The reactions of cyclotriphosphazene with 2-(2-hydroxyethylamino)ethanol. Spectroscopic studies of the derived products

Abstract

The reactions of cyclotriphosphazene (1) with 2-(2-hydroxyethylamino)-ethanol (2) were investigated. 2-(2-hydroxyethylamino)-ethanol (2) is a tri-functional reagent consisting of both aliphatic hydroxyl and the secondary amino groups and its nucleophilic substitution reactions with cylotriphosphazene can lead to different product types; open chain, spiro, ansa, bridged and their mixtures. The reactions with one, two and three equimolar ratios of 2-(2-hydroxyethylamino)-ethanol, in the presence of NaH at 0–10?°C and at room temperature gave the following cyclotriphosphazene derivatives: one mono-spiro, N₃P₃Cl₄[O–(CH₂)₂–NH–(CH₂)₂–O] (3, 1:1, r.t.); its isomer mono-ansa (5, 1:1, r.t.); one dispiro, N₃P₃Cl₂[O–(CH₂)₂–NH–(CH₂)₂–O]₂ (4, 1:1, r.t.); its isomer spiro-ansa (6, 1:2, r.t.); and one single-bridged compound with spiro substituted units, N₃P₃Cl₃[O–(CH₂)₂–NH–(CH₂)₂–O]₃N₃P₃Cl₃ (7, 1:3, at 0–10?°C); as well as single-, N₃P₃Cl₅[O–(CH₂)₂–NH–(CH₂)₂–O]N₃P₃Cl₅ (8, 1:2, r.t.), double-, N₃P₃Cl₄[O–(CH₂)₂–NH–(CH₂)₂–O]₂N₃P₃Cl₄ (9, 1:2, r.t.), and tri-bridged, N₃P₃Cl₃[O–(CH₂)₂–NH–(CH₂)₂–O]₃N₃P₃Cl₃ (10, 1:3, at 0–10?°C) derivatives. Triple-bridged derivative is the major product in this system. The structures of the novel-derived compounds were characterized by TLC-MS, FT-IR, elemental analysis, ¹H, and ³¹P NMR spectral.     

NMR-spektroskopische Untersuchungen an Mercaptophosphazenen. I. Verlauf der Reaktion von Natriumethylmercaptid mit Hexachlorocyclotriphosphazatrien bzw. Octachlorocyclotetraphosphazatetraen

N.M.R. Spectroscopic Investigations of Thiophosphazenes. I. Reactions of Sodium Ethylthiolate with Hexachlorocyclotriphosphazatriene and Octachlorocyclotetraphosphazatetraene By reactions of hexachlorocyclotriphosphazatriene with an excess of sodium ethylthiolate as a suspension in ether all of the possible geminal derivatives N₃P₃Cl_6?n(SEt)_n; n = 1–6, are formed in different quantities. Products from reactions of octachlorocyclotetraphosphazatetraene with sodium ethylthiolate, N₄P₄Cl_8?n(SEt)_n, likewise contain all of the geminally substituted derivatives up to n = 8 with the exception of the derivatives with n = 1 and n = 7. Compounds with n = 3, 4, or 5 exist in two geminal isomers respectively. Nongeminal ethylthiochlorophosphazenes were not found by any reaction. The formed compounds were isolated by chromatographic methods and studied by ³¹P n.m.r. spectroscopy.     

Synthesis and Structural Characterization of Singly,Doubly, and Triply Bridged Derivatives of Hexachlorocyclotriphosphazene with Bis(2-hydroxyethyl) Ether and 2,2-dimethylpropane-1,3-diol

Abstract

The reactions of hexachlorocyclotriphosphazene, N₃P₃Cl₆ (1), with 2,2-dimethylpropane-1,3-diol (2), and bis(2-hydroxyethyl) ether (3) have been previously reported. Although both reactions gave the expected spiro, ansa, and bridged type products, open-chain and triply bridged derivatives from both systems and singly bridged derivatives from 2,2-dimethylpropane-1,3-diol (2) were not isolated, and doubly bridged compounds were only detected in trace amounts in both systems. However, in a subsequent reinvestigation in tetrahydrofuran (THF) solution, the reaction of 1 with the diols 2 and 3 gave the open chain compounds N₃P₃Cl₅[O(CH₂)₂CMe₂OH] (4) and N₃P₃Cl₅[(OCH₂CH₂)₂OH] (5), the singly bridged compound N₃P₃Cl₅[(OCH₂)₂-CMe₂]N₃P₃Cl₅ (6), the doubly bridged compounds N₃P₃Cl₄[(OCH₂)₂CMe₂]₂N₃P₃Cl₄ (8) and N₃P₃Cl₄[(OCH₂CH₂)₂O]₂N₃P₃Cl₄ (9), and the triply bridged compounds N₃P₃Cl₃[(OCH₂)₂-CMe₂]₃N₃P₃Cl₃ (10) and N₃P₃Cl₃[(OCH₂CH₂)₂O]₃N₃P₃Cl₃ (11).

