Sodium Derivatives Research Articles

Exploiting σ/π Coordination Isomerism to Prepare Homologous Organoalkali Metal (Li, Na, K) Monomers with Identical Ligand Sets

Tetraamine Me(6)TREN has been used as a scaffold support to provide coordinative saturation in the complexes PhCH(2)M⋅Me(6)TREN (M=Li, Na, K). The Li derivative displays a Li−−C σ interaction with a pyramidalized CH(2) both in the solid state and in solution, and represents the first example of η(4) coordination of Me(6)TREN to lithium. In the sodium derivative, the metal cation slips slightly towards the delocalized π electrons whilst maintaining a partial σ interaction with the CH(2) group. For the potassium case, coordinative saturation successfully yields the first monomeric benzylpotassium complex, in which the anion binds to the metal cation exclusively through its delocalized π system resulting in a planar CH(2) group.

Effect of chain length on the formation of intramolecular and intermolecular products: Reaction of diols with cyclotriphosphazene

The reactions of cyclotriphosphazene, N3P3Cl6 (1), in a 1:1.2 stoichiometry with the sodium derivative of seven diols [ethane- (2a), 1,3-propane- (2b), 1,4-butane- (2c), 1,5-pentane- (2d), 1,6-hexane- (2e), 1,8-octane- (2f) and 1,10-decane- (2g) diol] in THF solution at room temperature have been used to investigate the effect of chain length on the formation of reaction products. Although no new products were found for the reaction of 1 with diols 2a–c compared to those in the literature using other bases and solution conditions, the reactions of 1 with the diols 2d–g gave six different types of products, whose structures have been characterized by elemental analysis, mass spectrometry, 1H and 31P NMR spectroscopy; ansa compounds N3P3Cl4[O(CH2)nO], (5d–5g); single-bridged compounds N3P3Cl5[O(CH2)nO]N3P3Cl5(6d–6f); double-bridged compounds N3P3Cl4[O(CH2)nO]2N3P3Cl4 (7d–7g, syn and anti) and triple-bridged compounds, N3P3Cl3[O(CH2)nO]3N3P3Cl3 (8d–f). Where suitable single crystals were obtained, X-ray crystallographic studies confirmed the structures of two ansa compounds (5d and 5f), one single-bridged compound (6e), and five double-bridged compounds (meso-anti for 7d, 7e, 7f and meso-syn for 7d and 7f). 31P NMR measurements of the reaction mixtures were used to quantify the formation of products for the reactions 1 with all the diols, 2a–g; it is found that, with increasing chain length of the diol, there is a decrease in the products formed by intramolecular reactions (spiro and ansa derivatives) and a concomitant increase in the amounts of products formed by intermolecular reactions (single-, double- and triple-bridged derivatives) of cyclophosphazene.

Spiro, ansa-derivatives of cyclotetraphosphazenes with a tetrafluorobutane-1,4-diol

The reaction of the octachlorocyclotetraphosphazene, N 4P 4Cl 8 ( 1), in three stoichiometries (1:1, 1:2 and 1:3) with the sodium derivative of the fluorinated diol, 2,2,3,3-tetrafluorobutane-1,4-diol ( 2), in THF solution at room temperature produced seven products, whose structures have been characterized by elemental analysis, mass spectrometry, 1H, 19F, 31P NMR spectroscopy and by X-ray crystallography, where suitable single crystals were obtained: the mono-spiro compound, N 4P 4Cl 6(OCH 2CF 2CF 2CH 2O) ( 3), its ansa isomer ( 4), cis- and trans-bis-spiro derivatives N 4P 4Cl 4(OCH 2CF 2CF 2CH 2O) 2 ( 5 and 6), tris-spiro compound N 4P 4Cl 2(OCH 2CF 2CF 2CH 2O) 3 ( 7), its mono-spiro-bis-ansa isomer ( 8) and tetrakis-spiro compound N 4P 4(OCH 2CF 2CF 2CH 2O) 4, ( 9). X-ray crystallographic studies confirmed that the structure of the mono-spiro-bis-ansa isomer ( 8) has been reported as a first example in the literature. The results of all reactions were compared with previous work on the reaction of hexachlorocyclotriphosphazene, N 3P 3Cl 6 with the sodium derivative of the diol ( 2), in a 1:1.2 mole ratio in the in the same solvent, THF, and with the reaction of octafluorocyclotetraphosphazene, N 4P 4F 8, with the silyl derivative of the diol ( 2), (Me 3SiOCH 2CF 2) 2, in a 1:0.4 mole ratio in THF.

