Preparation and structural characterization of di-μ-azido-bis[azido(2-aminopyridine)aquo]dicopper(II), [Cu(2-ampy)(N3)2(H2O)]2

Di-μ-azido-bis[azido(2-aminopyridine)aquo]dicopper(II), [Cu(2-ampy)(N₃)₂(H₂O)]₂, was synthesized and characterized by X-ray crystallography. The crystals are triclinic, space group P$\text{1}$, with a = 7.142(1), b = 7.812(1), c = 9.727(1) Å, a = 96.52(1), β = 95.52(1), γ = 113.47(1)°, and Z = 1. The structure was refined to R_F = 0.030 for 1960 observed MoKα diffractometer data. The dimeric molecule, which possesses a crystallographic inversion center, contains both terminal and μ(1)-bridging azido groups. Each copper(II) atom is further coordinated by a 2-aminopyridine ligand (via its ring N atom) and a water molecule to give a distorted square pyramid, with the metal atom raised by 0.17 Å above the N₄ basal plane [CuN (ring) = 2.001(2), CuN (azide) = 1.962(3)–2.018(2) Å] towards the apical aquo ligand [CuO = 2.371(2) Å]. Each water molecule forms an intramolecular O?HN (amine) acceptor hydrogen bond, and is linked by two OH?N (terminal azide) intermolecular donor hydrogen bonds to adjacent dimeric complexes to yield a layer structure parallel to (001). Infrared and electronic spectral data are presented and discussed.     

Effects of equatorial ligand bulk on the orientation of axial ligands in methyl organocobalt B12 models assessed by X-ray and NMR methods

We prepared two new analogues of ([CH₃Co((DO)(DOH)pn)L]⁺) [(DO)(DOH)pn = N²,N^2′-propane-1,3-diylbis(2,3-butanedione-2-imine-3-oxime)] B₁₂ models but with an O-BF₂-O unit replacing the O-H?O unit as follows: [CH₃Co((DO)(DOBF₂)pn)L]PF₆ with L = pyridine (py) and 1,5,6-trimethylbenzimidazole (Me₃Bzm). Our goal was to compare the properties of these new O-BF₂-O complexes with the well-established O-H?O analogues. The Co-CH₃¹H NMR shifts indicate that the BF₂ group makes the Co(III) less electron rich. The X-ray crystal structures determined for the new compounds were compared to the one known structure with L = imidazole (Im). With increasing size of L, in the series Im < py < Me₃Bzm, the plane of L orients so as to avoid the bulky BF₂ group. This orientation effect becomes apparent in the L ¹H NMR shifts, which are not sensitive to Co(III) electronic properties. Thus, in the O-BF₂-O versus the O-H?O analogue, the Me₃Bzm H4 signal shifts 0.41 ppm upfield from the anisotropic effect of the equatorial ligand double bonds. We advance the concept (applicable to a broad series of complexes) that steric interactions between L and the equatorial ligands are alleviated by a combination of Co-N_ax bond elongation and opening of the N_eq-Co-N_ax angles.     

Phosphane effects on formation and reactivity of [Ru(L)(PR3)(`N2Me2S2')] complexes with L=N2, N2H4, NH3, and CO

