Bis[(2-diphenyIphosphino)phenyl]phenylphosphine as an Inflexible Tridentate Ligand for Indium Trichloride

1999 ◽  
Vol 54 (11) ◽  
pp. 1417-1419 ◽  
Author(s):  
Marcus Sigl ◽  
Annette Schier ◽  
Hubert Schmidbaur
Keyword(s):  
Spin System ◽  
Phosphorus Atom ◽  
Nmr Spectra ◽  
Lone Pair ◽  
Bidentate Ligand ◽  
Tridentate Ligand ◽  
Molar Ratio ◽  
X Ray Diffraction ◽  
Ionic Complex ◽  
X Ray

Anhydrous indium trichloride reacts with [2-(Ph2P)C6H4]2PPh (TP) in the molar ratio 2:1 to give an ionic complex [(TP)InCl2]+ InCL4- in almost quantitative yield. The structure of the product has been determined by a single crystal X-ray diffraction study. In the cation the TP molecule acts only as a bidentate ligand via its two terminal phosphorus atoms [In-P1 2.5956(8), In-P2 2.5799(7) Å], Although the central phosphorus atom is also rather close to the metal atom [2.8259(8) Å], the In-P3 interaction is inefficient because of an adverse orientation of the lone pair of electrons at P3 owing to the steric inflexibility of the ligand. Accordingly, the 31P NMR spectra of the compound in CD2CI2 show large contact shifts and quadrupole broadening only for the signals of the two terminal phosphorus atoms, whereas the lines of the central phosphorus atom are less shifted and well resolved (AB2 spin system at -60°C).

scholarly journals Synthesis, Physical Properties and Enzymatic Degradation of Biodegradable Nanocomposites Fabricated Using Poly(Butylene Carbonate-Co-Terephthalate) and Organically Modified Layered Zinc Phenylphosphonate

Polymers ◽  
2020 ◽  
Vol 12 (9) ◽  
pp. 2149
Author(s):  
Li-Ying Tseng ◽  
Erh-Chiang Chen ◽  
Jie-Mao Wang ◽  
Tzong-Ming Wu
Keyword(s):  
Nmr Spectra ◽  
Enzymatic Degradation ◽  
Molar Ratio ◽  
Wide Angle ◽  
Mixing Process ◽  
X Ray Diffraction ◽  
X Ray ◽  
Transmission Electron ◽  
Organically Modified ◽  
Biodegradable Nanocomposites

A new biodegradable aliphatic-aromatic poly (butylene carbonate-co-terephthalate) (PBCT-85) with the molar ratio [BC]/[BT] = 85/15, successfully synthesized through transesterification and polycondensation processes, was identified using 1H-NMR spectra. Various weight ratios of PBCT/organically modified layered zinc phenylphosphonate (m-PPZn) nanocomposites were manufactured using the solution mixing process. Wide-angle X-ray diffraction and transmission electron microscopy were used to examine the morphology of PBCT-85/m-PPZn nanocomposites. Both results exhibited that the stacking layers of m-PPZn were intercalated into the PBCT-85 polymer matrix. The additional m-PPZn into PBCT-85 copolymer matrix significantly enhanced the storage modulus at −70 °C, as compared to that of neat PBCT-85. The lipase from Pseudomonas sp. was used to investigate the enzymatic degradation of PBCT-85/m-PPZn nanocomposites. The weight loss decreased as the loading of m-PPZn increased, indicating that the existence of m-PPZn inhibits the degradation of the PBCT-85 copolymers. This result might be attributed to the higher degree of contact angle for PBCT-85/m-PPZn nanocomposites. The PBCT-85/m-PPZn composites approved by MTT assay are appropriate for cell growth and might have potential in the application of biomedical materials.

Reaktive E=C (p-p)π-Systeme, XL. / Reactive E=C(p-p)π Systems, XL.