Crystal structure of MIVWO6 (M = Li, Na) compounds

Compounds of the composition MIVWO6 (M = Li, Na) were prepared by solid-phase synthesis at 600°C. The compounds crystallize in the mineral brannerite structure type. The sodium derivative was prepared and identified for the first time. The crystal structures of the compounds were refined by the Rietveld method (space group C2/m).

Synthesis of C-phosphorylated acetamidines containing CH-acidic methylene group

C-Phosphorylated acetamidines with the methylene group linked to dialkoxyphosphoryl and amidine groups possessing CH-acidic properties were obtained and characterized. At the reaction of these amidines with sodium one hydrogen atom is substituted to form sodium derivatives interesting as intermediates for the syntheses of the organophosphorus compounds of versatile nature. Based on the CH-acidity of C-phosphorylated acetamidines a convenient method is developed for the synthesis of C-phosphorylated bromoacetamidines.

Quantitative structure activity relationship (QSAR) studies on a series of off-target ion channel selective diltiazem sodium derivatives

QSAR studies were performed on a series of off-target ion channel selective diltiazem sodium derivatives. Diltiazem sodium derivatives have been analyzed in relation to their physicochemical and molecular properties. The activities of the compounds were found to be significantly correlated with the physicochemical parameters such as MR, MW, Pc, 0 χ, 1 χ, 2 χ, 5 χ and Xeq. It was found that the presence of group N H 2 at R 1 position was conducive for the inhibitory activity. The results are critically discussed on the basis of regression data and cross validation techniques. Poglani factor Q and the results of LOO (leave one out) method confirmed the reliability and predictability of the proposed models and it may be concluded that sterically hindered, denser and polar groups will favour the inhibitory activity (P IC 50 ).

Reaction of Lithium Cyanoaluminum Hydride with Selected Organic Compounds Containing Representative Functional Groups. Comparison of Reducing Characteristics between Lithium and Sodium Cyanoaluminum Hydrides

Lithium cyanoaluminum hydride (LCAH) was prepared by the metal cation exchange reaction of sodium cyanoaluminum hydride with lithium chloride in tetrahydrofuran. The reducing characteristics of LCAH were explored systematically by the reaction with selected organic compounds containing representative functional groups under the standardized conditions (tetrahydrofuran, 0 <TEX>${^{\circ}C}$</TEX>). The reducing ability of LCAH was also compared with of the sodium derivative, sodium cyanoaluminum hydride (SCAH). Generally, the reducing behavior of LCAH resembles that of SCAH closely, but the reactivity of LCAH toward representative organic functional groups appeared to be stronger than that of SCAH. Thus, the regent reduces carbonyl compounds, epoxides, amides, nitriles, disulfides, carboxylic acids and their acyl derivatives to the corresponding alcohols or amines, at a relatively faster rate than that of SCAH. The cyano substitution, a strong election-withdrawing group, diminishes the reducing power of the parent metal aluminum hydrides and hence effects the alteration of their reducing characteristics.

Thiosilicate der Selten‐Erd‐Elemente: IV. Die quasi‐isostrukturellen Verbindungen NaSm3S3[SiS4], CuCe3S3[SiS4], Ag0,63Ce3S2,63Cl0,37[SiS4] und Sm3S2Cl[SiS4] – Synthese, Kristallstruktur und Untersuchungen zur Silberionendynamik