Metal-sulfur complex fragments, to which small molecules like N₂, N₂H₂, N₂H₄, NH₃, or CO can bind, are desirable model compounds concerning enzymatic N₂ fixation.This paper reports on the effects of the phosphane co-ligand on formation and reactivity of [Ru(L)(PR₃)(`N<sub>2</sub>Me<sub>2</sub>S<sub>2</sub>')] [`N₂Me₂S₂'²⁻=1,2-ethanediamine-N,N^′-dimethyl-N,N^′-bis(2-benzenethiolate)(2−)] complexes with nitrogenase relevant ligands, especially N₂, N₂H₄, NH₃, and CO.Treatment of [Ru(NCCH₃)₄Cl₂] with Li₂`N<sub>2</sub>Me<sub>2</sub>S<sub>2</sub>', excessive LiOMe, bulky PPh<sub>3</sub> or PCy<sub>3</sub>, respectively, led to the formation of two series of [Ru(L)(PR<sub>3</sub>)(`N₂Me₂S₂')] complexes [for R=Ph: 1b, 1c (L=NCCH₃), 6b (L=N₂H₄), 7b (L=N₂), 8b_1-3 (L=CO), 9b (L=NH₃); for R=Cy: 1a (L=NCCH₃), 6a (L=N₂H₄), 7a (L=N₂), 8a (L=CO), 9a (L=NH₃)]. While the use of PPh₃ (θ=145°) yielded cis,trans and cis,cis isomers of [Ru(NCCH₃)(PPh₃)(`N<sub>2</sub>Me<sub>2</sub>S<sub>2</sub>')] (1b, 1c), no isomer formation was observed with the bulkier phosphane PCy<sub>3</sub> (θ=170°). Sterically less demanding phosphanes (θ=118-132°) afforded bisphosphane complexes [Ru(PR<sub>3</sub>)<sub>2</sub>(`N₂Me₂S₂')] [2d (R=Me), 2e (R=Et), 2f (R=nPr), and 2g (R=nBu)], which were practically inert and could only be converted in two cases and under drastic reaction conditions into the CO complexes [Ru(CO)(PR₃)(`N<sub>2</sub>Me<sub>2</sub>S<sub>2</sub>')] [4e (R=Et), 4f (R=nPr)]. The chelating bidentate phosphane dppe (bisdiphenylphosphanoethane) yielded exclusively the mononuclear complex [Ru(dppe)(`N₂Me₂S₂')] (3).     

A trinuclear copper(II) complex with 2,5-pyridine-dicarboxylato bridges - [Cu3(2,5-pydc)2(Me5dien)2(H2O)2(BF4)2] · H2O: Synthesis, crystal structure and magnetic properties

A trinuclear copper(II) complex, [Cu₃(2,5-pydc)₂(Me₅dien)₂(BF₄)₂(H₂O)₂] · H₂O 1, has been constructed from 2,5-pyridine-dicarboxylato bridges (2,5-pydc²⁻) and N,N,N′,N″,N″-pentamethyl-diethylenetriamine (Me₅dien) acting as a blocking ligand. The copper ions, within the centrosymmetric trinuclear cations, are connected by two 2,5-pydc²⁻ bridges, with an intramolecular Cu···Cu separation of 8.432 Å. The central copper ion exhibits an elongated octahedral geometry, with semicoordinated ions, while the terminal ones are pentacoordinated (distorted square-pyramidal geometry). The cryomagnetic investigation of 1 reveals an antiferromagnetic coupling of the copper(II) ions (J = −5.9 cm⁻¹, H = −JS_Cu1S_Cu2 − JS_Cu2S_Cu1a).     

温带针阔混交林土壤碳氮气体通量的主控因子与耦合关系

中高纬度森林地区由于气候条件变化剧烈,土壤温室气体排放量的估算存在很大的不确定性,并且不同碳氮气体通量的主控因子与耦合关系尚不明确。以长白山温带针阔混交林为研究对象,采用静态箱-气相色谱法连续4a(2005—2009年)测定土壤二氧化碳(CO2)、甲烷(CH4)和氧化亚氮(N2O)净交换通量以及温度、水分等相关环境因子。研究结果表明:温带针阔混交林土壤整体上表现为CO2和N2O的排放源和CH4的吸收汇。土壤CH4、CO2和N2O通量的年均值分别为-1.3 kg CH4hm-2a-1、15102.2 kg CO2hm-2a-1和6.13 kg N2O hm-2a-1。土壤CO2通量呈现明显的季节性规律,主要受土壤温度的影响,水分次之;土壤CH4通量的季节变化不明显,与土壤水分显著正相关;土壤N2O通量季节变化与土壤CO2通量相似,与土壤水分、温度显著正相关。土壤CO2通量和CH4通量不存在任何类型的耦合关系,与N2O通量也不存在耦合关系;土壤CH4和N2O通量之间表现为消长型耦合关系。这项研究显示温带针阔混交林土壤碳氮气体通量主要受环境因子驱动,不同气体通量产生与消耗之间存在复杂的耦合关系,下一步研究需要深入探讨环境变化对其耦合关系的影响以及内在的生物驱动机制。     

