Unusual products in the reactions of hexachlorocyclotriphosphazatriene with sodium aryloxides

Reactions of hexachlorocyclotriphosphazatriene, N₃P₃Cl₆ 1 , with sodium aryloxides have been studied. Compound 1 was found to react by the nucleophilic substitution pathway to yield monocyclophosphazenes [N₃P₃Cl₆(OC₆H₂Bu¹₃-2,4,6) 5 and N₃P₃Cl₄(OC₆H₂Me-4-Bu¹₂-2,6)₂ 6 ] and bi(cyclophosphazenes) ([Cl₅N₃P₃-P₃N₃Cl₄(OC₆H₃Bu¹₂-2,6)] 7 and [N₃P₃(OC₆H₃Bu¹₂-2,6)₅]₂ 8 ). The unusual bi(cyclophosphazenes) 7 and 8 are the first examples of two cyclotriphosphazene rings linked by a P(SINGLE BOND)P bond [2.193 (2) Å], which have been obtained by reacting 1 with ArONa. The structures of compounds 5–8 are ascertained by elemental analyses, ¹H-, ³¹P-¹³C-NMR, IR, and MS spectra. The molecular structure of monocyclic-phosphazene 5 was determined by X-ray diffraction techniques for further structural assignment. It crystallizes in the monoclinic space group P2₁/m with a = 6.144(2), b = 17.079(9), c = 13.181(9) Å, β = 92.79(7), and Z = 2, R = 0.074. Compound 5 is on a crystallographic mirror plane, and there is only a half molecule in the asymmetric unit. © 1996 John Wiley & Sons, Inc.     

Vibrational spectra of bromo- and chloro-fluorotriphosphazenes

Infrared and Raman spectra have been obtained for the nongeminally substituted mixed halides N₃P₃Br_nF_6-n, and N₃P₃Cl_nF_6-n using the pure cis or trans isomers for n = 2 and 3, but isomer mixtures when n = 4. The spectra are compared with those for the corresponding geminally substituted compounds and by comparison with data for the homogeneously substituted hexahalides the bands between 1300 cm⁻¹ and 150 cm⁻¹ are tentatively assigned.     

The role played by the amino and carboxyl groups in the formation of the geometric and electronic structure of phenoxy substituted cyclophosphazenes

A quantum-topological analysis of the electron density calculated by the density functional theory method in the B3LYP/6-31G(d,p) approximation was performed to determine and quantitatively characterize four types of noncovalent interactions in mono-and disubstituted 4-aminophenoxy-and 4-carboxyphenoxycyclotriphosphazenes P₃N₃Cl₅OC₆H₄NH₂, P₃N₃Cl₄(OC₆H₄NH₂)₂, P₃N₃Cl₅OC₆H₄COOH, and P₃N₃Cl₄(OC₆H₄COOH)₂. These are C-H…N hydrogen bonds between a nitrogen atom of the phosphazene ring and a hydrogen atom of the benzene ring, C-H…C interactions between a carbon atom of one phenoxy group and a hydrogen atom of the other such group (C-H…π interactions), N-H…N interactions between nitrogen and hydrogen atoms of neighboring amino groups, and C-O…C interactions between oxygen atoms of neighboring carboxyl groups. This system of noncovalent bonding interactions determines the mutual orientation of oxyphenyl fragments. The total energy of interatomic contacts estimated from the local potential energy of electrons at the corresponding critical bond points is larger for the amino than for the carboxyl group. It follows that the amino group has the strongest effect on the mutual orientation of oxyphenyl fragments. The effect of the carboxyl group is weaker.     