AbstractThiosilicates of the Rare‐Earth Elements: IV. The quasi‐isostructural Compounds NaSm3S3[SiS4], CuCe3S3[SiS4], Ag0,63Ce3S2,63Cl0,37[SiS4] and Sm3S2Cl[SiS4] – Synthesis, Crystal Structure and Investigations of the Silver‐Cation MotionThe four lanthanoid(III) thiosilicates NaSm3S3[SiS4] (1), CuCe3S3[SiS4] (2), Ag0,63Ce3S2,63Cl0,37[SiS4] (3) and Sm3S2Cl[SiS4] (4) crystallize all hexagonally in the non‐centrosymmetric space group P63 (no. 173) showing basically the same structure. Besides an eightfold square‐antiprismatic sulfide coordination sphere about the M3+ cations these compounds display discrete tetrahedral thiosilicate units [SiS4]4− which are trigonally distorted. All tops of the remaining pyramids point into the same direction along the c axis and therefore the structure needs to be non‐centrosymmetric. However, the main feature of these crystals are channels along [001], built up by non‐silicon bonded sulfide anions and providing trigonal planar (CN = 3) and trigonal antiprismatic (CN = 6) voids. In the sodium derivative (1) the Na+ cations reside almost in the center of the latter ones exhibiting a trigonally distorted octahedral surrounding (CN = 6) while the Cu+ cations of the respective thiosilicate (2) are situated in the middle of an (S2−)3 triangle (CN = 3), just 7 pm above its plane. The same is true for the silver compound (3) with the exception of the Ag+ cations sitting about 53 pm above the sulfide triangle and showing a marked under‐occupation along with a very large U33 displacement parameter. These facts lead to the assumption that (3) could be a promising material for ionic Ag+ conduction. In order to maintain electroneutrality the silver derivative has to contain a certain amount of Cl− anions (CeCl3 was used as fluxing agent) substituting S2− which was doubtlessly confirmed by WDX analyses. In the absence of any monovalent cation (A+) the analogous structure is realized in (4) displaying an empty channel along [001] and a complete substitution of one sulfide by one chloride anion per formula unit, also confirmed by electron‐beam microanalysis.

Formation of spiro and ansa derivatives in the reaction of 2,2,3,3,4,4-hexafluoropentane-1,5-diol with cyclotriphosphazene: Comparison with 2,2,3,3-tetrafluorobutane-1,4-diol

Reaction of cyclophosphazene, N 3P 3Cl 6 ( 1), with the sodium derivative of the fluorinated diol, 2,2,3,3,4,4-hexafluoropentane-1,5-diol ( 2), in THF solution at room temperature afforded five isolated products, whose structures have been characterised by X-ray crystallography and 1H, 19F and 31P NMR spectroscopy: the mono-spiro compound, N 3P 3Cl 4(OCH 2CF 2CF 2CF 2CH 2O) ( 3), its ansa isomer ( 4), a di-spiro derivative N 3P 3Cl 2(OCH 2CF 2CF 2CF 2CH 2O) 2 ( 5), its spiro-ansa ( 6) isomer and the tri-spiro compound N 3P 3(OCH 2CF 2CF 2CF 2CH 2O) 3 ( 7). Quantitative 31P NMR measurements of the soluble portion of the reaction mixture show that in the reaction of ( 1) with the sodium derivative of the fluorinated pentanediol ( 2) there is a small preference for spiro compounds compared to ansa compounds (ratio ca. 1.3:1), similar to the analogous reaction of ( 1) with the sodium derivative of the fluorinated butanediol where there is a slightly greater proportion of spiro compared to ansa compounds (ratio ca. 1.5:1). The relative proportions of spiro and ansa compounds is likely to depend on the fine balance in stabilities of the different medium-sized rings in the fluorinated pentanediol (spiro, 8- and ansa, 10-membered rings) compared to the fluorinated butanediol (spiro, 7- and ansa, nine-membered rings) derivatives of cyclophosphazene.

Synthesis, structural characterization and reactivity of new tin bridged ansa-bis(cyclopentadiene) compounds: X-ray crystal structures of Me 2Sn(C 5Me 4R-1) 2 (R = H, SiMe 3)

The organo-tin compounds, Me 2Sn(C 5H 4R-1) 2 (R = Me ( 1), Pr i ( 2), Bu t ( 3), SiMe 3 ( 4)) and Me 2Sn(C 5Me 4R-1) 2 (R = H ( 5), SiMe 3 ( 6)), were prepared by the reaction of Me 2SnCl 2 with the lithium or sodium derivative of the corresponding cyclopentadiene. Compounds 1– 6 have been characterized by multinuclear NMR spectroscopy ( 1H, 13C, 119Sn). In addition the molecular structures of 5 and 6 were determined by single crystal X-ray diffraction studies. The transmetalation reaction of 1– 6 with ZrCl 4 or [NbCl 4(THF) 2] gave the corresponding metallocene complexes in high yields.