Salts of cationic platinum dithiolenes with anionic platinum complexes: structural characterization of [Pt(Me2pipdt)2][Pt(SCN)4] (Me2pipdt = N,N-dimethyl-piperazine-2,3-dithione)

[Pt(Me₂pipdt)₂](BF₄)₂ salts [Me₂pipdt = N,N^′-dimethyl-piperazine-2,3-dithione] bearing cationic dithiolene complexes react with (Bu₄N)₂[Pt(X)₄] (X = SCN, CN) to form [Pt(Me₂pipdt)₂][Pt(SCN)₄ ] (1) and [Pt(Me₂pipdt)₂][Pt(CN)₄] (2) salts by metathesis. Black crystals of 1 have been structurally characterized showing that the two metals lie on inversion centers and exhibit a square planar coordination. The Pt-S bond distances in the anion complex (2.324(2) Å) are longer than in the cation complex (2.280(2) Å) whereas the C-S bond distances are shorter in SCN⁻ (average 1.669 Å) than in Me₂pipdt (average 1.694 Å). The chelating Me₂Pipdt ligand is found disordered in the λ/δ conformations with site occupancies of 50/50, respectively. The cation and anion complexes run parallel to a.     

Syntheses and characterization of the W(II) and W(III) N2 complexes, [WCl2(PMe3)3]2N2 and [WCl3(PMe3)2]2N2

Refluxing WCl₄(PMe₃)₃ under a nitrogen atmosphere in the presence of two equivalents of sodium amalgam leads to a reduction to the W(II) complex [cis,mer-WCl₂(PMe₃)₃]₂N₂ (1), which can be converted to [mer,trans-WCl₃(PMe₃)₂]₂N₂ (2) via appropriate oxidation/chlorination. Structural data have been obtained for both complexes, and demonstrate significantly increased steric crowding in 1 due to PMe₃/PMe₃ interactions. The N-N bond distances in the two compounds are similar, at 1.279(4) and 1.243(18) Å, respectively.     

Synthesis and characterization of [Ru(NO)(bpp)Cl · 2H2O] [bpp = N,N′-bis(2-pyridinecarboxamide)-1,3-propane dianion] and [Ru(NO)(bpe)Cl · 2H2O] [bpe = N,N′-bis(2-pyridinecarboxamide)-1,2-ethane dianion]

Two ruthenium nitrosyl bis-pyridyl/biscarboxamido compounds, [Ru(NO)(bpp)Cl · 2H₂O] [bpp = N,N′-bis(2-pyridinecarboxamide)-1,3-propane dianion] and [Ru(NO)(bpe)Cl · 2H₂O] [bpe = N,N′-(bis-2-pyridinecarboxamide)-1,2-ethane dianion] have been characterized by ¹H NMR, ¹³C{¹H} NMR, and IR spectroscopies, electrospray ionizaton mass spectrometry, and X-ray crystallography.     

Copper and manganese complexes with C2-multitopic ligands. X-ray crystal structure of [Cu(N,N′-bis[(S)-prolyl]phenylenediamine)H2O]. Catalytic properties

Eight mononuclear complexes with multitopic C₂-symmetry ligands, [Cu(L)]ClO₄, [Mn(L)Cl(H₂O)]PF₆, (L=N,N′-bis[(S)-prolyl]phenylenediamine (1), N,N′-bis[(S)-N-benzylprolyl]phenylenediamine (2), N,N′-bis{[(S)-pyrrolidin-2-yl]methyl}phenylenediamine (3), N,N′-bis-{[(S)-N-benzyl-pyrrolidin-2-yl]methyl}phenylenediamine (4)) have been prepared and characterised by analytical (elemental analysis, and mass spectroscopy) and FT IR, NMR and electronic spectroscopies. The data show that the ligands are neutral and coordinate to the metal in a tetradentate manner. The N,N′-bis[(S)-prolyl]phenylenediamine ligand also appears as an anionic species, (LH-2), and the single crystal structure determination of the respective complex, [Cu(1)]H₂O, is reported. This new family of Cu-complexes catalyse the cyclopropanation of styrene with ethyl and t-butyl diazoacetate to afford cis/trans 2-phenylcyclopropan-1-carboxylates with good yields and selectivity against dimerisation and low ee (<10%). On the other hand, the manganese and copper complexes also catalyse the oxidation of organic sulfides to sulfoxides with high selectivity, and moderate to low enantioselectivity. If an excess of oxidant were used the reaction yields sulfone as only product with excellent yield.     

