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Three cationic nonporous copper(I) coordination polymers containing bis-pyrazolyl flexible ligands have been prepared and characterized, namely, {[Cu(μ-bdb)1.5](PF6)}n (1), {[Cu(μ-bpb)2](PF6)}n (2)...

Studies on nano-sized particles have been the range for the past 10–15 years. With rapid growth of metal oxide nanotechnologies during the last decades, the application of this material in the field of catalysis has become a substantial research area. In the past decades, the utilization of transition metal oxide nanoparticle catalysts for industrial application in the synthesis of important chemical intermediates has been investigated by industrial and academic communities. Compared to other catalysts, one of the outstanding properties of metal oxide nanoparticles in catalysis is represented by the high selectivity which allows discrimination within chemical groups and geometrical positions, favoring high yields of the desired product. This review is devoted to dealing with the application of transition metal oxide nanoparticles as catalyst for oxidations of sulfides, alcohols, olefins, and alkanes toward the synthesis of a variety of organic compounds, such as sulfoxides, aldehydes and ketones, carboxylic acids, epoxides and alcohols.

Four new non-porous CuI-coordination polymers [Cu2(μ3-I)2(μ-bpb)]n (1a), [Cu(μ2-I)(μ-bpb)]n (1b), [Cu4(μ2-I)4(μ-bpmb)4]n (2), and [CuI(μ-bdb)]n (3) (bpb = 1,4-bis(pyrazolyl)butane; bpmb = 1,4-bis[(pyrazolyl)methyl]benzene; bdb = 1,4-bis[(3,5-dimethylpyrazolyl)methyl]benzene) have been successfully prepared and their structures fully characterized by single-crystal X-ray diffraction, FT-IR spectroscopy, PXRD and elemental analysis. Crystallographic investigation revealed that 1a, 1b, and 2 exhibit two-dimensional (2D) structures; in 1a parallel [Cu2I2]n staircase motifs are cross-linked into two-dimensional sheets by bpb linkers with a fully extended conformation, while in the structures of 1b and 2 Cu2I2 rhomboid dimers are linked by bpb and pbmb ligands, respectively, into two-dimensional sheets with a 44-sql net. Differently, compound 3 shows a one-dimensional (1D) zigzag chain structure with monomeric CuI units. All the four non-porous coordination polymers show the ability to capture volatile iodine in the gas phase. The solid-state photoluminescence properties of 1a, 1b, and 2 have also been investigated. The iodine-adsorbed samples 1a-I2, 1b-I2, and 2-I2 show no fluorescence behavior.

The new zirconocene compound, Cp2Zr(C9H9O)2, was successfully prepared from the reaction of zirconocene dichloride with 1-indanol in 1:2 molar ratio in dry chloroform at the presence of triethylamine (Et3N) and in an inert atmosphere. This compound was characterized by (1H and 13C) NMR, elemental analysis, FT-IR, UV–Vis, TGA and mass spectrum data. The catalytic activity of the synthesized compound for the acetylation of 2-naphtol and benzyl alcohol with acetic anhydride as an acetylating reagent in the solvent free conditions was also investigated. The Cp2Zr(C9H9O)2 as a catalyst affords an efficient and simple method for the acetylation of 2-naphtol and benzyl alcohol.

Surface functionalization of organometallic derivatives of phosphazenenanosphere (PNS) by the metal-coordinated Schiff base through (3-chloropropyl)trimethoxysilane as a silicon linker and spacer was investigated. The PNS's derivative of 4,4′-sulfonyldiphenol (BPS) was added to Si–H 2 saldien under ultrasonic irradiation. Metal ion (Mn 2+ , Ni 2+ or Zn 2+ ) was loaded on the PNS–Si–H 2 saldien as desired metal salt. The structure and morphology was characterized by means of FT-IR, TGA, SEM, EDX and X-ray diffraction. The average diameters of nanosphere compounds are in the range of 250–300 nm.

The stannocanes of the type [O(CH2CH2S)2SnR2](R=Me1,Bun2,Ph3) have been synthesized in an improved method by the reaction of R2SnCl2 with 2, 2′-oxydiethanethiol O(CH2CH2SH)2 in molar ratio of 1:1 at the presence of sodium ethoxide in anhydrous ethanol. The reactions are carried out under inert atmosphere. These compounds have been extensively characterized by FT-IR, UV-Vis spectrophotometry, multi-nuclear (1H, 13C, 119Sn) NMR, elemental analysis and mass spectrometry. The obtained data clearly indicates that, there is a strong interaction between oxygen atom of the ligand as a donor and Sn atom of the organotin species as a Lewis acid acceptor. Therefore, the resulted dithiostannocanes possess a transannular secondary bonding and hypervalency at the central Sn atom which leads to an increase in the coordination number of tin from four to five-coordinated tin.