1995 ◽  
Vol 50 (1) ◽  
pp. 94-100 ◽  
Author(s):  
Thomas Albers ◽  
Joseph Grobe ◽  
Duc Le Van ◽  
Bernt Krebs ◽  
Mechtild Läge
Keyword(s):  
Molecular Structure ◽  
Main Product ◽  
Chloroform Solution ◽  
Lone Pair ◽  
Secondary Amines ◽  
Molar Ratio ◽  
Electronic Interaction ◽  
X Ray Diffraction ◽  
X Ray ◽  
New Compounds

The reaction of bis(trifluoromethyl)arsane 2 with secondary amines R2NH in a molar ratio of 1:3 at -60 °C allows the preparation of trifluoromethyl arsaalkenes of the type F3CAs=C(F)NR2 in moderate yields (15-35%) [NR2 = NMe2 (3a), NMeEt (3b), NEt2 (3c)]. The main product of the reaction of 2 with Me2NH is the 1,1-diamino compound F3CAs=C(NMe2)2 (4a). With ethyl(isopropyl)- or di(isopropyl)amine the corresponding derivatives F3CAs=C(F)NEt(iPr) (3d) and F3CAs=C(F)N(iPr)2 (3e), respectively, are formed only in traces (3d), or not at all (3 e). However, 3d and 3e can be prepared by reacting perfluoro-2-arsapropene with the corresponding secondary amines. The new compounds 3 a to 3 e can be stored at 20 °C in chloroform solution for hours without decomposition and show Z configuration without exception. The molecular structure of 1-(diethylamino)-1,3,3,3-tetrafluoro-2-arsapropene 3c, determined by an X-ray diffraction study on single crystals, indicates a strong electronic interaction of the lone pair on nitrogen with the AsC double bond. This results in a trigonal planar arrangement at the nitrogen atom, a strongly shortened sp2-CN-bond (1.312 Å), an elongated AsC distance (1.867 Å), and an almost planar skeleton of the molecule.

Synthese und Struktur- und Konformationsanalyse von Triphenylphosphonium-bis(diphenylarsino)methylid

1984 ◽  
Vol 39 (11) ◽  
pp. 1456-1462 ◽  
Author(s):  
Hubert Schmidbaur ◽  
Peter Nußstein ◽  
Gerhard Müller
Keyword(s):  
Single Crystal ◽  
Spectroscopic Data ◽  
Heavy Atom ◽  
Lone Pair ◽  
Molar Ratio ◽  
Single Bond ◽  
X Ray Diffraction ◽  
Trans Conformation ◽  
X Ray ◽  
Lone Pairs

Abstract Triphenylphosphonium -diphenylarsinomethylide (1) and -bis-(diphenylarsino)methylide (2) are easily available through transylidation processes using Ph3P = CH2 and Ph2AsCl as the starting materials in the appropriate molar ratio. Analytical and spectroscopic data are presented for both ylides. The structure of 2 was studied in detail by single-crystal X-ray diffraction. The basic PCAs2 skeleton is found to deviate strongly from planarity. The Ph2As-substituents adopt a cis/trans conformation relative to the ylidic P = C bond with the directions of the lone pairs of electrons at the arsenic atoms in the heavy atom plane as expected for a maximum compensation of the electrostatic vectors. For 1, a cis-conformation of the lone pair of electrons and a large PCAs angle are predicted on the basis of NMR analogies with the phosphorus homologues. Single bond rotational barriers appear to be much lower for 1 and 2, however, than for the corresponding phosphino-substituted ylides.

scholarly journals Syntheses, Reactivities, Characterization, and Crystal Structures of Dipalladium Complexes Containing the 1,3-pyrimidinyl Ligand: Structures of [Pd(PPh3)(Br)]2(μ,η2-C4H3N2)2, [Pd(Br)]2(μ,η2-Hdppa)2, and [{Pd(PPh3)(CH3CN)}2(μ,η2-C4H3N2)2][BF4]2

Molecules ◽  
2020 ◽  
Vol 25 (9) ◽  
pp. 2035
Author(s):  
Hsiao-Fen Wang ◽  
Kuang-Hway Yih ◽  
Gene-Hsiang Lee
Keyword(s):  
Single Crystal ◽  
Crystal Structures ◽  
Room Temperature ◽  
Palladium Complex ◽  
Chloroform Solution ◽  
Bidentate Ligand ◽  
Tridentate Ligand ◽  
Spectroscopic Methods ◽  
X Ray Diffraction ◽  
X Ray