Syntheses, electrolytic behaviour and antifungal activities of Zn(II) complexes of isomers of 3,10-C-meso-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane (L). Crystal and molecular structure of [ZnLB(NO3)]NO3 (LB = a,e,a,e-L)

The isomeric cyclam ligands Me₈[14]anes, designated by L_A, L_B and L_C, produce, on reaction with zinc(II)nitrate, zinc(II)sulphate or zinc(II)chloride corresponding complexes, i.e. dinitrato/mononitrato-nitrate complexes [ZnL(NO₃)₂]/[ZnL(NO₃)](NO₃) (L = L_A, L_B or L_C, where the indices A, B and C refer to differing orientations of the four methyl groups on secondary carbons of Me₈[14]ane)_, the diaqua-sulphates [ZnL(H₂O)₂]SO₄ (L = L_A, L_B or L_C), and the diaqua dichloride and dichlorido complexes [ZnL(H₂O)₂]Cl₂ (L = L_A or L_C) or [ZnL_BCl₂], respectively. The complexes have been characterised on the basis of elemental analyses, IR, UV-Vis, ¹H and ¹³C NMR spectroscopies, magnetic and conductance data. The structure of [ZnL_B(NO₃)](NO₃) has been determined by X-ray crystallography. The zinc centre is coordinated to a N₄O donor set in a square-pyramidal geometry. The complexes show differing electrolytic behaviour in different solvents. In chloroform, the complexes are non-electrolytes, indicating that both anions are coordinated to Zn²⁺. Antifungal activity of the ligands and complexes against the phytopathogenic fungi Alternaria alternata and Colletotrichum corcolei have been investigated, and positive results were noted.     

New versatile phosphorus ligands containing SPNSO skeleton - synthesis and characterization of (SPPh2)(O2SR)NH acids (R=Me, C6H4Me-4) and their alkaline metal salts. Crystal and molecular structures of (SPPh2)(O2SR)NH

New phosphorus ligands of the type (SPPh₂)(O₂SR)NH [R=Me (1), C₆H₄Me-4 (2)] were prepared as white crystalline solids using the reactions between Li[HN(S)PPh₂] and RSO₂Cl. They were easily converted into their alkali metal salts, M[(SPPh₂)(O₂SR)N] (M=Li, Na, K). Both the free acids and their alkali metal salts were characterised by multinuclear (¹H, ¹³C, ³¹P) NMR spectroscopy. The molecular structures of the free acids were established by single crystal X-ray diffraction. They crystallize in the tetragonal space group I4₁/a (1) and the triclinic space group P−1 (2), respectively. In both compounds the acidic proton is attached to nitrogen and the molecular units are associated through SO?H-N intermolecular hydrogen bonding [H?O 2.216 in 1 and 2.029 Å in 2]. A supramolecular chain-like structure is formed in 1 and dimeric units are built in 2. For both compounds a conformation close to syn-syn can be considered for the SP(C)₂-N-SC(O)₂ fragment.     

Versatile reaction of the potential host system [(Me3Sn) 4Ru(CN) 6]∞ with 4-thiopyridone/4-mercaptopyridine in water

Single crystals of three derivatives of the structurally still incompletely characterized coordination polymer [(Me₃Sn)₄Ru(CN)₆] 1b have been prepared and subjected to crystallographic studies: [1b · 4H₂O]=2b forms stacks of puckered _∞²[Ru{μ-CNSn(Me₃)NC}₂] sheets interlinked by hydrogen bonds in making use of two additional CNSn(Me₃)OH₂ ligands and quasi-zeolitic water. Mild drying of 2b leads to the “missing link” between 1b and 2b, [1b · 2H₂O], 3b. The structure of [1b · 2tp] (tp=4-thiopyridone) consists of a three-dimensional, negatively charged host framework comprising (via Sn-S bonds) one “aromatic” thione linkage and a [Me₃Sn · tp]⁺guest ion involving a more zwitterionic form of tp. Slow uptake of Me₃SnCl from the gas phase by an aqueous solution of K₄[Ru(CN)₆] and tp afforded the novel assembly [1b · 2H₂O · 0.8pms · 0.2pds] (pms/pds=4,4^′-dipyridylmono-/disulfide), the supramolecular architecture of which resembles that of 2b. Bridging pms or pds molecules occupy equivalent interlayer sites, and the pms/pds ratio is likely to vary. At least three further assemblies containing again 1b and either tp or pds/pms have likewise been isolated, however, not as single crystals.     