The reaction of dichlorostannanes R2SnCl2 (R=Me 1, Bun 2) with piperazine ligand in molar ratio 1:2, in dry methylene dichloride, in an inert atmosphere leads to the synthesis of R2Sn(C4H9N2)2(R=Me 1, Bun 2). In a similar manner, The reaction between Ph2SnCl2 and piperazine in dry ethanol in molar ratio 1:1 produces [Ph2Sn(C4H8N2)]2 (3). The yields of these new products were excellent and they have been fully characterized by FT-IR, UV–Vis, multinuclear (1H, 13C, 119Sn) NMR spectroscopy and mass spectrometry, as well as elemental analysis. The spectroscopic results indicate that the piperazine ligand is coordinated to tin atom of organotin moieties, through the nitrogen atoms. Furthermore, the ligand behaves as a bidentate fashion in (1) and (2) and gives 1:2 substitution products, while in the complex (3) the two six-membered rings bind in bidentate-chelate forms between the two Sn atoms.

Three new water-soluble organotin complexes R2Sn(5-BrSalGT)Cl [R = Ph, Me] and Ph2Sn(2-OHNaphGT)Cl have been synthesized by the reaction of R2SnCl2 (R = Ph or Me) with Schiff bases derived from condensation of Girard-T reagent with 5-bromosalicylaldehyde and 2-naphthaldehyde, (5-BrH2SalGT)Cl (1) and (2-OHH2NaphGT)Cl (2). The synthesized compounds have been investigated by elemental analysis, conductometric measurements, IR, 1H NMR, and 119Sn NMR spectroscopy. These data show that the deporotonated ligand is coordinated to Sn(IV) via ONO atoms and six-coordinate zwitterionic complexes are formed. The ligands and their complexes were investigated for their in vitro toxicity against Gram-positive (Bacillus subtilis and Staphylococcus aureus) and Gram-negative (Escherichia coli and Pseudomonas aeruginosa) bacteria. The results show remarkable antibacterial activity against the studied bacteria. All complexes exhibit more inhibitory effects than the parent ligand. The anticancer activity of all compounds were also performed on HN5 cell line and (2-OHH2NaphGT)Cl with concentration of 1 mg mL−1 was found to show higher anticancer activity than other compounds.

The reaction of 2-thiazoline-2-thione (TZDSH) with SnR2Cl2 (R=Ph 1, Me 2, Bu 3) in dry ethanol in the presence of sodium ethoxide leads to [SnR2(C3H4NS2)2] (1, 2, and 3), respectively. Reaction between TZDSH and SnPh2Cl2 in dichloromethane and dry ethanol in an inert atmosphere produces [SnPh2Cl2(C3H5NS2)2] (4). The yields of the products were over 80%. These new complexes have been characterized by IR, UV-Vis, multinuclear (1H, 13C, and 119Sn) NMR spectroscopy, and mass spectrometry, as well as elemental analysis.

The reaction between hexachlorocyclotriphosphazenes (N3P3Cl6) and three equivalents of bis-salicylidene ethylene diamine (HOC6Hsu4-CH=N-CH2-)2 (salen) was investigated in two different experimental conditions. In the presence of anhydrous Na2CO3 in stirring tetrahydrofuran (THF) medium, the reaction led to a 50:50 mixture of tris[bis(salicylidene)ethylenediamine] cyclotriphosphazene, spiro-N3P3[(OC6H4-CH=N-CH2-)2]3 (1) and ansa (2) fully substituted products, whereas, in toluene solution, N3P3Cl6 with salen (3) and Al2O3/KOH afforded the spiro (1), as the only isolable compound. The spectroscopic data revealed that the oxygen atoms of salen moieties were selectively bonded to the three phosphorus atoms of the phosphazene ring. The new derivatives of cyclotriphosphazenes were characterized by IR spectrophotometry 1H NMR, 31P NMR spectral data and elemental analysis.