The doubly bridged derivatives were also isolated in better yields relative to earlier reports. The substituted cyclotriphosphazenes have been characterized by elemental analysis, mass spectrometry, as well as by ¹H, ³¹P, and ¹³C NMR spectroscopy. It is found that with variation of the solvent there is a decrease in the product formed by intramolecular reactions (spiro and ansa derivatives) and a concomitant increase in the amount of products formed by intermolecular reactions (singly, doubly, and triply bridged derivatives) of cyclophosphazene.     

Phosphorus-nitrogen compounds: Reinvestigation of the reactions of hexachlorocyclotriphosphazene with 1,4-butane- and 1,6-hexane-diols—NMR studies of the products

Reactions of hexachlorocyclotriphosphazene N₃P₃Cl₆ (1) with 1,4-butane-(2) and 1,6-hexane-diols (3) in (1:1:2, 1:2:4, and 1:3:6) stoichiometries in THF solution at room temperature (r.t.) and under refluxing conditions yield a total of 15 products: two open chain, N₃P₃Cl₅[O(CH₂)_nOH] (n = 4, 6) (4, 5), two mono-spiro, N₃P₃Cl₄[O(CH₂)_nO] (n = 4, 6) (6, 7), two mono-ansa, N₃P₃Cl₄[O(CH₂)_nO] (n = 4,6) (8, 9), two dispiro, N₃P₃Cl₂[O(CH₂)_nO]₂ (n = 4, 6) (10, 11), two spiro-ansa, N₃P₃Cl₂[O(CH₂)_nO]₂ (n = 4, 6) (12, 13), one tri-spiro, N₃P₃[O(CH₂)₄O]₃ (14), two single-bridged, N₃P₃Cl₅[O(CH₂)_nO]N₃P₃Cl₅ (n = 4, 6) (15, 16), one double-bridged, N₃P₃Cl₄[O(CH₂)₆O]₂N₃P₃Cl₄ (17), and one tri-bridged, N₃P₃Cl₃[O(CH₂)₆O]₃N₃P₃Cl₃ (18) derivatives. Their structures have been elucidated by MS, ³¹P, and ¹H NMR spectroscopy. The results obtained, based on the synthesis, characterization, product types, and the relative yields, are compared with those of previous studies on the reactions of 1 with 1,2-ethane-, 1,3-propane-, 1,4-butane-, 1,5-pentane-, and 1,6-hexane-diols.     

Darstellung,Kristallstrukturen und Schwingungsspektren von [Pt(N3)6]2– und [Pt(N3)Cl5]2–, 195Pt‐ und 15N‐NMR‐Spektren von [Pt(N3)nCl6–n]2– und [Pt(15NN2)n(N215N)6–n]2–, n = 0–6