Transition metal containing dendrimers based on cyclophosphazene units

The series of complexes [N₃P₃(OC₆H₅)₅OC₆H₄CH₂CN·MCl_n]PF₆, N₃P₃(OC₆H₄CH₂CN)₆·(MCl_n)₆](PF₆)₆, [N₃P₃(OC₆H₅)₅OC₆H₄CH₂CN·MCl_n−1]Cl and [N₃P₃(OC₆H₄CH₂CN)₆·(MCl_n−1)₆]Cl₆, MCl_n=MnCl₂, FeCl₃, CoCl₂, NiCl₂, CuCl₂ have been synthesized by reaction of the corresponding cyclophosphazene ligands: N₃P₃(OC₆H₅)₅OC₆H₄CH₂CN (L₁) and N₃P₃(OC₆H₄CH₂CN)₆ (L₂) with the respective salts MCl_n in CH₃OH as solvent and in presence or absence of NH₄PF₆. The new compounds were characterized by elemental analysis and IR, UV–Vis and EPR spectroscopy as well as electrochemical methods. The reaction of CuCl₂ with the ligand L₁ affords the copper (I) complex. [N₃P₃(OC₆H₅)₅OC₆H₄CH₂CN·Cu]PF₆ instead the expected Cu(II) complex, which was characterized by multinuclear NMR. For comparison, the complex [N₃P₃(OC₆H₅)₅OC₆H₄CH₂CN·ZnCl]PF₆ was also prepared. The hexametalladendrimers of iron exhibits a six-electron reduction while that the correspondent monometalladendrimers exhibit a single one-electron reduction. Upon coordination νCN increase in a similar way to crystal field effects dependence with the metal.     

New organotin(IV) complexes with a potentially multi-site ligand based on the cyclotriphosphazene platform: Synthesis and spectral studies

A functionalized cyclotriphosphazene with four pyrazolyl substituents, N₃P₃(MeNC₂H₄O)(dmp)₄ where dmp = 3,5-dimethylpyrazole, has been synthesized and characterized. The reaction of this potentially multi-site coordinating cyclotriphosphazene with diorganotin(IV) dichlorides, SnR₂Cl₂ (R = Ph, Me), leads to dinuclear [(SnPh₂Cl₂)₂{N₃P₃(MeNC₂H₄O)(dmp)₄}] (1) and mononuclear [(SnMe₂Cl₂){N₃P₃(MeNC₂H₄O)(dmp)₄}] (2) complexes. These new compounds were characterized by elemental analysis and IR, ¹H, ³¹P and ¹¹⁹Sn NMR spectroscopy. On the basis of these data, in the complex 1 pyrazolylcyclotriphosphazene acts as a bis-bidentate ligand and coordinates to two SnPh₂Cl₂ molecules via two geminal pyrazolyl nitrogen atoms. As for complex 2, coordination to one SnMe2Cl2 molecule occurs through two nongeminally substituted pyrazolyl nitrogens. The ₁₁₉Sn NMR data are consistent with the increasing of coordination number of tin(IV) in solution.     

Reductive elimination reaction of rhenium complexes trans-(η-C5Me5)Re(CO)2(chloroaryl)Cl

Thermal reaction of the chloroaryl-chloride complexes trans-(η⁵-C₅Me₅)Re(CO)₂(Ar^Cl)Cl (Ar^Cl = 3-ClC₆H₄, 3-ClC₆H₃(4-Me) and 3,5-Cl₂C₆H₃) in acetonitrile did not interconvert to the cis isomer, instead the complex ReCl(CO)₂(NCMe)₃ and the corresponding 5-Ar^Cl-1,2,3,4,5-pentamethylcyclopentadiene were formed. Similar reductive elimination products were obtained when the starting rhenium complexes were reacted with trimethylphosphite in toluene.     

Optimized synthesis of selected 4-oxybenzaldehyde and 2,2-dioxybiphenyl cyclotriphosphazene derivatives

Abstract

Selected 4-oxybenzaldehyde and 2,2-dioxybiphenyl cyclotriphosphazene derivatives were synthesized via substitution reactions through tailored control. The reactions of cyclotriphosphazene with 4-oxybenzaldehyde and 2,2-dioxybiphenyl gave the following synthesized derivatives: one mono-substituted open-chain compound, N₃P₃Cl₅(O₂C₇H₅) (1, 69%); mono spiro, N₃P₃Cl₄(O₂C1₂H₈) (2, 91.1%); non-gem tri-substituted, N₃P₃Cl₃ (O₆C₂₁H₁₅) (3, 17%); dispiro, N₃P₃Cl₂(O₄C₂₄H₁₆) (4, 92.3%); penta-substituted, N₃P₃Cl(O₁₀C₃₅H₂₅) (5, 92%);hexa-substituted, N₃P₃(O₁₂C₄₂H₃₀). Most of these derivatives (1–6) are obtained with good yield (up to 97%), This work provides a simple and available approach to obtain versatile cyclotriphosphazene derivatives, which is expected to further promote the use of HCCP as phosphorus platform for the construction of multi-functional materials.     