A novel organotin(IV) complex has been prepared from and the N, O and S donor ligand, 5-(p-dimethylaminobenzylidene) rodanine (HL). The ligand is deprotonated in the presence of a base and the complex with the general formula is formed. This complex was fully characterized by IR, NMR and NMR and elemental analysis. Spectroscopic data indicate the ligand is coordinated through the oxygen atom to the tin and the coordination number of four is supported by NMR data in solution.

The new cyclic phosph(V)azane ligand [(C6H5N)P(O)H]2 (2) is obtained from the reaction between PCl3 and PhNH2 in toluene followed by controlled hydrolysis of the product in an H2O–CHCl3 solution. Compound 2 is the first example of P(V) dimer [(µ-NC6H5)P(H)=O]2, a P2N2 ring with two P(O)H moieties. The reaction of 2 with ZnCl2 in a molar ratio of 1 : 1 in tetrahydrofuran yields the cyclophosph(V)azane complex Cl2Zn[(C6H5N)P(O)H]2 (3) in which Zn–O bonds form directly between a cyclic phosph(V)azane ligand and Zn(II). The products have been characterized by infrared, multinuclear (1H, 31P, 13C) NMR, mass spectrometry, and elemental analysis.

1,3,2,4-Diazadiphosphetidines as easily prepared, cheap, and air-stable P(III) containing ligands are successfully used for the efficient C–C bond formation via Suzuki–Miyaura, Sonogashira–Hagihara...

Reaction of the Grignard reagent, p-ClC6H4MgCl, with SiCl4 in toluene gave (p-ClC6H4)2SiCl2, which was treated with KHF2 to give (p-ClC6H4)2SiF2 (1). Reaction of the latter with [(Me3Si)3C]Li in THF leads to the preparation of [(Me3Si)3C](p-ClC6H4)2SiF (2). Treatment of (2) with LiAlH4 gave [(Me3Si)3C](p-ClC6H4)2SiH (3) and [(Me3Si)3C](p-ClC6H4)(C6H5)SiH (4). [(Me3Si)3C](p-ClC6H4)SiCl2 (5) was also prepared from the reaction of (p-ClC6H4)SiCl3 with [(Me3Si)3C]Li in a similar manner. The new highly sterically hindered organosilicon reagents (2) to (5) have been fully characterized by IR, 1H and 13C NMR, and mass spectrometry as well as elemental analysis.

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.

1,3,2,4-Diazadiphosphetidine-based phosphazane class have been used as a new generation of heterogeneous bidentate P(III) ligands containing nitrogen for base-free Pd(II) catalyzed C–C bond formation through Heck coupling reaction of aryl iodides, bromides and chlorides in water with styrene, n-butyl acrylate, 1-octene, and cyclohexene. The reactions occur heterogeneously in water and homogenously or partially heterogeneously in appropriate organic solvents. The ligand together with its Pd(0) complex is easily separated by filtration and reused for several runs.

Aminolysis of N3P3CI6 by an oxodiamine, bis-(2-ortho-aminophenoxyethyl) ether, has been carried out under various experimental conditions and new products with different architectures have been obtained. The reaction in diethyl ether when using a Na2CO3-water interface process gives the mono-BINO as major product. Reaction on Al2O3/KOH leads to the spirocyclic compound, while, when the reaction is carried out in toluene in the presence of NEt3, a mixture of mono- and di-BINO products are obtained. These new products have been characterized by IR, 1H and 31P NMR spectroscopy.

The substitution reaction of bis(anilino)phosphine oxide (C 6 H 5 NH) 2 P(O)H (1) with trans-PtCl 2 (SEt 2 ) 2 yields the novel unprecedented phosph(V)azane-platinum complex cis-Pt(SEt 2 ) 2 Cl[HNPhP(O)NPh(HNEt 3 )] (3). In this reaction, the bis(anilino)phosphine oxide undergoes P–H activation and a Pt(II)–P(V) bond instead of Pt–N bond forms. 31 P NMR spectra readily distinguish between the “N” and “P” bonding modes. The reaction requires the presence of triethylamine (TEA) as a base in order to deprotonate the phosphazane ligand and is separated as Et 3 NH+Cl−, whereas HTEA+ exists in the final product 3 and is acting as charge balancing and H-bond structure directing agent. The products have been fully characterized by means of IR; MS; UV-Vis; and 1 H, 13 C, and 31 P NMR spectroscopy.

