One-pot carbanionic synthesis of P1,P2-diglycosyl, P1,P1,P2-triglycosyl, and P1,P1,P2,P2-tetraribosyl methylenediphosphonates

Novel lithiated carbanions derived from ethyl glycosyl- and diglycosyl methylphosphonates were used in a direct and convenient synthesis of P1,P2-diglycosyl, P1,P1,P2-triglycosyl, and P1,P1,P2,P2-tetraribosyl methylenediphosphonates involving a one-pot methylidenediphosphonylation of sugars.     

Synthesis and thermal kinetic study of phosphoric acid,P, P′-1, 4-phenylene P,P, P′, P′-tetraphenyl ester

Journal of Thermal Analysis and Calorimetry - A phosphorous flame retardant of phosphoric acid, P, P′-1, 4-phenylene P, P, P′, P′-tetraphenyl ester (PAPTE) was synthesized by...     

Chemistry of Several Sterically Bulky Molecules with P=P,P=C,and C≡P Bond

Several sterically protected, low-coordinate organophosphorus compounds with P=P, P=C, and C≡P bond are described in this study. Molecules such as diphosphenes, phosphaalkenes, 1-phosphaallenes, 1,3-diphosphaallenes, 3,4-diphosphinidenecyclobutenes, and phosphaalkynes are stabilized with an extremely bulky 2,4,6-tri-t-butylphenyl (Mes*) group. The synthesis, structures, physical, and chemical properties of these molecules are discussed, together with some successful applications in catalytic organic reactions.     

ChemInform Abstract: Theoretical Study of the Stability of Molecular P2, P4, and P8.

Ab initio calculations for P2, P4 and P8 on the SCF level and with inclusion of valence correlation effects, except for P8.     

Struktur und Farbigkeit von P,P′-Tetra-t-butyl-und P,P′-Tetraphenyl-oxalsäurediphosphid und Derivaten

The unexpected violet colour of P,P-tetraphenyl-oxalic acid diphosphide (3) stimulated the synthesis of the following derivatives: P,P-tetra-t-butyl-oxalic acid diphosphide (2), N,P-tetraphenyl-oxalic acid amide phosphide (4) and P, -triphenyl-glyoxylic acid phosphide (5). The compounds could be prepared by the reaction of the corresponding acyl chlorides with diorganyl-(trimethylsilyl) phosphine; (organyl=t-butyl and phenyl). The electronic transitions of green-blue2 and red5 in the 450–700 nm region are discussed, also theirv C=O in the ir spectrum. These results are interpreted in connection with the molecule structures of2 and3 which have been determined by X-ray crystal structure analysis. In2 the framework P–C(O)–C(O)–P is only slightly distorted from a coplanartrans-position, in3 somewhat more. The bonds at P have the expected pyramidal arrangement. The direction of the lone pairs at the P-atoms, derived from this bond arrangement, is discussed with respect to the electronic transitions in acyl phosphides.

     

t-BuOK-mediated hydrophosphination of functionalized alkenes: a novel synthesis of chiral P,N- and P,P-ligands

A novel synthesis of effective chiral P,N- and P,P-ligands has been developed by using a t-BuOK-mediated hydrophosphination of chiral alkenylpyridines and alkenylphosphine oxides. Ir complexes of chiral P,N-ligands 1 and 3 gave high enantioselectivities for the hydrogenation of (Z)-alpha-(acetamido)cinnamate 25 and (E)-1,2-diphenylpropene leading to the hydrogenated products with up to 97% ee.     

Ternary early-transition-metal palladium pnictides Zr3Pd4P3, Hf3Pd4P3, HfPdSb, and Nb5Pd4P4