In a refluxing chloroform solution, the η1-pyrimidinyl {pyrimidinyl = C4H3N2} palladium complex [Pd(PPh3)2(η1-C4H3N2)(Br)], 1 exhibited intermolecular displacement of two triphenylphosphine ligands to form the doubly bridged η2-pyrimidinyl Dipalladium complex [Pd(PPh3)(Br)]2(μ,η2-C4H3N2)2, 3. The treatment of 1 with Hdppa {Hdppa = N,N-bisdiphenyl phosphinoamine} in refluxing dichloromethane yielded the doubly bridged Hdppa dipalladium complex [Pd(Br)]2(μ,η2-Hdppa)2, 4. Complex 1 reacted with the bidentate ligand, NH4S2CNC4H8 and, NaS2COEt, and the tridentate ligand, KTp {Tp = tris(pyrazoyl-1-yl)borate}, to form the η2-dithio η1-pyrimidinyl complex [Pd(PPh3)(η1-C4H3N2)(η2-SS)], (5: SS = S2CNC4H8; 6: SS = S2COEt) and η2-Tp η1-pyrimidinyl complex [Pd(PPh3)(η1-C4H3N2)(η2-Tp)], 7, respectively. Treatment of 1 with AgBF4 in acetonitrile at room temperature resulted in the formation of the doubly bridged η2-pyrimidinyl dipalladium complex [{Pd(PPh3)(CH3CN)}2(μ,η2-C4H3N2)2][BF4]2, 8. All of the complexes were identified using spectroscopic methods, and complexes 3, 4, and 8 were determined using single-crystal X-ray diffraction analyses.

scholarly journals THE INTERACTION BETWEEN [Pt(µ-Cl)(Safrole-1H)]2 AND 1,3-DIISOPROPYLBENZIMIDAZOLIUM BROMIDE IN THE PRESENCE OF Ag2O

2020 ◽  
Vol 58 (6) ◽  
pp. 728
Author(s):  
Nguyen Thi Thanh Chi
Keyword(s):  
Single Crystal ◽  
Nmr Spectra ◽  
Molar Ratio ◽  
Trans Position ◽  
Dimeric Complex ◽  
X Ray Diffraction ◽  
Factors Affecting ◽  
X Ray ◽  
In Trans ◽  
Main Factors

The interaction of the dimeric complex [Pt(µ-Cl)(Saf)]2 (1) (Saf: deprotonated safrole) with the salt iPr2-bimy·HBr in the presence of Ag2O in acetone solvent was studied. The obtained products were mixed complexes of [PtCl(Saf)(iPr2-bimy)] (2) and [PtBr(Saf)(iPr2-bimy)] (3) with different molar ratio (PI, PII, PIII)  depended on the used molar ratio of 1:salt:Ag2O. In the case of this ratio being 1:2:1.1, the mixture PI with 75% for the complex 2 was obtained. When concentration of the salt was increased, the product was PII with the molar ratio of 2 : 3 of 1 : 3. However, when both the salt and Ag2O were increased at the same time, 2 and 3 in PIII had equal molar proportions. The two main factors affecting the 2 : 3 molar ratio are the different solubility of AgCl and AgBr and the different coordinating ability of Cl- and Br- ligands. The structure of 2 and 3 was determined by 1H NMR spectra and single crystal X-ray diffraction. The results reveal that Saf in 2 and 3 coordinates with Pt(II) via C=Colefinic and C5 of benzene ring. Meanwhile, iPr2-bimy coordinates with Pt(II) through CNCN and is in trans-position compared with the C=Colefinic bond.