Functionalized cyclotriphosphazenes with four pyrazolyl substituents have been employed for the synthesis of two new organotin complexes. These new compounds have been characterized by elemental analysis and IR, 1H, 31P and 119Sn NMR spectroscopy. On the basis of these data, pyrazolylcyclotriphosphazene is bis-bidentate neutral ligand coordinating to two SnMe2Cl2 molecules in the resulting adducts. Coordination occurs only via the pyrazolyl nitrogens; cyclotriphosphazene ring nitrogens are not involved in coordination. The 119Sn NMR data are consistent with increasing of coordination number of tin(IV) in solution.

The reactions of bis(anilino)phosphine oxide (C 6 H 5 NH) 2 P(O) H with (C 5 H 5 )2TiCl2 or Me2SiCl2 in a 1:1 molar ratio in THF results in the isolation of new phosph(V)azane complexes (C5H5)2Ti[(N C6H5)2P(O)H] (1) or Cl 2 Si[(N C 6 H 5 )2P(O)H] (2), respectively. In these reactions, HCl or CH4 elimination occurs and N-Ti or N-Si bonds form directly between a bis(anilino)phosphine oxide ligand and organotitanium or organosilicon compounds. The products(1) and (2) have been fully characterized by elemental analysis as well as 1 H, 31 P, 29 Si NMR, and IR spectroscopy.

The new ligand {[(C6H5NH)P(O)H](NC6H5)[(C6H5NH)P(O)H]} ( 2 ) was synthesized by heating bis(anilino)phosphine oxide (C6H5NH)2P(O)H ( 1 ) at 110°C and elimination of aniline. The treatment of 2 with SnBu2 Cl2 in the presence of triethylamine (TEA) in dry THF yielded the novel compound Bu n 2Sn{[Et3NH(NPh)P(O)H](NPh)p(O)H]}2 ( 3 ) in which the phosphazane ligand acts as a bidentate ligand. The products have been characterized by means of elemental analysis, IR, MS, and multinuclear NMR ( 1H, 13C, 31P, and 119Sn) spectroscopy. The spectroscopic data are consistent with the bounding of the phosph(V)azane ligand through both oxygen and phosphorus atoms to Sn(IV) center in the final compound 3 . TEA is used as a base in order to deprotonate the phosphazane ligand and is separated as Et3 NH + Cl − , whereas HTEA + exists in the title product 3 and is acting as a charge balancing and H-bond structure directing agent.

Reactions of phosph(V)azane derivatives of bis(anilino)phosphine oxide (PhNH)2P(O)H (1) with AlCl3 and SiCl4 produce two new phosph(V)azane complexes, AlCl[(NPh)2P(O)H] (2) and SiCl2[(NPh)2P(O)H] (3). In these reactions, an HCl elimination occurs and M─N bonds (M = Si, Al) form directly between a bis(anilino)phosphine oxide ligand with aluminum and silicon halides. The reactions do not require any base to deprotonate the phosphazane ligand. The final products have been fully characterized by means of elemental analysis and IR, MS, and multinuclear NMR (1H, 13C, 31P, 27Al, and 29Si) spectroscopy.

The phosphazane derivatives ( L 1–3 ) were readily obtained by reaction of different ratios of PCl 3 and PhNH 2 . The L 1–3 derivatives were found to be efficient ligands in the palladium-catalyzed Suzuki C C coupling reactions in water. It was determined that with the use of L 1–3 /Pd(OAc) 2 system as a catalyst, aryl halides undergo Suzuki cross-couplings with arylboronic acids to give the desired products in moderate to excellent yields.

The new complexes [Ph2SnCl(BuACDA)] (1), [Ph3Sn(BuACDA)] (2), [Bu2Sn(BuACDA)2] (3), [Ph2SnCl- (EtACDA)] (4), [Ph3Sn(EtACDA)] (5) and [Bu2Sn(EtACDA)2] (6) have been prepared from reactions between 2-N-butylamino-1-cyclopentene-1-carbodithioic acid (BuACDA) or 2-N-ethylamino-1-cyclopentene-1-carbodithioic acid (EtACDA) and Ph2SnCl2, Ph3SnCl or Bu2SnCl2. The 1H NMR, 119Sn NMR, UV-Vis and IR data and the elemental analyses support the structures of these organotin compounds. In all these complexes, the S–H proton has been removed and coordination takes place through the carbodithioate group. The 119Sn NMR data are consistent with the presence of five-coordinated tin(IV) in solution. Structures of 1 and 3 have also been confirmed by single crystal X-ray crystallography. The crystals of both are triclinic with space group . In the structure of 1, the tin environment is distorted trigonal bipyramidal with the Cl and one of the sulfur atoms in apical positions. In the structure of 3 the overall geometry at tin is...