trans‐Di­chloro­tetrakis(4‐methylpyrimidine‐N1)­ruthenium(II)

The title compound, trans‐[Ru^IICl₂(N¹‐mepym)₄] (mepym is 4‐methylpyrimidine, C₅H₆N₂), obtained from the reaction of trans,cis,cis‐[Ru^IICl₂(N¹‐mepym)₂(SbPh₃)₂] (Ph is phenyl) with excess mepym in ethanol, has fourfold crystallographic symmetry and has the four pyrimidine bases coordinated through N¹ and arranged in a propeller‐like orientation. The Ru—N and Ru—Cl bond distances are 2.082 (2) and 2.400 (4) Å, respectively. The methyl group, and the N³ and Cl atoms are involved in intermolecular C—H?N and C—­H?Cl hydrogen‐bond interactions.     

The investigation of stereogenic properties of cyclotriphosphazene derivatives with two different chiral centres

Hexachlorocyclotriphosphazene N₃P₃Cl₆ and gem-disubstituted cyclotriphosphazene derivatives N₃P₃Cl₄X₂ (X = Ph, PhS, PhNH) were reacted with N-methyl-1,3-propanediamine and 3-amino-1-propanol to give compounds (9a-12a, 9b-12b) which exist as cis and trans geometric isomers and are two different racemic isomers, respectively to describe the stereogenic properties of a series of chiral cyclotriphosphazene compounds with two different centres of chirality. The geometric isomers were separated by column chromatography on silica gel and analysed by elemental analysis, mass spectrometry, and ³¹P and ¹H NMR spectroscopies, and also the geometric forms (cis or trans) of 9b, 10a, 11a, 11b and 12a have been determined by the X-ray crystallography. The enantiomers of all racemic compounds have been analysed by the changes in ³¹P NMR spectra on addition of a Chiral Solvating Agent (CSA), (R)-(+)-2,2,2-trifluoro-1-(9′-anthryl)ethanol. On the other hand, the racemic forms of chiral cyclotriphosphazene derivatives have been confirmed by contribution of chiral HPLC methods which have been developed for this study.     

Synthesis,Crystal Structure and Characterization of Hexakis[2‐methoxy‐4‐formylphenoxy]cyclotriphosphazene

The new cyclotriphosphazene derivative N₃P₃(OC₆H₃OCH₃COH)₆ ( 1 ) was synthesized from hexachlorocyclotriphosphazene, N₃P₃Cl₆, and 4‐hydroxy‐3‐methoxybenzaldehyde in acetonitrile in the presence of K₂CO₃. The structure of 1 was verified by means of elemental analysis, IR, ¹H NMR, ¹³C NMR, ³¹P NMR spectra, thermal analysis and X‐ray diffraction.     

Molybdänhalogenidcluster mit sechs terminalen Alkoholatliganden: (C18H36N2O6Na)2[Mo6Cl8(OCH3)6] · 6CH3OH und (C18H36N2O6Na2)2[Mo6Cl8(OC6H5)6]

Molybdenum(II) Halide Clusters with six Alcoholate Ligands: (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OCH₃)₆] · 6CH₃OH and (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OC₆H₅)₆] . The reaction of Na₂[Mo₆Cl₈(OCH₃)₆] and 2,2,2-crypt yields (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OCH₃)₆] · 6 CH₃OH ( 1 ), which is converted to (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OC₆H₅)₆] ( 2 ) by metathesis with phenol. According to single crystal structure determinations ( 1 : P3 1c, a=14.613(3) Å, c=21.036(8) Å; 2 : P3 1c, a=15.624(1) Å, c=19.671(2) Å) the compounds contain anionic clusters [Mo₆Cl₈ⁱ(OR^a)₆]^2? ( 1 : d(Mo—Mo) 2.608(1) Å to 2.611(1) Å, d(Mo—Cl) 2.489(1) Å to 2.503(1) Å, d(Mo—O) 2.046(4) Å; 2 : d(Mo—Mo) 2.602(3) Å to 2.608(3) Å, d(Mo—Cl) 2.471(5) Å to 2.4992(5) Å, d(Mo—O) 2.091(14) Å). Electronic interactions of the halide cluster and the phenolate ligands in [Mo₆Cl₈(OC₆H₅)₆]^2? is investigated by means of UV/VIS spectroscopy and EHMO calculations.     