Synthesis, Crystal Structures, and Vibrational Spectra of [Pt(N₃)₆]^2– and [Pt(N₃)Cl₅]^2–, ¹⁹⁵Pt and ¹⁵N NMR Spectra of [Pt(N₃)_nCl_6–n]^2– and [Pt(¹⁵NN₂)_n(N₂¹⁵N)_6–n]^2–, n = 0–6 By ligand exchange of [PtCl₆]^2– with sodium azide mixed complexes of the series [Pt(N₃)_nCl_6–n]^2– and with ¹⁵N‐labelled sodium azide (Na¹⁵NN₂) mixtures of the isotopomeres [Pt(¹⁵NN₂)_n(N₂¹⁵N)_6–n]^2–, n = 0–6 and the pair [Pt(¹⁵NN₂)Cl₅]^2–/[Pt(N₂¹⁵N)Cl₅]^2– are formed. X‐ray structure determinations on single crystals of (Ph₄P)₂[Pt(N₃)₆] ( 1 ) (triclinic, space group P1, a = 10.175(1), b = 10.516(1), c = 12.380(2) Å, α = 87.822(9), β = 73.822(9), γ = 67.987(8)°, Z = 1) and (Ph₄As)₂[Pt(N₃)Cl₅] · HCON(CH₃)₂ ( 2 ) (triclinic, space group P1, a = 10.068(2), b = 11.001(2), c = 23.658(5) Å, α = 101.196(14), β = 93.977(15), γ = 101.484(13)°, Z = 2) have been performed. The bond lengths are Pt–N = 2.088 ( 1 ), 2.105 ( 2 ) and Pt–Cl = 2.318 Å ( 2 ). The approximate linear azido ligands with N^α–N^β–N^γ‐angles = 173.5–174.6° are bonded with Pt–N^α–N^β‐angles = 116.4–121.0°. In the vibrational spectra the PtCl stretching vibrations of (n‐Bu₄N)₂[Pt(N₃)Cl₅] are observed at 318–345, the PtN stretching modes of (n‐Bu₄N)₂[Pt(N₃)₆] at 401–428 and of (n‐Bu₄N)₂[Pt(N₃)Cl₅] at 408–413 cm^–1. The mixtures (n‐Bu₄N)₂[Pt(¹⁵NN₂)_n(N₂¹⁵N)_6–n], n = 0–6 and (n‐Bu₄N)₂[Pt(¹⁵NN₂)Cl₅]/(n‐Bu₄N)₂[Pt(N₂¹⁵N)Cl₅] exhibit ¹⁵N‐isotopic shifts up to 20 cm^–1. Based on the molecular parameters of the X‐ray determinations the vibrational spectra are assigned by normal coordinate analysis. The average valence force constants are f_d(PtCl) = 1.93, f_d(PtN^α) = 2.38 and f_d(N^αN^β, N^βN^γ) = 12.39 mdyn/Å. In the ¹⁹⁵Pt NMR spectrum of [Pt(N₃)_nCl_6–n]^2–, n = 0–6 downfield shifts with the increasing number of azido ligands are observed in the range 4766–5067 ppm. The ¹⁵N NMR spectrum of (n‐Bu₄N)₂[Pt(¹⁵NN₂)_n(N₂¹⁵N)_6–n], n = 0–6 exhibits by ¹⁵N–¹⁹⁵Pt coupling a pseudotriplett at –307.5 ppm. Due to the isotopomeres n = 0–5 for terminal ¹⁵N six well‐resolved signals with distances of 0.03 ppm are observed in the low field region at –201 to –199 ppm.     

Metal derivatives of thiosemicarbazones: crystal and molecular structures of mono- and di-nuclear copper(I) complexes with N1-substituted thiosemicarbazones

The reactions of copper(II) chloride with a series of N¹-substituted thiosemicarbazones, {R¹(H)C²=N³–N²(H)–C¹(=S)–N¹HMe, R¹ = furan, Hftsc-N-Me; thiophene, Httsc-N-Me; phenyl, Hbtsc-N-Me} in 1 : 2 molar ratio yield copper(I) complexes : sulfur-bridged dinuclear complexes, [Cu₂Cl₂(μ-S-Hftsc-N-Me)₂(η¹-S-Hftsc-N-Me)₂] (1), [Cu₂Cl₂(μ-S-Httsc-N-Me)₂(η¹-S-Httsc-N-Me)₂] (2), and a mononuclear complex [CuCl(η¹-S–Hbtsc-N-Me)₂] (3). Complexes 1–3 have been characterized by elemental analysis (C, H, N), spectroscopy (IR, ¹H NMR) and X-ray crystallography. The Cu(μ-S)₂Cu cores in 1 and 2 form parallelograms with unequal bond distances {Cu–S, 2.2831(3), 2.5955(4) Å (1); 2.2641(9), 2.8006(10) Å (2)}. Bond angles at sulfur and copper are, Cu–S–Cu, S–Cu–S, 69.86(11), 110.12(17)° (1); 75.84(3), 104.16(3)° (2), respectively. The Cu ··· Cu separations are 2.806 Å (1) and 3.141 Å (2) with each copper center a distorted tetrahedron (96.67–119.28°). Bond parameters of 3, Cu–S, 2.227(3), 2.224(3) Å, and 118.97–121.11° are different.     