Metal Complexes of Biologically Important Ligands, CLXXV [1]. Pentamethylcyclopentadienyl Halfsandwich Complexes of Rhodium(III) and Iridium(III) with Schiff Bases from 2-(Diphenylphosphino)- benzaldehyde and α-Amino Acid Esters

2010 ◽  
Vol 65 (6) ◽  
pp. 679-686 ◽  
Author(s):  
Bernhard Schreiner ◽  
Barbara Wagner-Schuh ◽  
Wolfgang Beck
Keyword(s):  
Schiff Base ◽  
Amino Acid ◽  
Schiff Bases ◽  
Ester Group ◽  
Tridentate Ligand ◽  
Molar Ratio ◽  
Amino Acid Esters ◽  
X Ray Diffraction ◽  
X Ray ◽  
Acid Esters

The reactions of the chlorido-bridged complexes [Cp*M(Cl)(μ-Cl)]2 (M = Rh, Ir) with Schiff bases (P-N-O) from 2-(diphenylphosphino)benzaldehyde and α-amino acid esters afford the complexes Cp*M(Cl)2(P-N-O) in which the ligands function as monodentate P donors (M = Ir) or as bidentate P-N donors (M = Rh). These complexes can be converted into cationic complexes [Cp*M(Cl)(P-NO)]+ with bidentate P-N ligands by treatment with NH4PF6. The cationic complexes [Cp*M(Cl)(PN- O)]+Cl− have been detected also in solutions of Cp*M(Cl)2(P-N-O). The P-N-coordinated complex [Cp*Rh(Cl)(Ph2P-C6H4-C(H)=N-C(H)(CH2Ph)CO2Me)]+PF6− was characterized by X-ray diffraction. From Cp*M(Cl)2(P-N-O) and AgBF4 or AgPF6 (molar ratio 1 : 2) the dicationic complexes [Cp*M(P-N-O)]2+ are formed in which the ester group is also coordinated to the metal atom. The Schiff base from 2-(diphenylphosphino)benzaldehyde and allylglycine ester acts as a tridentate ligand, however with coordination of the C=C allyl group instead of the ester function.

Reaktive E=C(p-p)π-Systeme, XLIII [1] Darstellung und Charakterisierung P-Phosphino- oder P-Arsino-substituierter Fluorphosphaalkene des Typs R2E-P=C(F)NEt2 (R = Me, CF3, Me2N; E = P, As) / Reactive E=C(p-p)-π Systems XLIII [1] Synthesis and Characterization of P-Phosphino or P-Arsino Substituted Fluorophosphaalkenes of the Type R2E-P=C(F)NEt2 (R= Me, CF3, Me2N; E = P As)

1996 ◽  
Vol 51 (6) ◽  
pp. 778-784 ◽  
Author(s):  
Joseph Grobe ◽  
Duc Le Van ◽  
Jost Winnemöller ◽  
Bernt Krebs ◽  
Mechtild Läge
Keyword(s):  
Lone Pair ◽  
Molar Ratio ◽  
Analogous Reaction ◽  
X Ray Diffraction ◽  
X Ray ◽  
Nitrogen Lone Pair ◽  
Type Interaction ◽  
The Stability ◽  
High Yields

Abstract The easily accessible phosphaalkene HP=C(F)NEt2 (lb) reacts with halophosphanes or -arsanes R2EX (X = Cl, I) in the presence of NEt3 to give P-phosphino- or -P-arsino substituted fluorophosphaalkenes of the type RiE-P=C(F)NEti (2 - 6) in high yields (60 - 85 %) [R2E: (CF3)2P (2), Me2N(CF3)P (3), Me2P (4), (CF3)2As (5), Me2As (6)]. The analogous reaction of ib with CF3PI2 (molar ratio 1:2) unexpectedly leads to the triphosphetene Et2N - C=P-PCF3-PCF3 (7). The stability of compounds 2 - 6 as a function of R2E decreases from As to P and from CF3 to Me, respectively. Compounds 2 - 6 generally show the Z-configuration and have been characterized by thorough spectroscopic investigations (MS,IR; 1H, 19F, 11C, 31PNMR). A single crystal X-ray diffraction study of 2 proves the π-type interaction of the nitrogen lone pair with the P=C bond thus enhancing the stability of the system and the PP bond order

Effect of Hydrated Metal Salts on the Coordination Product of Cobalt(II) halide and PNP Type Ligand, 2,6-bis(di-tertbutylphosphinomethyl) pyridine