Two new metal derivates of the alumosiloxane [Ph 2SiO] 8[AlO(OH)] 4: [Ph 2SiO] 8[AlO 2(Na)] 4 · 5(THF) and [Ph 2SiO] 8[AlO(OH)] 2[AlO 2] 2[Zn(OH)] 2 · 2(OEt 2)

When the polycyclic alumosiloxane [Ph 2SiO] 8[AlO(OH)] 4 is allowed to react with either cyclopentadienyl sodium in tetrahydrofuran or with dimethyl zinc in diethyl ether the organic ligands on the metal elements are eliminated as cyclopentadiene or methane and the metals are bonded to oxygen atoms in the alumosiloxane forming [Ph 2SiO] 8[AlO 2(Na)] 4 · 5(THF) or [Ph 2SiO] 8[AlO(OH)] 2[AlO 2] 2[Zn(OH)] 2 · 2(OEt 2), respectively. X-ray structure determinations reveal that in the sodium derivative the original polycycle rests almost unchanged while in the zinc derivative the inner skeleton is rearranged.

Reduced Pain of Intraarticular Hyaluronate Injection With the Reciprocating Procedure Device

Greater than 50% of patients report significant pain with intraarticular injection of hyaluronate. The reciprocating procedure device (RPD), also known the reciprocating syringe, has 2 plungers that reciprocate with each other, permitting one-handed operation. The RPD increases physician control of the needle and is proposed to reduce patient pain during syringe procedures. To determine in a randomized controlled trial whether the RPD induces less pain than the traditional syringe during intraarticular hyaluronate therapy for the knee. Eighty intraarticular injection procedures of the knee were randomized to either the conventional syringe or the RPD using hyaluronate sodium derivative (Hylan G-F-20). Outcome measures included physician's estimate of pain, patient pain (Visual Analogue Pain Scale [VAPS]), procedure duration, operator satisfaction, complications, and response to the injected medication. Patients reported 85% more pain than physicians estimated. Fifty-one percent (19/37) of subjects experienced moderate to severe pain with the conventional syringe, while only 14% (6/43) experienced pain with the RPD. The RPD reduced pain scores (RPD VAPS score: 2.12 +/- 2.15; conventional syringe VAPS score: 4.22 +/- 3.25; P < 0.001), reduced procedure time (RPD: 1.34 +/- 1.09, conventional syringe: 1.90 +/- 1.35 minutes, P < 0.001), and improved physician satisfaction (RPD VASS Score: 9.02 +/- 0.80, conventional syringe 5.69 +/- 1.33, P < 0.001). Patients have considerably more pain with intraarticular needle introduction and injectable hyaluronate therapy than physicians estimate. The RPD reduces patient pain, reduces procedure time, and improves needle introduction compared with the conventional syringe for hyaluronate injection therapy for the knee.

Sodium 3,5-dinitropyridin-4-olate dihydrate

The six-membered ring of the 3,5-dinitropyridin-4-olate anion in the title dihydrated sodium derivative, Na+·C5H2N3O5−·2H2O, exists in the pyridone form with C=C and C=O double bonds, and the negative charge formally residing on the N atom. The anions link the Na+ ions, each of which is coordinated by four water mol­ecules, into a linear chain that runs along the c axis of the unit cell. The chains are bridged by the water mol­ecules into a sheet structure. The anion and the Na+ ion lie on a mirror plane.

Alkali metal complexes of sterically demanding amino-functionalised secondary phosphanide ligands

The reaction between {(Me(3)Si)(2)CH}PCl(2) (4) and one equivalent of either [C(6)H(4)-2-NMe(2)]Li or [2-C(5)H(4)N]ZnCl, followed by in situ reduction with LiAlH(4) gives the secondary phosphanes {(Me(3)Si)(2)CH}(C(6)H(4)-2-NMe(2))PH (5) and {(Me(3)Si)(2)CH}(2-C(5)H(4)N)PH (6) in good yields as colourless oils. Metalation of 5 with Bu(n)Li in THF gives the lithium phosphanide [[{(Me(3)Si)(2)CH}(C(6)H(4)-2-NMe(2))P]Li(THF)(2)] (7), which undergoes metathesis with either NaOBu(t) or KOBu(t) to give the heavier alkali metal derivatives [[{(Me(3)Si)(2)CH}(C(6)H(4)-2-NMe(2))P]Na(tmeda)] (8) and [[{(Me(3)Si)(2)CH}(C(6)H(4)-2-NMe(2))P]K(pmdeta)] (9) after recrystallization in the presence of the corresponding amine co-ligand [tmeda = N,N,N',N'-tetramethylethylenediamine, pmdeta = N,N,N',N'',N''-pentamethyldiethylenetriamine]. The pyridyl-functionalized phosphane 6 undergoes deprotonation on treatment with Bu(n)Li to give a red oil corresponding to the lithium compound [{(Me(3)Si)(2)CH}(2-C(5)H(4)N)P]Li (10) which could not be crystallized. Treatment of this oil with NaOBu(t) gives the sodium derivative [{[{(Me(3)Si)(2)CH}(2-C(5)H(4)N)P]Na}(2) x (Et(2)O)](2) (11), whilst treatment of with KOBu(t), followed by recrystallization in the presence of pmdeta gives the complex [[{(Me(3)Si)(2)CH}(2-C(5)H(4)N)P]K(pmdeta)](2) (12). Compounds 5-12 have been characterised by (1)H, (13)C{(1)H} and (31)P{(1)H} NMR spectroscopy and elemental analyses; compounds 7-9, and 12 have additionally been characterised by X-ray crystallography. Compounds 7-9 crystallize as discrete monomers, whereas 11 crystallizes as an unusual dimer of dimers and 12 crystallizes as a dimer with bridging pyridyl-phosphanide ligands.