The reaction of hexachlorocyclotriphosphazatriene with P-aminophenol

The reaction of hexachlorocyclotriphosphazatriene (1) with p-aminophenol (2) produced two new products: the open chain compound N₃P₃Cl₅(NHC₆H₄OH) (3), and the bridged compound N₃P₃Cl₅(NHC₆H₄O)N₃P₃Cl₅(4). The compounds 3 and 4 were separated and characterized by elemental analysis, massspectrometry and NMR spectroscopy. The molecular structures of compounds 3 and 4 were determined by X-ray crystallography. Compound 3 is the first example of cyclotriphosphazene including (p-hydroxyphenyl) amino group and compound 4 was the first example of the N-substituted p-aminophenoxy group with cyclotriphosphazene.     

Neue Spiroverbindungen aus Cyclophosphazenen und Cyclodi[phosphadiazan]en

New Spiro Compounds from Cyclophosphazenes and Cyclodi[phosphadiazanes] Chlorocyclophosphazenes (Cl₂P = N)₃ and (Cl₂p = N)₄ react with dihydrazidophosphoric acid derivatives in THF in the presence of triethylamine to give the spirocyclic compounds Cl₄N₃P₃(NHN(CH₃))₂P(S)OC₆H₅, Cl₆N₄P₄(NHNH)₂P(S)OC₆H₅. Constitutions have been confirmed by MS, NMR, IR and elemental analysis.     

Preparation and properties of dinitrogen complexes of molybdenum and tungsten with trimethylphosphine as coligand : III. Synthesis and properties of cis-[W(N2)2(PMe3)4], trans-[W(C2H4)2(PMe3)4] and [M(N2)(PMe3)5] (M = Mo,W). The crystal and molecular structure of [Mo(N2)(PMe3)5]

The reduction of [WCl₄(PMe₃)₃] with dispersed sodium, under dinitrogen, gives cis-[W(N₂)₂(PMe₃)₄], while under ethylene trans-[W(C₂H₄)₂(PMe₃)₄] is obtained. The ethylene complex can also be prepared by displacement of the dinitrogen molecules in cis-[W(N₂)₂(PMe₃)₄] by ethylene at room temperature and pressure. Interaction of cis-[M(N₂)₂(PMe₃)₄] complexes (M = Mo, W), with PMe₃, under helium or argon, yields [M(N₂)(PMe₃)₅]. The molybdenum complex crystallizes in the orthorhombic space group Pnma, with a 22.063(6), b 12.106(4), c 9.745(4) Å. The Mo—P distance trans to the dinitrogen ligand (2.483(7) Å) is slightly longer than the average of the other four Mo—P bonds (2.460(5) Å).     

Syntheses,Molecular Structures,and Complex Formation of Geminal Di(2-pyridylmethylamino)-substituted Cyclotriphosphazenes

N₃P₃Cl₆ reacts with 2-(aminomethyl)pyridine under formation of the stable geminal difunctionalized compound gem-N₃P₃Cl₄(NHCH₂(C₅H₄N)-2)₂ 1 . The chlorine atoms can be substituted by reacting 1 with sodium phenoxide to yield gem-N₃P₃(OC₆H₅)₄(NHCH₂(C₅H₄N)-2)₂ 2 . A vicinal di(pyridylmethylamino)-substituted compound, vic-N₃P₃(OC₆H₅)₄(NHCH₂(C₅H₄N)-2)₂ 3 can be obtained from the reaction of vic-N₃P₃(OC₆H₅)₄Cl₂ with 2-(aminomethyl)pyridine. Decomposition to [Cu(NH₂CH₂(C₅H₄N)-2)₂(NO₃)₂] 4 occurs when 1 is exposed to copper(II) nitrate · H₂O. By contrast, 2 forms the stable copper complex [Cu(NO₃)₂ · ( 2 )] 2 a in which the copper atom is bonded to three nitrogen atoms of the new chelating ligand and three oxygen atoms of the unsymmetrically coordinated nitrate groups. The structures of 1 , 2 , and 2 a were determined by X-ray crystallography.     