Reactions of cyclochlorotriphosphazatriene with 2-mercaptoethanol. Calorimetric and spectroscopic investigations of the derived products

Abstract

The reactions of hexachlorocyclotriphosphazatriene, N₃P₃Cl₆ (1) with 2-mercaptoethanol, 2-HS-CH₂-CH₂-OH (2), in (1:1, 1:2 and 1:3) mole ratios, in excess of NaH, in THF and diethylether solutions yield a total of 6 novel products: one mono spiro, N₃P₃Cl₄[O-CH₂-CH₂-S] (3); one mono-substituted open chain, N₃P₃Cl₅[S-CH₂-CH₂-OH] (4); one dispiro, N₃P₃Cl₂[O-CH₂-CH₂-S]₂ (5); one tri-substituted open chain, N₃P₃Cl₃[S-CH₂-CH₂-OH]₃ (6); one tris-spiro, N₃P₃[O-CH₂-CH₂-S]₃ (7) and one disubstituted open chain, N₃P₃Cl₄[S-CH₂-CH₂-OH]₂ (8) derivatives. The spiro products (3, 5 and 7) are formed as the major products in this system and all of the synthesized compounds are found to be stable at room temperature. The structures of the derived compounds were elucidated by elemental analysis, TLC-MS, ³¹P and ¹H NMR spectral data. For evaluation of melting behavior of derivatives (6) and (7), thermal transition peaks and their corresponding enthalpies were determined via DSC technique.     

Synthesis,characterization, and transfer hydrogenation of Ru(II)-N-heterocyclic carbene complexes

A new series of ruthenium(II) N-heterocyclic carbene complexes [RuL^1,2,3(p-cymene)Cl₂] (3a–c) (where L is a N-heterocyclic carbene), have been synthesized via transmetalation. The new ruthenium(II)-NHC complexes were applied to transfer hydrogenation of acetophenone derivatives and aldehydes using 2-propanol as a hydrogen source and KOH as a co-catalyst. The results show that the corresponding alcohols could be obtained in good yield with high catalyst activity (up to 100%) under mild conditions. [RuL¹(p-cymene)Cl₂] (3a) is much more active than the other complexes in transfer hydrogenation. Reactions, catalyzed by 3a–c, showed the highest reaction rates and yields of alcohol when the substrates bear more electron-withdrawing substituents. All new compounds were characterized by IR, elemental analysis, LC–MS (ESI), and NMR spectroscopy.     

Zinc(II) complexes of 2-pyridine-derived N (4)- p -tolyl thiosemicarbazones: study of in vitro antibacterial activity

Reaction of N(4)-p-tolyl-2-formylpyridine thiosemicarbazone (H2Fo4pT), N(4)-p-tolyl-2-acetylpyridine thiosemicarbazone (H2Ac4pT), and N(4)-p-tolyl-2-benzoylpyridine thiosemicarbazone (H2Bz4pT) with ZnCl₂ gave [Zn(H2Fo4pT)Cl₂] (1), [Zn(H2Ac4pT)Cl₂] (2), and [Zn(H2Bz4pT)Cl₂] (3). In the first two complexes a tridentate N_py–N–S thiosemicarbazone binds to the zinc while in the latter N–S coordination occurs. Upon coordination the antibacterial activity against Salmonella typhimurium increases in 1 and 3.     

1-(2-Hydroxyethyl)-5-mercapto-1H-tetrazole as ligand in Cu(I) complexes with or without X-ions (X = Cl,Br, I): synthesis,crystal structures and properties

Four Cu(I) complexes with 1-(2-hydroxyethyl)-5-mercapto-1H-tetrazole (Hhmt) as a ligand, [Cu(hmt)]_n (1), [Cu₂Cl(hmt)]_n (2), [Cu₄Br(hmt)₃]_n (3), and [Cu₄I(hmt)₃]_n (4), have been synthesized. In 1–4, hmt adopts a μ₄-η^1?:^? η^1?:^? ηS² coordinate mode to join the adjacent Cu(I) ions, which form different two-dimensional (2-D) structures. In 1, the neighboring four Cu(I) atoms are connected by μ₄-hmt to form a 2-D structure. In 2, the Cu(I) ions are firstly connected with Cl ions to form a 1-D [Cu₄Cl₂] subunit chain, which then have been bridged by hmt to form a 2-D structure. However, the inorganic [Cu₄Br] and [Cu₄I] motifs are respectively connected by hmt to form 2-D structures in isostructural 3 and 4. In addition, the fluorescent properties and the thermal stability properties of 1–4 have been investigated.     