HLB number of Vitamins C, E, coenzyme Q 10 derivatives and their transportation efficiency into skin

We have been proposing a new delivery system of medicines and supplements. Derivatives of vitamin C, E and coenzyme Q 10 were examined regarding the relationship between the hydrophile-lipophile balance (HLB) number and the transdermal transportation efficiency into the skin. Non-invasive vibrational spectroscopies, infrared attenuated total reflection (IR-ATR) and near-infrared diffusive reflection (NIR-DR) methods were used in order to evaluate transported materials in the skin. Vitamin C derivatives of sodium l-ascorbyl-2-phosphate (hereafter abbreviated as APS) and sodium l-ascorbyl-2-phosphate-6-palmitate (APPS) were examined. APPS contains both a hydrophilic group and a hydrophobic group, since APS has been modified to APPS by deriving palmitic acid ester in the 6-OH position. APPS has the value of HLB around 9.0, while APS has that of 20. The iontophoretic efficiency of APPS is higher than APS. Vitamin E derivatives of DL-α-tocopheryl N, N-dimethylglycinate (TDMG) and α-tocopheryl acetate (TA) were examined regarding the transdermal transportation effect. Those HLB numbers are 2.3 and 0, respectively. TA is hydrophobic, while TDMG has a hydrophilic terminal group of dimethylglycine HCl materials. Coenzyme Q 10 (CoQ 10) is hydrophobic and a portion of benzoquinone is also hydrophobic, thus, HLB = 0. CoQ 10 has been modified to a reduced form of CoQ 10 (CoH 2Q 10) by NaBH 4. CoH 2Q 10 has a hydroquinone structure of hydrophilic property and HLB = 3.9. Supersonic perforation transported a greater amount of CoH 2Q 10 into the skin than CoQ 10. The balance of the hydrophilic group and the hydrophobic group in the transported material is an important factor for the effective transportation into the skin.

C→N migration of methoxycarbonyl and acetyl groups in reactions of functionally substituted carbanions with aryl isocyanates. Kinetics and mechanism of the reactions

The kinetics and mechanism of C→N migrations of methoxycarbonyl and acetyl groups in the reactions of the sodium derivative of methyl (2-cyano-2-phenyl)acetate and 1,1-diacetyl-2-phenyl-2-tributylphosphonioethanide with aryl isocyanates were studied by spectrophotometry. The reactions afford a prereaction complex via a concerted mechanism, according to which the nucleophilic attack of the carbanionic center to the carbon atom of the isocyanate group and the subsequent nucleophilic attack of the nitrogen atom to the carbonyl carbon atom, resulting in the C-C bond cleavage, occur almost simultaneously in the framework of the same transition state.