Hydrolytic stability of SnCl4 and GaCl3 in the formation of [cis-SnCl4(H2O)2] · 18-crown-6 · 2H2O and [[2,2,2]cryptand + 2H][GaCl4]2

The combination of anhydrous SnCl₄ with 18-crown-6 in aqueous conditions results in formation of the non-hydrolysed product [cis-SnCl₄(H₂O)₂] · 18-crown-6 · 2H₂O. The X-ray crystal structure shows extensive intermolecular hydrogen bonding involving the cis-octahedral SnCl₄(H₂O)₂ units, the uncoordinated water molecules and the crown ether. Similarly, [2,2,2]cryptand reacts with an aqueous solution formed by adding anhydrous GaCl₃ to slightly acidic water, affording [[2,2,2]cryptand + 2H⁺][GaCl₄]₂.     

A solution thermodynamic study of the Cu(II) and Zn(II) complexes of EBTA: X-ray crystal structure of the dimeric complex [Cu2(EBTA)(H2O)3]2

The copper(II) complex of the acyclic EBTA ligand (H₄EBTA = 1,2-bis(2-aminoethoxy)benzene-N,N,N′,N′-tetraacetic acid) has been prepared and characterized by X-ray analysis. The two copper ions of the dinuclear unit present the same distorted octahedral coordination polyhedra. The EBTA ligand is shared between two copper coordination centres, with the formation of centrosymmetric dimers, which are linked in a supramolecular tridimensional structure via additional interactions through the coordinated waters molecules with adjacent carboxylic oxygen atoms. The stability and protonation constants of EBTA with Cu(II) and Zn(II) ions indicate a higher stability of these complexes with respect to the corresponding complexes with the more flexible EGTA ligand (H₄EGTA = ethyleneglycol-bis(2-aminoethylether)-N,N,N′,N′-tetraacetic acid). On the other hand, the lower stability of [Gd(EBTA)]⁻ than [Gd(EGTA)]⁻ results in a decreased overall selectivity (lower K_sel) of EBTA towards Gd(III) and suggests that this complex may undergoes transmetallation reactions under physiological conditions.     

Coordination chemistry of lanthanides with cryptands. An X-ray and spectroscopic study of the complex Nd2(NO3)6 [C18H36O6N2]·H2O

By reacting neodymium nitrate hexahydrate with the cryptand 〈222〉 in methanol, the complex Nd₂-(NO₃)₆[C₁₈H₃₆O₆N₂]·H₂O was obtained and analyzed by single-crystal X-ray diffraction. The cell is triclinic P$\text{1}$ with a = 14.870(2) Å, b = 13.261(2) Å, c = 8.832(1) Å, α = 91.2(1)°, β = 93.4(1)°, γ = 87.6(1)°, Z = 2 and U = 1736.6 ų. The structure was refined by least-squares methods to the conventional R = 0.039 for 6177 observed reflections. The compound contains the cations [Nd〈222〉(NO₃)]²⁺ and the anions [Nd(NO₃)₅·H₂O]^2?, and is isostructural with the samarium analogue. Solid state fluorescence spectra of the title complex were measured at room and liquid nitrogen temperature, and the transitions ⁴F_3/2 → ⁴I_9/2 and ⁴F_3/2 → ⁴I_11/2 analyzed.     

A novel ferromagnetic coupling one-dimensional complex {Cu(II)(NIT3Py)2[N(CN)2]2(H2O)2}

The novel ferromagnetic coupling one-dimensional complex {Cu(NIT3Py)₂[N(CN)₂]₂(H₂O)₂} (NIT3Py=2-(3^′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) was synthesized and characterized structurally and magnetically. It crystallizes in the monoclinic space group C2/c. The Cu(II) ion is in a distorted octahedral environment. The units of {Cu(NIT3Py)₂[N(CN)₂]₂(H₂O)₂} were connected as one-dimensional structure by the intermolecular hydrogen bonds. Magnetic measurements show that there are intramolecular ferromagnetic interactions and intermolecular antiferromagnetic interactions within the chain.     