2018 ◽  
Author(s):  
Tasneem Siddiquee ◽  
Abdul Goni
Keyword(s):  
Metal Salts ◽  
Molar Ratio ◽  
Pincer Complexes ◽  
Asymmetric Unit ◽  
X Ray Diffraction ◽  
Pincer Ligand ◽  
Tetrahedral Geometry ◽  
X Ray ◽  
Distorted Tetrahedral Geometry ◽  
Cobalt Center

Chemical treatment of CoX<sub>2</sub><b><sup>. </sup></b>6H<sub>2</sub>O (X = Cl, Br, I) with the potentially tridentate PNP pincer ligand 2,6-bis(di-<i>tert</i>-butylphosphinomethyl)pyridine in 1:1 molar ratio results in cobalt(II) halide-PNP pincer complexes. The effect of the hydrated metal source on molecular structure and geometry of the complexes was studied by single crystal X-ray diffraction analysis. The complexes are neutral and the cobalt center adopts a penta-coordinate system with potential atropisomerization. Within the unit cell there are two distinct molecules per asymmetric unit. One of the two phosphorus atoms in the PNP ligand was observed to be partially oxidized to phosphinoxide. Disorder in the structure reflects a mixture of square pyramidal and distorted tetrahedral geometry.

The Electron Effect of Aromatic Group: Control Conformation of 2-Aromatic Cyclododecanone Derivatives

2020 ◽  
Vol 24 (10) ◽  
pp. 1139-1147
Author(s):  
Yang Mingyan ◽  
Wang Daoquan ◽  
Wang Mingan
Keyword(s):  
1H Nmr ◽  
13C Nmr ◽  
Nmr Spectra ◽  
Coupling Constants ◽  
The Other ◽  
Repulsive Interaction ◽  
X Ray Diffraction ◽  
X Ray ◽  
Electron Effect ◽  
Group Control

2-Phenylcyclododecanone and 2-cyclohexylcyclododecanone derivatives were synthesized and characterized by 1H NMR, 13C NMR, HR-ESI-MS and X-ray diffraction. Their preferred conformations were analyzed by the coupling constants in the 1H NMR spectra and X-ray diffraction, which showed the skeleton ring of these derivatives containing [3333]-2-one conformation, and the phenyl groups were located at the side-exo position of [3333]-2-one conformation due to the strong π-π repulsive interaction between the π- electron of benzene ring and π-electron of carbonyl group. The cyclohexyl groups were located at the corner-syn or the side-exo position of [3333]-2-one conformation depending on the hindrance of the other substituted groups. The π-π electron effect played a crucial role in efficiently controlling the preferred conformation of 2-aromatic cyclododecanone and the other 2-aromatic macrocyclic derivatives with the similar preferred square and rectangular conformations.

Preparation, properties and structure of some intermediate nido- and arachno-monocarbaboranes

1981 ◽  
Vol 46 (10) ◽  
pp. 2345-2353 ◽  
Author(s):  
Karel Baše ◽  
Bohumil Štíbr ◽  
Jiří Dolanský ◽  
Josef Duben
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Nmr Spectra ◽  
Liquid Ammonia ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Starting Compound

The 6-N(CH3)3-6-CB9H11 carbaborane reacts with sodium in liquid ammonia with the formation of 6-CB9H12- which was used as a starting compound for preparing the 4-CB8H14, 9-L-6-CB9H13 (L = (CH3)2S, CH3CN and P(C6H5)3), 1-(η5-C5H5)-1,2-FeCB9H10-, and 2,3-(η5-C5H5)2-2,31-Co2CB9H10- carboranes. The 4-CB8H14 compound was dehydrogenated at 623 K to give 4-(7)-CB8H12 carborane. Base degradation of 6-N(CH3)3-6-CB9H11 in methanol resulted in the formation of 3,4-μ-N(CH3)3CH-B5H10. The structure of all compounds was proposed on the basis of their 11B and 1H NMR spectra and X-ray diffraction was used in the case of the transition metal complexes.

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