Graft copolymerization of methacrylonitrile on caesarweed fibers by ceric ion/isopropanol redox pair

AbstractThe graft copolymerization of methacrylonitrile to caesarweed fiber and its sodium derivative by ceric ions in the presence of isopropanol was investigated in aqueous media. The percentage graft yield decreased initially and then increased with the concentration of isopropanol, but the graft levels of sodium caesarweed fibers were much lower. The graft reaction in the presence of isopropanol was characterized by the high frequency of grafting, up to 2.81 × 102 Ng/104 anhydroglucose units, and the low molecular weight of the grafted polymer, not higher than 0.94 × 103. The molecular weight of the grafted polymer showed a negative dependence on the concentration of isopropanol, suggesting the involvement of the latter in the transfer reactions with growing grafted polymer chains, which permitted calculation of the transfer constant, kA/kp, for the process: 7.91 × 10−2. The graft yield percent was found to be negatively dependent on the concentration of ceric ions for grafting of methacrylonitrile on sodium caesarweed fibers, but the molecular weight of the grafted polymer showed no clear‐cut trend with ceric ion concentration. The graft yield percent increased with temperature in the range of 30°C–50°C and decreased markedly at 70°C. The calculated activation energy of the graft reaction was 10.5 kcal/mol. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 353–358, 2006

Synthesis and characterization of some organo-all-tin dendrimers with different peripheral substituents

The synthesis of the first all-tin-dendrimer Sn[(CH 2) 4SnPh 3] 4 ( 2) results from complete hydrostannation of tetra(but-3-enyl)stannane ( 1) with triphenyltin hydride. Selective cleavage of one phenyl group from each dendron of 2 with anhydrous HCl results in Sn[(CH 2) 4Sn(Cl)Ph 2] 4 ( 3), which on treatment with LiAlH 4 yields the corresponding hydride derivative Sn[(CH 2) 4Sn(H)Ph 2] 4 ( 4) containing four reactive Sn–H bonds. The cyclopentadienyl derivative Sn[(CH 2) 4Sn(C 5H 5)Ph 2] 4 ( 5) as well as the transition metal substituted derivatives Sn[(CH 2) 4Sn{Co(CO) 4}Ph 2] 4 ( 6), Sn[(CH 2) 4Sn{Fe(CO) 2C 5H 5}Ph 2] 4 ( 7), and Sn[(CH 2) 4Sn{Mn(CO) 5}Ph 2] 4 ( 8) have been prepared by coupling of 3 with the appropriate Grignard or sodium derivatives of the transition metal moieties. The new compounds were characterized by elemental analyses, IR, 1H-, 13C- and 119Sn NMR spectroscopy and MALDI-TOF mass spectrometry.

Synthesis of deramciclane* labeled with tritium in various positions

Abstract[(1R)‐endo]‐(+)‐3‐bromocamphor was dehalogenated with tritium gas to [3‐3H]camphor and via [3‐3H]phenylborneol converted to [3‐3H]deramciclane isolated as the fumarate salt (specific activity 51.8 GBq/mmol). This three step synthesis from [3‐3H]camphor gave an overall yield of 22%.Benzyloxy‐acetic acid methyl ester was reduced with sodium‐borotritide to 2‐benzyloxy‐ethanol‐[1‐3H], and through a four step procedure was converted to 2‐dimethylaminoethyl‐[2‐3H] chloride. The latter was condensed with the sodium derivative of 2‐phenylborneol giving rise to [2‐dimethylamino‐[2‐3H]ethoxy]deramciclane isolated as the fumarate (specific activity 8.177 GBq/mmol). This six step synthesis from [3H]NaBH4 gave an overall yield of 6%. Copyright © 2005 John Wiley &amp; Sons, Ltd.

Titanium Triamidotriamine Compounds: Syntheses, Structures and Redox Properties

AbstractThe preparation of 1,4,7‐{NH(2‐C6H4F)SiMe2}3‐1,4,7‐triazacyclononane (H3N3‐F[9]N3) and 1,4,8‐{N(H)PhSiMe2}3‐1,4,8‐triazacycloundecane (H3N3[11]N3), and their sodium derivatives Na3N3‐F[9]N3(THF)2 and Na3N3[11]N3(THF)2, is described. The reaction of [TiCl3(THF)3] with Na3N3‐F[9]‐N3(THF)2 and Na3N3[11]N3(THF)2 leads to [Ti{N3‐F[9]N3}] and [Ti{N3[11]N3}]. The titanium complexes react readily with I2 to give the TiIV derivatives [Ti{N3‐F[9]N3}]I and [Ti{N3[11]N3}]I. All titanium compounds display distorted trigonal prismatic geometries where the metal is coordinated to the six nitrogen donors. Fluxional processes that convert the conformations of the five‐ and six‐membered metallacycles and the Δ and Λ enantiomers of [Ti{N3[11]N3}]I have been identified in solution. (© Wiley‐VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2005)