Synthesis of fac-[Os(CO)3(L)Me2] (L = THF or MeCN) and some reactions with PPh3 and trityl salts

The reaction of cis-[Os(CO)₄Me₂] with Me₃NO in the THF or MeCN yields the complexes fac-[Os(CO)₃(L)Me₂] (where L = THF or MeCN). Whereas the THF complex is unstable and only characterised spectroscopically, fac-[Os(CO)₃(MeCN)Me₂] has been isolated as a white solid and fully characterized by both analytical and spectroscopic methods. These complexes fac-[Os(CO)₃(L)Me₂] are shown to be useful intermediates. Thus, reaction with PPh₃ gives fac-[Os(CO)₃(PPh₃)Me₂] in good yield.Reactions of fac-[Os(CO)₃(L)Me₂] (L = CO or MeCN) with CPh₃PF₆ or B(C₆F₅)₃ have been investigated. Whereas cis-[Os(CO)₄Me₂] showed no reaction with either CPh₃PF₆ or B(C₆F₅)₃, the reaction of fac-[Os(CO)₃(MeCN)Me₂] with CPh₃PF₆ in CH₂Cl₂ occurred over 16 h at room temperature to give an unstable cationic product and CPh₃Me. The reaction was monitored by both IR and NMR spectroscopies. When this reaction of fac-[Os(CO)₃(MeCN)Me₂] was carried out in the presence of a trapping ligand such as MeCN, the stable cationic product [Os(CO)₃(MeCN)₂Me]⁺ could be isolated and identified spectroscopically.     

Synthesis, characterization and thermal decomposition of dioxouranium(VI) complexes with N,N-diarylidene-S-propyl-thiosemicarbazone: Crystal structure of [UO2(L)(C4H9OH)]

Reactions of salicyl- and 3,5-dichlorosalicylaldehyde-S-propyl-thiosemicarbazones with salicyl- and 3,5-dichlorosalicylaldehyde in the presence of UO₂(CH₃COO)₂ in different alcohols yielded stable solid complexes corresponding to the general formula [UO₂(L)ROH] (R: propyl-, butyl-, pentyl-, and octyl-). The complexes were characterized by means of elemental analysis, IR and ¹H NMR spectroscopies. The thermal stabilities of the alcohol solvated complexes were investigated in air and nitrogen atm., and determined their decomposition phases. In the crystal structure of the [UO₂(L)(C₄H₉OH)], the U(VI) centre is seven-coordinated in a distorted pentagonal bipyramidal geometry involving O,O,N,N atoms of two phenolic and two imine groups and one oxygen atom of alcohol molecule in basal plane and two O atoms of dioxo group in apical positions. The title structure is stabilized by one intramolecular interaction of types C-H?Cl and by two intermolecular interactions of types O-H?O and C-H?π (benzene) leading to the molecular chain along the [0 1 0] direction.     

Synthesis and structure of an organosamarium aryloxide complex, (C5 Me5)2 Sm(OC6HMe4-2,3,5,6)

Bis(pentamethylcyclopentadienyl)samarium bis- (tetrahydrofuranate), (C₅Me₅)₂Sm(THF)₂, reacts with 2,3,5,6-tetramethylphenol in toluene to yield (C₅Me₅)₂Sm(OC₆HMe₄-2,3,5,6). The compound crystallizes in the space group P2₁/c with a = 8.725(3) Å, b=18.821(6) Å, c=18.461(6) Å, β= 111.17(2)°, V = 2827(2) ų and D_c=1.340 g cm⁻³ for Z = 4. Molecules of the aryloxide complex are monomeric and exhibit a bent metallocene structure with a nearly linear Sm---O---C(aryloxide) linkage: Sm---O = 2.13(1) Å, O---C = 1.29(2) Å, and Sm---O---C = 172.3(13)°. Reaction of the samarium complex with phenyllithium produces the previously- characterized species (C₅Me₅)₂Sm(C₆H₅)(THF).     

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..