Organoimido complexes of tungsten and rhenium: Oxo-imido and bis-imido complexes of tungsten(VI), and phenylimido complexes of rhenium(VI) and (V). The X-ray crystal structures of [W(NCMe3)(NPh)Cl2(bipy)] and [Re(NPh)Cl3(NH2CMe3)2]

Reaction of Me₃CNH₂ or Me₃SiNHCMe₃ with WOCl₄ gives a mixture containing [W(O)(NCMe₃)Cl₂(NH₂CMe₃)]_x which on further reaction with 2,2′-bipyridyl (bipy) gives [W(NCMe₃)₂Cl₂(bipy)] and insoluble oxo complexes. Reaction of WOCl₄ with p-MeC₆H₄N(SiMe₃)₂ and then bipy gives [W(NC₆H₄Me-p)₂Cl₂(bipy)] and [W(O)(NC₆H₄Me-p)Cl₂(bipy)]; [W(NPh)Cl₄]₂ reacts with p-MeC₆H₄N(SiMe₃)₂ and then bipy to give [W(NPh)(NC₆H₄Me-p)Cl₂(bipy)]. [W(NCMe₃)(μ-NPh)Cl₂(NH₂CMe₃)]₂ and bipy give [W(NCMe₃)(NPh)Cl₂(bipy)] (6). ReOCl₄ reacts with PhNCO to give [Re(NPh)Cl₄]_x which in tetrahydrofuran (THF) or MeCN give the adducts [Re(NPh)Cl₄(THF)] and [Re(NPh)Cl₄(MeCN)]. [Re(NPh)Cl₄]_x reacts with Me₄NCl to give [Me₄N][Re(NPh)Cl₅], with PPh₃ to give [Re(NPh)Cl₃(PPh₃)₂] and with Me₃ SiNHCMe₃ gives [Re(NPh)Cl₃(NH₂CMe₃)₂] (12). The complexes were characterized by elemental analysis, IR, ¹H and ¹³C NMR spectroscopy. The structures of [W(NCMe₃)(NPh)Cl₂(bipy)] (6) and [Re(NPh)Cl₃(NH₂CMe₃)₂] (12) were determined by single-crystal X-ray diffraction methods. Crystals of (6) are orthorhombic, space group P2₁2₁2₁, with a = 8.879(3) Å, b = 13.036(3) Å, c = 18.837(4) Å; crystals of (12) are orthorhombic, space group Pbcn with a = 14.140(1) Å, b = 11.806(1), Å, c = 11.936(3) Å. Both structures were solved by Patterson and Fourier methods and refined to R values of 0.053 for the 2138 observed data for (6) and 0.035 for the 1108 observed data for (12). In complex (6) the tungsten atom is in a distorted octahedral environment comprising cis-t-butylimido and phenylimido groups, trans chlorides and bidentate bipy. The bipy nitrogens lie trans to the imid o functions. Observed distances are: WN_phenylimido 1.774(8) Å, WN_t-butylimido 1.754(10) Å, WCl 2.412(3) and 2.390(3) Å and WN_bipy 2.312(10) Å and 2.333(9) Å. Interaction between the t-butylimido methyl groups and bipy is relieved by lengthening of one WN_bipy bond. In complex (12) the rhenium atom is in a distorted octahedral environment comprising three chloride ligands, two trans-t-butylamine ligands and a phenylimido ligand. Observed distances are: ReN_phenylimido 1.709(11) Å, ReN_t-butylamine 2.187(7) Å, and ReCl 2.404(2) and 2.411(5) Å. The complex attains an 18-electron count without π-bonding from the chloro ligands.     