Several ternary palladium pnictides of the early transition metals have been prepared by arc-melting of the elemental metals and the binary pnictides ZrP, HfP, HfSb2, or NbP, and their structures have been determined by X-ray diffraction methods. The phosphides M3Pd4P3 (M = Zr, Hf) adopt a new structure type (Pearson symbol oP40), crystallizing in the orthorhombic space group Pnma with Z = 4 and unit cell parameters of a = 16.387(2), b = 3.8258(5), and c = 9.979(1) A for Zr3Pd4P3 and a = 16.340(2), b = 3.7867(3), and c = 9.954(1) A for Hf3Pd4P3. The antimonide HfPdSb was identified by powder X-ray diffraction (orthorhombic, Pnma, Z = 4, a = 6.754(1) A, b = 4.204(1) A, and c = 7.701(2) A) and confirmed to be isostructural to ZrPdSb, which adopts the TiNiSi-type structure. The phosphide Nb5Pd4P4 adopts the Nb5Cu4Si4-type structure, crystallizing in the tetragonal space group I4/m with Z = 2, a = 10.306(1) A, and c = 3.6372(5) A. Coordination geometries of pentacapped pentagonal prisms for the early transition metal, tetracapped distorted tetragonal prisms for Pd, and tricapped trigonal prisms for the pnicogen are found in the three structures; tetracapped tetragonal prisms for Nb are also found in Nb5-Pd4P4. In common with many metal-rich compounds whose metal-to-nonmetal ratio is equal or close to 2:1, the variety of structures formed by these ternary palladium pnictides arises from the differing connectivity of pnicogen-filled trigonal prisms. Pnicogen-pnicogen bonds are absent in these structures, but metal-metal bonds (in addition to metal-pnicogen bonds) are important interactions, as verified by extended Hückel band structure calculations on Zr3Pd4P3.     

P1,P2-diimidazolyl derivatives of pyrophosphate and bis-phosphonates--synthesis, properties, and use in preparation of dinucleoside tetraphosphates and analogs

P(1),P(2)-Diimidazolyl derivatives of pyrophosphate and halomethylene-bis-phosphonates have been synthesized and characterized, and the mechanism of their formation was studied. These reagents enable synthesis of dinucleoside tetraphosphates and tetraphosphonates conveniently and in high yields.     

Chiral Proline‐Based P,O and P,N Ligands for Iridium‐Catalyzed Asymmetric Hydrogenation

Two new classes of proline‐based P,O and P,N ligands were prepared and applied in the iridium‐catalyzed asymmetric hydrogenation of alkenes. Both types of ligands induced high enantioselectivities in the hydrogenation of trisubstituted C?C bonds. Iridium complexes derived from P,O ligands bearing sterically demanding amide or urea groups at the pyrrolidine N‐atom proved to be especially efficient catalysts for the conjugate reduction of α,β‐unsaturated esters and ketones, whereas analogous P,N ligands led to better results with dialkyl‐phenyl‐substituted alkenes and an allylic alcohol as substrates.     

31P solid state NMR studies of metal selenophosphates containing [P2Se6]4-, [P4Se10]4-, [PSe4]3-, [P2Se7]4-, and [P2Se9]4- ligands

31P solid-state nuclear magnetic resonance (NMR) spectra of 12 metal-containing selenophosphates have been examined to distinguish between the [P(2)Se(6)](4-), [PSe(4)](3-), [P(4)Se(10)](4-), [P(2)Se(7)](4-), and [P(2)Se(9)](4-) anions. There is a general correlation between the chemical shifts (CSs) of anions and the presence of a P[bond]P. The [P(2)Se(6)](4-) and [P(4)Se(10)](4-) anions both contain a P[bond]P and resonate between 25 and 95 ppm whereas the [PSe(4)](3-), [P(2)Se(7)](4-), and [P(2)Se(9)](4-) anions do not contain a P[bond]P and resonate between -115 and -30 ppm. The chemical shift anisotropies (CSAs) of compounds containing [PSe(4)](3-) anions are less than 80 ppm, which is significantly smaller than the CSAs of any of the other anions (range: 135-275 ppm). The smaller CSAs of the [PSe(4)](3-) anion are likely due to the unique local tetrahedral symmetry of this anion. Spin-lattice relaxation times (T(1)) have been determined for the solid compounds and vary between 20 and 3000 s. Unlike the CS, T(1) does not appear to correlate with P-P bonding. (31)P NMR is also shown to be a good method for impurity detection and identification in the solid compounds. The results of this study suggest that (31)P NMR will be a useful tool for anion identification and quantitation in high-temperature melts.     

Novel Chemistry of the Aromatic 1,2,4-Triphospholyl and 1,3,-Diphospholyl Anions,P 3 C 2 t Bu 2 and P 2 C 3 t Bu 3 , and the 1,3,5-Triphosphabenzene,P 3 C 3 t Bu 3

Oxidative coupling of the P 3 C 2 t Bu 2 anion with I 2 affords a convenient synthetic route to the remarkable hexaphosphapentaprismane cage P 6 C 4 t Bu 4 , which undergoes ready insertion reactions of carbene like fragments such as S, Se, Te, SnR 2 specifically into the P--P bond, which in turn connects the two P 3 C 2 t Bu 2 fragments. Di- and tri-phospholyl compounds MP 3 C 2 t Bu 2 (M = Ga, In, Tl), M'(P 3 C 2 t Bu 2 ) 2 (M' = Zn, Cd, Hg), and [1 + 4] cyclo-additions of the triphosphabenzene, P 3 C 3 t Bu 3 , and extrusion of the t BuC or P moeities from the 6-membered ring are presented.     