N‐Methylimidazolkomplexe des Berylliums: [Be(Me‐Im)4]I2 und [Be3(μ‐OH)3(Me‐Im)6]Cl3

Tetra(N‐methylimidazole)‐beryllium‐di‐iodide, [Be(Me‐Im)₄]I₂ ( 1 ), was prepared from beryllium powder and iodine in N‐methylimidazole suspension to give yellow single crystal plates, which were characterized by X‐ray diffraction and IR spectroscopy. Compound 1 crystallizes tetragonally in the space group I 2d with four formula units per unit cell. Lattice dimensions at 100(2) K: a = b = 1784.9(1), c = 696.2(1) pm, R₁ = 0.0238. The structure consists of homoleptic dications [Be(Me‐Im)₄]²⁺ with short Be–N distances of 170.3(3) pm and iodide ions with weak interionic C–H ··· I contacts. Experiments to yield crystalline products from reactions of N‐methylimidazole with BeCl₂ and (Ph₄P)₂[Be₂Cl₆], respectively, in dichloromethane solutions were unsuccessful. However, single crystals of [Be₃(μ‐OH)₃(Me‐Im)₆]Cl₃ ( 2 ) were obtained from these solutions in the presence of moisture air. According to X‐ray diffraction studies, two different crystal individuals ( 2a and 2b ) result, depending on the starting materials BeCl₂ and (Ph₄P)₂[Be₂Cl₆], respectively [ 2a : Space group P2₁/n, Z = 4; 2b : Space group P , Z = 2]. As a side‐product from the reaction of N‐methylimidazole with (Ph₄P)₂[Be₂Cl₆] single crystals of (Ph₄P)Cl·CH₂Cl₂ ( 3 ) were identified crystallographically (P2₁/n, Z = 4) which are isotypical with the corresponding known bromide (Ph₄P)Br·CH₂Cl₂.     

Phosphorus-Nitrogen Compounds: The Reactions of Hexachlorocyclotriphosphazatriene with Pentane-1,5-Diol. Nuclear Magnetic Resonance Studies of The Products

Abstract

From the reactions of hexachlorocyclotriphosphazatriene, N₃P₃Cl₆ (1) with pentane-1,5-diol (2) in dichloromethane solution, the following derivatives have been isolated: 2,2-spiro(1′,5′-pentanedioxy)-4,4,6,6-tetrachlorocyclotriphosphazatriene, N₃P₃Cl₄[O(CH₂)₅O] (3); its ansa isomer, 1,3-ansa(1′,5′-pentanedioxy)-1,3,5,5-tetrachlorocyclotriphosphazatriene, (4); bis spiro(1′,5′-pentanedioxy)-6,6-dichlorocyclotriphosphazatriene, N₃P₃Cl₂[O(CH₂)₅O]₂ (5); its spiro-ansa isomer, (1′,5′-pentanedioxy)-1,3-dichlorocyclotriphosphazatriene (6); as well as the bino(1,5-pentanedioxy)-di-(pentachlorocyclotriphosphazatriene), N₃P₃Cl₅ [O(CH₂)₅O]N₃P₃Cl₅ (7), and tri-bino(1,5-pentanedioxy)-di (trichlorocyclotriphosphazatriene), N₃P₃Cl₃[O(CH₂)₅O]₃N₃P₃Cl₃, (8) derivatives. Their structures were established by MS and NMR with the use of ¹H, ¹³C, and ³¹P spectroscopy. Product types and relative yields are compared with those of the previously investigated diol derivatives. The yield of the mono-ansa product (25%) obtained in this system was considerably increased relative to those of the propane-1,3-diol derivative (11.2%) and decreased relative to the 2,2-dimethyl-propane-1,3-diol (36.2%), and bis(2-hydroxyethyl) ether (34.5%) derivatives.     

