(H2O)2](SO4), 1) take place upon addition of Cl-, NCS-, N3(-), CO3(2-) and CO to give [Fe(L1)X2] (2, X = Cl; 4, X = NCS; 5, X=N3), [Fe(L1)(kappa2-O(2)CO)], 6 and [Fe(L1)(CO)2](SO4), 7. The unsymmetrical mono-substituted intermediates [Fe(L1)(H2O)(CO)](SO(4)) and [Fe(L(1))(CO)(kappa(1)-OSO(3))] (8/9) have been identified spectroscopically en-route to 7. Treatment of 1 with acetic anhydride affords the acylated derivative [Fe{(AcOCH2)P{CH2N(CH2P(CH2OAc)2)CH2}2P(CH2OAc)}(kappa2-O(2)SO2)] (abbreviated to [Fe(L2)(kappa2-O(2)SO2)], 10), which has increased solubility over 1 in both organic solvents and water. Treatment of 1 with glycine does not lead to functionalisation of L1, but substitution of the aqua ligands occurs to form [Fe(L(1))(NH(2)CH(2)CO(2)-kappa(2)N,O)](HSO(4)), 11. Compound 10 reacts with chloride to form [Fe(L(2))Cl(2)] 12, and 12 reacts with CO in the presence of NaBPh4 to form [Fe(L2)Cl(CO)](BPh4) 13b. Both of the chlorides in 12 are substituted on reaction with NCS- and N3(-) to form [Fe(L2)(NCS)2] 14 and [Fe(L2)(N3)2] 15, respectively. Complexes 2.H2O, 4.2H2O, 5.0.812H2O, 6.1.7H2O, 7.H2O, 10.1.3CH3C(O)CH3, 12 and 15.0.5H2O have all been crystallographically characterised.     

Novel acetate polyoxomolybdate "host" accommodating a zigzag-chainlike "guest" of five edge-shared sodium cations: Na(21)[[Na(5)(H(2)O)(14)]within[Mo(46)O(134)(OH)(10)(mu-CH(3)COO)(4)]].CH(3)COONa. approximately equal to 95H(2)O

A novel ESR-silent polyoxomolybdate Na(21)([Na(5)(H(2)O)(14)][Mo(46)O(134)(OH)(10)(mu-CH(3)COO)(4)]).CH(3)COONa.approximately equal to 90H(2)O (3) was simply synthesized in high yield by reducing an acidified aqueous solution of Na(2)MoO(4).2H(2)O and CH(3)COONa.3H(2)O. The structure of 3 is constructed by a 46-member crown-shaped anion, [Na(5)(H(2)O)(14)]within[Mo(V)(20)Mo(VI)(26)O(134)(OH)(10)(mu-CH(3)COO)(4)](21-), 3a, which is built up by three different but related building blocks in a new mode and further connected into layers via Na(+) and hydrogen bonds. Crystal data of compound 3: triclinic space group P(-1); a = 16.4065(3), b = 17.4236(2), c = 20.8247(3) A; alpha= 87.57, beta= 67.9810(10), gamma= 80.6970(10)o; V = 5445.08(14) A(3); Z = 1; D(calcd) = 2.902. Structure solution and refinement are based on 19014 reflections, R = 0.0750.     

Solid state structure and solution behaviour of organoselenium(II) compounds containing 2-{E(CH2CH2)2NCH2}C6H4 groups (E = O, NMe)

Cleavage of the Se-Se bond in [2-{O(CH(2)CH(2))(2)NCH(2)}C(6)H(4)](2)Se(2) (1) and [2-{MeN(CH(2)CH(2))(2)NCH(2)}C(6)H(4)](2)Se(2) (2) by treatment with SO(2)Cl(2), bromine or iodine (1 : 1 molar ratio) yielded [2-{O(CH(2)CH(2))(2)NCH(2)}C(6)H(4)]SeX [X = Cl (3), Br (4), I (5)] and [2-{MeN(CH(2)CH(2))(2)NCH(2)}C(6)H(4)]SeI (6). The compounds were characterized in solution by NMR spectroscopy (1H, 13C, 15N, 77Se, 2D experiments). The solid-state molecular structures of 1-3, 4.HBr, 5 and 6 were established by single crystal X-ray diffraction. In all cases T-shaped coordination geometries, i.e. (C,N)SeSe (1, 2), (C,N)SeX (3, 5, 6; X = halogen) or CSeBr(2) (4.HBr), were found. Supramolecular associations in crystals based on hydrogen contacts are discussed.     

Formation and reactivity of the Os(IV)-azidoimido complex, PPN[Os(IV)(bpy)(Cl)(3)(N(4))

Reactions between the Os(VI)-nitrido complexes, [OsVI(L2)(Cl)3(N)] (L2 = 2,2'-bipyridine (bpy) ([1]), 4,4'-dimethyl-2,2'-bipyridine (Me2bpy), 1,10-phenanthroline (phen), and 4,7-diphenyl-1,10-phenanthroline (Ph2phen)), and bis-(triphenylphosphoranylidene)ammonium azide (PPNN3) in dry CH3CN at 60 degrees C under N2 give the corresponding Os(IV)-azidoimido complexes, [OsIV(L2)(Cl)3(NN3)]- (L2 = bpy = [2]-, L2 = Me2bpy = [3]-, L2 = phen = [4]-, and L2 = Ph2phen = [5]-) as their PPN+ salts. The formulation of the N42- ligand has been substantiated by 15N-labeling, IR, and 15N NMR measurements. Hydroxylation of [2]- at Nalpha with O<--NMe3.3H2O occurs to give the Os(IV)-azidohydroxoamido complex, [OsIV(bpy)(Cl)3(N(OH)N3)] ([6]), which, when deprotonated, undergoes dinitrogen elimination to give the Os(II)-dinitrogen oxide complex, [OsII(bpy)(Cl)3(N2O)]- ([7]-). They are the first well-characterized examples of each kind of complex for Os.