Aminobis(phenolate)s of imidomolybdenum(VI) and -tungsten(VI)

The reactions of trans-[MoO(ONO^Me)Cl₂] 1 (ONO^Me = methylamino-N,N-bis(2-methylene-4,6-dimethylphenolate) dianion) and trans-[MoO(ONO^tBu)Cl₂] 2 (ONO^tBu = methylamino-N,N-bis(2-methylene-4-methyl-6-tert-butylphenolate) dianion) with PhNCO afforded new imido molybdenum complexes trans-[Mo(NPh)(ONO^Me)Cl₂] 3 and trans-[Mo(NPh)(ONO^tBu)Cl₂] 4, respectively. As analogous oxotungsten starting materials did not show similar reactivity, corresponding imido tungsten complexes were prepared by the reaction between [W(NPh)Cl₄] with aminobis(phenol)s. These reactions yielded cis- and trans-isomers of dichloro complexes [W(NPh)(ONO^Me)Cl₂] 5 and [W(NPh)(ONO^tBu)Cl₂] 6, respectively. The molecular structures of 4, cis-6 and trans-6 were verified by X-ray crystallography. Organosubstituted imido tungsten(VI) complex cis-[W(NPh)(ONO^tBu)Me₂] 7 was prepared by the transmetallation reaction of 6 (either cis or trans isomer) with methyl magnesium iodide.     

Synthese und Kristallstrukturen von Quecksilber(II)-iodid-Komplexen mit 3- und 4-pyridylmethylamino- sowie 4-pyridylmethoxy-substituierten Cyclophosphazen-Liganden

Synthesis and Crystal Structures of Mercury(II) Iodide Complexes with 3- and 4-Pyridylmethylamino- and 4-Pyridylmethoxy Substituted Cyclophosphazene Ligands Multifunctional cyclophosphazene ligands with 2-, 3-, and 4-pyridylalkylamino- or 4-pyridylmethoxy groups, N₃P₃(OC₆H₅)₅(NHCH₂(C₅H₄N-2)) ( 1 ), N₃P₃(OC₆H₅)₅ · (NHCH₂(C₅H₄N-3)) ( 2 ), N₃P₃(OC₆H₅)₅(NHCH₂(C₅H₄N-4)) ( 3 ) and N₃P₃(OC₆H₅)₅(OCH₂(C₅H₄N-4)) ( 4 ) are accessible through reactions of monochlorpentaphenoxycyclotriphosphaza-1,3,5-trien with aminomethylpyridine or pyridyl methanolate. 1 does not react with mercury(II) iodide whereas 2–4 yield the metal complexes 2 a , 3 a , and 4 a by interactions of the pyridyl nitrogen atoms. The X-ray single crystal structure analyses of these compounds shows that 2 a and 4 a are dimers, whereas 3 a is a HgI₂ polymer with syndiotacticaly arranged ligands.     

The preparation of cis- and trans-[PtH(C6Cl5)(PEt3)2 and a study of the “hydride-donor capacity” of the complexes trans- [PtH(C6X5(PEt3)2] (X = F and Cl)

The preparations of cis- and trans-[PtH(C₆Cl₅)(PEt₃)₂] by thermal decomposition of cis- and trans-[Pt(OCHO)(C₆Cl₅)(PEt₃)₂], respectively, are reported. Also described are cis- and trans-[Pt(SnCl₃)(C₆Cl₅)(PEt₃)₂], obtained by treating SnCl₂ with cis- and trans-[PtCl(C₆,Cl₅)(PEt₃)₂], respectively. It is shown that while trans- [PtH(C₆Cl₅)(PEt₃)₂] does not form hydride-bridged complexes in the presence of trans-(PtH(MeOH)(PEt₃)₂]⁺, the corresponding complex trans-[PtH(C₆)(PEt₃)₂] reacts with the same solvento complex, in methanol, giving labile [(PEt₃)₂HPt(-μH)Pt(C₆F₅)(PEt₃)₂]⁺.     

Organometallic formate complexes of platinum(II)

The compounds trans-[Pt(OCHO)R(PPh₃)₂] (R = C₆Cl₅; 2,3,4,6-C₆HCl₄; 2,3,4,5-C₆HCl₄; 2,5-C₆H₃Cl₂) have been prepared by treatment of [PtIR(PPh₃)₂] with AgClO₄ followed by reaction with NaOCHO in methanol. The cis isomers have been obtained by the direct reaction of HCO₂H with compounds containing PtHg bonds. For these and the analogous compounds containing C₆F₅ ligands, the dependence of J(³¹P¹⁹⁵Pt) on R has been studied, and the effects of cis-R shown to be in the opposite direction from those of trans-R ligands.