Syntheses,characterization, and crystal structures of ruthenium(II)/(III) complexes with tridentate salicylaldiminato ligands

Treatment of [Ru(PPh₃)₃Cl₂] with one equivalent of tridentate Schiff base 2-[(2-dimethylamino-ethylimino)-methyl]-phenol (HL) in the presence of triethylamine afforded a ruthenium(III) complex [RuCl₃(κ²-N,N-NH₂CH₂CH₂NMe₂)(PPh₃)] as a result of decomposition of HL. Interaction of HL and one equivalent of [RuHCl(CO)(PPh₃)₃], [Ru(CO)₂Cl₂] or [Ru(tht)₄Cl₂] (tht = tetrahydrothiophene) under different conditions led to isolation of the corresponding ruthenium(II) complexes [RuCl(κ³-N,N,O-L)(CO)(PPh₃)] (2), [RuCl(κ³-N,N,O-L)(CO)₂] (3), and a ruthenium(III) complex [RuCl₂(κ³-N,N,O-L)(tht)] (4), respectively. Molecular structures of 1·CH₂Cl₂, 2·CH₂Cl₂, 3 and 4 have been determined by single-crystal X-ray diffraction.     

Metal derivatives of thiosemicarbazones: crystal structure of [chloro bis(triphenylphosphino) (thiophene-2-carbaldehyde thiosemicarbazone) copper(I)] complex

Reactions of copper(I) halides (X = Cl, Br, I) with thiophene-2-carbaldehyde thiosemicarbazone and triphenylphosphine in 1 : 1 : 2 molar ratio yield tetrahedral mononuclear complexes, [CuX(η¹-S-Httsc)(Ph₃P)₂] (X = Cl, 1; Br, 2; I, 3), characterized by elemental analysis, IR, NMR (¹H, ¹³C, ³¹P), and single crystal X-ray crystallography (1). The unit cell of 1 has two independent distorted tetrahedral molecules (1a and 1b) with different bond parameters. One acetonitrile is entrapped between them. Crystal data: C₈₆H₇₇Cl₂Cu₂N₇P₄S₄ 1: triclinic, P-1, a = 12.8810(9), b = 18.5049(13), c = 18.7430(13) Å, α = 63.7130(10), β = 89.0960(10), γ = 85.5010(10)°, V = 3992.4(5) ų, Z = 2, R _(int) = 0.0314. Bond parameters: 1a, Cu(1A)–Cl(1A), 2.3803(5); Cu(1A)–S(1A), 2.3822(5); Cu(1A)–P(1A), 2.2498(5) Å; P(1A)–Cu(1A)–P(2A), 124.294(19)°; 1b, Cu(1B)–Cl(1B), 2.3975(5); Cu(1B)–S(1B), 2.3756(5); Cu(1B)–P(1B), 2.2777(5) Å; P(1B)–Cu(1B)–P(2B), 127.156(19)°.     

The reactions of non-gem-hexanedioxytetrachlorocyclotriphosphazene with 2-(2-hydroxyethyl)thiophene,benzyl alcohol and 1,1,3,3-tetramethylguanidine. Spectroscopic studies of the derived products

Abstract

Reactions of non-gem-hexanedioxytetrachlorocyclotriphosphazene (1) with monofunctional nucleophilic reagents, 2-(2-hydroxyethyl)thiophene (2), benzyl alcohol (3) and 1,1,3,3-tetramethylguanidine (4) were investigated. The reactions, using an excess of NaH, in THF solutions, under refluxing conditions and with 1:2?mole ratios allow the synthesis of the following novel cyclotriphosphazene derivatives: 2,4-dichloro-2,4-(hexane-1,6-dioxy)-6,6-[2-(2-ethoxy)hiophene]-cyclotriphosphazatriene, N₃P₃Cl₂[O(CH₂)₆O-(C₆H₈OS)₂] (5); 2,4-(hexane-1,6-dioxy)-2,4,6,6-[2-(2-ethoxy) thiophene]-cyclotriphosphazatriene, N₃P₃[O(CH₂)₆O-(C₆H₈OS)₄] (6); 2,4-dichloro-2,4-(hexane-1,6-dioxy)-6,6-(methoxybenzene)-cyclotriphosphazatriene, N₃P₃Cl₂[O(CH₂)₆O-(C₆H₅CH₂O)₂] (7); 2,4-(hexane-1,6-dioxy)-2,4,6,6-(methoxybenzene)-cyclotriphosphazatriene, N₃P₃[O(CH₂)₆O-(C₆H₅CH₂O)₄] (8); and 2,4-dichloro-2,4-(hexane-1,6-dioxy)-6,6-(1,1,3,3-tetramethyguanidine)-cyclotriphosphazatriene, N₃P₃Cl₂[O(CH₂)₆O-HN-CN₂(CH₃)₄] (9). The structures of the synthesized compounds (5–9) have been characterized by elemental analysis, TLC-MS, ¹H, ¹³C and ³¹P {+¹H} and {?¹H} NMR spectral data.     