Hexachlorocyclotriphosphazene (NPCl 2 ) 3 , reacted with 2,3-di(o-hydroxyphenylene)quinoxalin in the presence of a base, to yield tris[2,3-di(o-oxyphenylene)quinoxalin]cyclotriphosphazene. The synthesis of 2,3-di(o-hydroxy phenylene)quinoxaline was carried out through three steps: benzoin condensation, oxidation, and reaction of diketone with diamine. The products were characterized by 1 HNMR, 31 PNMR, IR, and mass spectral data.

Condensation of coordinated acetonitrile and one of the amine ligands in [(NH 3 ) 4 Co·μ(NH 2 ,NO 2 )·Co(NH 3 ) 4 ](CF 3 SO 3 ) 4 . H 2 O ( 2c ) results in the formation of a bridging acetamidino group. It is assumed that an intramolecular reaction occurred in which a coordinated amido ligand attack the substituted acetonitrile group to yield the third bridge. In this process the amido and acetonitrile groups which are coordinated to adjacent cobalt centers should bear a syn relationship. Synthesis and characterization of [(NH 3 ) 3 Co·μ(CH 3 C(NH) 2 ,NH 2 ,NO 2 )·Co(NH 3 ) 3 ](CF 3 SO 3 ) 3 ( 5 ) is reported here.

The dithiocarboxylato complexes of tin, Bz2SnCl(EtACDA) (1a) Bz=benzyl, Bz2Sn(EtACDA)2 (1b), and Bz3Sn(EtACDA) (1c) have been synthesized by the reaction of Bz2SnCl2 or Bz3SnCl with 2-N-ethylamino-1-cyclopentene-1-carbodithioic acid (HEtACDA). The reaction of 2-amino-1-cyclopente-1-carbodithioic acid (H2ACDA) with benzylamine, gave 2-N-benzylamino-1-cyclopente-1-carbodithioic acid (HBzACDA) (2), which reacts with Bz2SnCl2 or Bz3SnCl to give Bz2SnCl(BzACDA) (3a), Bz2Sn(BzACDA)2 (3b) and Bz3Sn(BzACDA) (3c). The products were characterized by IR and NMR (1H, 13C and 119Sn) spectroscopies and elemental analysis. The crystal structures of 1c, 2 and 3b have also been determined. In all the complexes Sn is bound asymmetrically to the dithiocarboxylato ligand through two sulfur atoms. The orientation of the ligands is determined by NH⋯S hydrogen bonds.

The catalyst generated in situ from Pd(OAc)2 and LIG shows good activity in the Suzuki reaction of aryl halides (I) with arylboronic acids (II).

The organotin(IV) chlorides R n SnCl 4− n ( n =2, R= n Bu or Ph; and n =3, R=Ph) react with 2-amino-1-cyclopentene-1-carbodithioic acid (ACDA) to give [Ph 2 SnCl(ACDA)] ( 1 ), [Ph 2 Sn(ACDA) 2 ] ( 2 ), [Ph 3 Sn(ACDA)] ( 3 ) and [Bu 2 Sn(ACDA) 2 ] ( 4 ). The new complexes have been characterized by elemental analysis, UV–Vis, IR, 1 H NMR, 119 Sn NMR spectroscopy and mass spectrometry. On the basis of 119 Sn NMR data the effective coordination number in solution is five. The structures of 1 , 3 and 4 have been confirmed by X-ray crystallography. Crystals of 1 are monoclinic with space group P 2 1 / n . The tin environment is distorted trigonal bipyramid with Cl and sulfur atoms in apical positions. Crystals of 3 are orthorombic, P 2 1 2 1 2 1 , and the structure is distorted trigonal bipyramid with one sulfur and phenyl in the axial position. Complex 4 crystallizes in the triclinic space group, P 1, and the Sn atom shows extremely irregular octahedral coordination with four S atoms laying in the equatorial plane. In all complexes ACDA coordinates as an anisobidentate ligand and its orientation lends to form a NH⋯S intramolecular hydrogen bond. The packing is also stabilized by intermolecular hydrogen bonding.