Synthesis and structural characterization of geminal and non-geminal 1,1,3,3-tetramethylguanidine substituted derivatives of cyclotriphosphazene: Thermal and spectroscopic investigations of the products

Abstract

The reactions of hexachlorocyclotriphosphazene, N₃P₃Cl₆ (1) with 1,1,3,3-tetramethyl-guanidine (2) in (1:1:2, 1:2:4 and 1:3:6) stoichiometries in THF and dichloromethane solutions under reflux yield a total of 4 novel products: three non-geminal derivatives, N₃P₃Cl₄[NCN₂(CH₃)₄]₂ (3), N₃P₃Cl₃[NCN₂(CH₃)₄]₃ (4) and N₃P₃Cl₂[NCN₂(CH₃)₄]₄ (5); and one hexa-substituted product, N₃P₃[NCN₂(CH₃)₄]₆ (6). The structures of 3-6 have been determined mainly by elemental analysis, MS, ³¹P and ¹H NMR spectral data. Furthermore, thermal characteristics of the synthesized compounds 4 and 6 were evaluated using Differential Scanning Calorimetric (DSC) measurements. NMR spectroscopic data, product types and relative yields are compared with those of the previously investigated derivatives of N₃P₃Cl₆ (1) with mono and difunctional reagents.     

Copper(I) and copper(II) complexes with pyrazine-containing pyridylalkylamide ligands N-(pyridin-2-ylmethyl)pyrazine-2-carboxamide and N-(2-(pyridin-2-yl)ethyl)pyrazine-2-carboxamide

Four copper(II) complexes and one copper(I) complex with pyridine-containing pyridylalkylamide ligands N-(pyridin-2-ylmethyl)pyrazine-2-carboxamide (HL^pz) and N-(2-(pyridin-2-yl)ethyl)pyrazine-2-carboxamide (HL^pz?) were synthesized and characterized. The X-ray crystal structures of [Cu₂(L^pz)₂(4,4?-bipy)(OTf)₂] (1, OTf?=?trifluoromethanesulfonate, 4,4?-bipy?=?4,4?-bipyridine) and [Cu(L^pz)(py)₂]OTf·H₂O (2, py?=?pyridine) revealed binuclear and mononuclear molecular species, respectively, while [Cu(L^pz)(μ₂-1,1-N₃)]_n (3), [Cu(L^pz?)(μ₂-1,3-N₃)]_n (4), and [Cu(HL^pz)Cl]_n (5) are coordination polymer 1-D chains in the solid state.     

C–H-Aktivierung: Synthese und Eigenschaften von Acetonato(C)acidophthalocyaninato(2–)metallaten(III) von Rhodium und Iridium; Kristallstruktur von Tetra(n-butyl)ammoniumacetonato(C)-azidophthalocyaninato(2–)iridat(III)

C–H-Activation: Syntheses and Properties of Acetonato( C )-acidophthalocyaninato(2–)metallates(III) of Rhodium and Iridium; Crystal Structure of Tetra(n-butyl)ammonium Acetonato( C )azidophthalocyaninato(2–)iridate(III) Phthalocyaninato(2–)metallate(I) of rhodium and iridium reacts with carbonyl substrates like acetone or acetylacetone and halides or pseudohalides forming acetonato(C)- or acetylacetonato(C)acidophthalocyaninato(2–)metallates(III), that are isolated as tetra(n-butyl)ammonium complex salts (ⁿBu₄N)[M(R)(X)pc^2–] (M = Rh, Ir; R = aC, acaC; X = Cl, I, N₃, SCN/NCS). (ⁿBu₄N)[Ir(aC)(N₃)pc^2–] · 0,25(C₂H₅)₂O · 0,5 CH₂Cl₂ crystallizes in the triclinic space group P1 with cell parameters a = 16.267(8) Å, b = 17.938(3) Å, c = 18.335(4) Å, α = 74.77(2)°, β = 73.73(3)°, γ = 84.25(3)°, V = 4954(3) ų, Z = 4. There are two crystallographically independent anions, differing by the orientation of the azido ligand either towards an isoindole group or a N_aza bridge of the phthalocyaninate, while the σ-C bonded acetonate is always oriented towards an isoindole group (gauche and ecliptical configuration). The Ir–C distances are 2.12(1) and 2.14(1) Å. Due to the trans influence of the acetonate-C atom the Ir-azide-N distances of 2.22(1)/2.24(1) Å are longer than expected. The electrochemical properties and the optical, vibrational, and ¹H-NMR spectra are discussed.     

Derivatives of cis-NPCl2(NSOCl)2 and (NPCl2)2NSOCl. Part XIV—synthesis and nuclear magnetic resonance study of dimethylamino derivatives of NPCl2(NSOPh)2 and (NPCl2)2NSOPh

The compounds trans-NPCl_2?n(NMe₂)_n(NSOPh)₂(n=0-2iNPCl_2?n NMe₂)_n (NSOPh)₂ (n=0-2) and N₂P₂Cl_4?nl_4?n(NMe₂)_nNSOP₂P₂Cl_4?n(NMe₂)_nNSOPh(n=0-4), were prepared from their chloro-precursors. The substitution follows a completely non-geminal pathway, and all possible isomers are formed. The observed relative abundance of these isomers shows that the phenyl group exhibits a strong directing effect on the incoming amine. The ¹H, ³¹P and ¹³C NMR spectra of the most abundant isomers are reported. ²J(CP) couplings within the PNMe₂ grouping are affected by the number of substituents at the phosphorus atom. Almost linear relationships exist between the degree of substitution and the chemical shift of C-1 and C-4 of the phenyl groups. The effect of substitution on the ¹³C chemical shifts of these groups is ascribed to inductive effects.     

Syntheses of phenoxo-bridged Zn(II) and metallamacrocyclic Hg(II) complexes of organochalcogen (Se,Te) substituted Schiff-bases: structure and DNA-binding studies of Zn(II) complexes

The coordination of organochalcogen (especially Se and Te) substituted Schiff-bases L¹H, L²H, L³H, and L⁴H toward Zn(II) and Hg(II) has been studied. Reactions of these ligands with ZnCl₂ in 1?:?1 molar ratio gave binuclear complexes [{2-[PhX(CH₂) _n N?=?C(Ph)]-6-[PhCO]-4-MeC₆H₂O}₂Zn₂Cl₂] (where X?=?Se, n?=?2 (1); X?=?Se, n?=?3 (2); X?=?Te, n?=?2 (3); and X?=?Te, n?=?3 (4)) with partial hydrolytic cleavage of proligands. In these complexes, two partially hydrolyzed ligand fragments coordinate tridentate (NOO) with two Zn's. Reaction of HgBr₂ with L¹H and L²H in 1?:?1 molar ratio gave monometallic complexes [C₆H₂(4-Me)(OH)[2,6-{C(Ph)?=?N(CH₂) _n Se(Ph)}₂HgBr₂]] (n?=?2 (5) or 3 (6)) and under similar conditions with L³H and L⁴H gave bimetallic complexes [C₆H₂(4-Me)(OH)[2,6-{C(Ph)?=?N(CH₂) _n Te(Ph)}₂Hg₂Br₄]] (n?=?2?(7) or 3 (8)) in which the ligands coordinate with metal through selenium or tellurium, leaving the imino nitrogen and phenolic oxygen uncoordinated. The proligands L¹H, L²H give 14- or 16-membered metallamacrocycles through Se–Hg–Se linkages and L³H, L⁴H give 16- or 18-membered metallamacrocycles through Te–Hg–Br–Hg–Te linkages. All the complexes were characterized by elemental analyses, ESIMS, FTIR, multinuclear NMR, UV-Vis, and conductance measurements. The redox properties of the complexes were investigated by cyclic voltammetry (CV). Complexes 1–4 exhibited ligand-centered irreversible oxidation processes. Complexes 5 and 6 showed metal-centered quasi-reversible single electron transfer, whereas dinuclear complexes 7 and 8 displayed two quasi-reversible, one-electron transfer steps. A single-crystal X-ray structure determination of 1 showed that the coordination unit is centrosymmetric with Zn(II) in square-pyramidal coordination geometry and the two square pyramids sharing an edge. The Zn?···?Zn separation is 3.232?Å. The DNA-binding properties of 1 and 3 with calf thymus DNA were explored by a spectrophotometric method and CV.