The reaction of a polydentate N,S ligand, 1′-amino-1′-cyclohexyl 2-cyclohexylideneamino-1-cyclohexene-1-dithiocarboxylate (ACCCD), with Ph2SnCl2, Ph3SnCl and Me2SnCl2 was investigated. The new adducts have been characterized by UV–Vis, 1H NMR, IR, mass spectroscopy and elemental analysis. These data are consistent with 1:1 adducts. The ligand behaves as a bidentate and shows both nitrogen and sulfur coordination. There is also evidence that the ligand ACCCD exhibits some interest in forming possible inter-/intra-molecular hydrogen bonds through Cl⋯H2N interactions in Me2SnCl2 and Ph2SnCl2 adducts. The UV–Vis spectra indicate that the compounds partially dissociate in chloroform.

Regioselective reactivity, molecular cleft selectivity, and conformational properties have been examined in the skeletally stabilized triphosphazanes C 6 H 4 N 2 [P(NEt 2 ) 2 ] 2 PNEt 2 (4), C 6 H 4 N 2 -[P(S)(NEt 2 ) 2 ] 2 PCl (5), and C 6 H 4 N 2 [P(S)(NEt 2 ) 2 ] 2 P(S)NEt 2 (9) and in a series of new derivatives. 3 is oxidized/coordinated regioselectively by O 3 , Se, PhN 3 , and BH 3 to C 6 H 4 N 2 [P(O)(NEt 2 ) 2 ] 2 PNEt 2 and C 6 H 4 N 4 [P(O)(NEt 2 ) 2 ] 2 P(O)NEtz

The new diazadiphosphetidine shown in the scheme efficiently promotes the Heck reaction of aromatic iodides, bromides, and chlorides with activated and unactivated alkenes in water.

Potassium ferrate in the presence of copper(II) sulfate pentahydrate can convert 1-phenyl ethanol, 4-chloro-1-phenyl ethanol and 2-phenyl ethanol into ester products with good or excellent yields.The reactions have been carried out inn-hexane at room temprature.The effect of other metal salts, as activators, have been also examined instead of copper sulfate.

Synthese et reactivite de PhN(PCl 2 ) 2 Mo(CO) 4 , PhN[P(NHPh) 2 ] 2 Mo(CO) 4 , [(PhNH)PNPh] 3 Mo(CO) 4 et [(PhNH)P 2 (NPh) 2 ] 2 NPhMo(CO) 4 . Structure cristalline du 2eme

The 1,3,2,4-diazadiphosphetidine-based dimer ((PhNH)PNPh)/sub 2/ (1) or trimer ((PhNH)PNPh)/sub 3/ (2) forms from (Et/sub 2/N)/sub 3/P-PhNH/sub 2/ transamination or PhN(P(NHPh)/sub 2/)/sub 2/ thermolysis reactions. 2 is an intermediate in the formation of 1 from PhN(P(NHPh)/sub 2/)/sub 2/. An x-ray single-crystal diffraction analysis of the solvate 2-C/sub 2/-H/sub 5/OH has been carried out. 2-C/sub 2/H/sub 5/OH is monoclinic, space group C2/c, with a = 23.156 (9) /angstrom/, b = 14.533 (5) /angstrom/, c = 22.243 (8) /angstrom/, ..beta.. = 110.63 (3)/degrees/, Z = 8, d/sub calcd/ = 1.24 g/cm/sup 3/, and d/sub obsd/ = 1.15 g/cm/sup 3/ (24/degrees/C, Mo K..cap alpha..). 2 c C/sub 2/H/sub 5/OH refined to R = 0.069 and R/sub w/ = 0.083 for 1850 independent reflections. 2 contains PhNH- and -N(PH)P(NHPh)/sub 2/ substituents at phosphorus atoms of the 1,3,2,4-diazadiphosphetidine ring. 2 has approximately C/sub s/ molecular symmetry. Complete characterization data for 1 are given. The /sup 31/P NMR spectrum of 1, in contrast to that of 2, is temperature dependent. Below -40/degrees/C, 1 in toluene assumes an unsymmetrical conformation of approximately C/sub s/ symmetry in which the PhNH groups are rotated opposite to each other, with respect to the lone-pair electrons of the P/sub 2/N/sub 2/ ringmore » phosphorus atoms. The dimer (1)-trimer (2) interconversion is discussed and related to more general phosphazane oligomerization. 37 references, 6 figures, 3 tables.« less

Iso-PrNH 2 reacts with fac (CO) 3 Mo(PCl 3 ) 3 to form fac -[( i -PrNH) 3 P] 3 Mo(CO) 3 , a complex containing a unique combination of secondary amino-group functionality and trisaminophosphino) substitution on molybdenum.