A general and efficient method for the preparation of unsymmetrical bidentate P,N and P,S ligands

A general and efficient preparation of chiral and achiral P,N and P,S ligands is described where ligands are prepared by reacting a variety of 2- or α-lithio N- or S-heterocycles and a lithiated phosphine with 1,2-cyclic sulfates.     

Design,synthesis, and evaluation of matrix metalloprotease inhibitors bearing cyclopropane-derived peptidomimetics as P1' and P2' replacements

We have previously used trisubstituted cyclopropanes as peptide replacements to induce conformational constraints in known pseudopeptide inhibitors of a number of important enzymes. Cyclopropane-derived peptide mimics are novel in that they are among the few replacements that locally orient the peptide backbone and the amino acid side chain in a predefined manner. Although these dipeptide isosteres have been employed to orient amino acid side chains mimicking the gauche(-) conformation of chi(1)-space, their ability to project the side chains into an anti orientation has not been evaluated. As a first step toward this goal, the conformationally constrained pseudopeptides 8 and 10 and their corresponding flexible analogues 9 and 11 were prepared and tested as inhibitors of matrix metalloproteinases (MMPs). These compounds are analogues of 4 and 5, which were known to be potent MMP inhibitors. The anti orientations of the isopropyl side chain in 8 and the aromatic ring in 10 relative to the peptide backbone substituents on the cyclopropane were predicted to correspond to the known orientations of the P1' and P2' side chains of 5 when bound to MMPs. Hence, 8 and 10 were designed explicitly to probe topological features of the S1' or the S2' binding pockets of the MMPs. They were also designed to explore the importance of the P1'-P2' amide group, which is known to form highly conserved hydrogen bonds in several MMP-inhibitor complexes, and the viability of introducing a retro amide linkage between P2' and P3'. Pseudopeptides 8 and 9 were found to be weak competitive inhibitors of a series of MMPs. Any entropically favorable conformational constraints that were induced by the cyclopropane in 8 were thus overwhelmed by the loss of the hydrogen bonding capability associated with the P1'-P2' amide group. On the other hand, compounds 10 and 11, which contain a P2'-P3' retro amide group, were modest competitive inhibitors of a series of MMPs. The results obtained for 10 and 11 suggest that there may be a loss of hydrogen bonding capability associated with introducing the P2'-P3' retro amide group. However, because the conformationally constrained pseudopeptide 10 was significantly more potent than its flexible analogue 11, trisubstituted cyclopropanes related to 3 may serve as useful rigid dipeptide replacements in some biologically active pseudopeptides.     

Ruthenium(II) carbonyl complexes of P,P and P,O donor diphosphine ligands,Ph2P(CH2)nPPh2 and Ph2P(CH2)nP(O)Ph2, n = 2, 3 and their activities in catalytic transfer hydrogenation reactions

The polymeric precursor [RuCl₂(CO)₂]_n reacts with the ligands, P∩P (a, b) and P∩O (c, d), in 1:1 M ratio to generate six-coordinate complexes [RuCl₂(CO)₂(?²-P∩P)] (1a, 1b) and [RuCl₂(CO)₂(?²-P∩O)] (1c, 1d), where P∩P: Ph₂P(CH₂)_nPPh₂, n = 2(a), 3(b); P∩O: Ph₂P(CH₂)_nP(O)Ph₂, n = 2(c), 3(d). The complexes are characterized by elemental analyses, mass spectrometry, thermal studies, IR, and NMR spectroscopy. 1a–1d are active in catalyzed transfer hydrogenation of acetophenone and its derivatives to corresponding alcohols with turnover frequency (TOF) of 75–290 h^?1. The complexes exhibit higher yield of hydrogenation products than catalyzed by RuCl₃ itself. Among 1a–1d, the Ru(II) complexes of bidentate phosphine (1a, 1b) show higher efficiency than their monoxide analogs (1c, 1d). However, the recycling experiments with the catalysts for hydrogenation of 4-nitroacetophenone exhibit a different trend in which the catalytic activities of 1a, 1b, and 1d decrease considerably, while 1c shows similar activity during the second run.     

Theoretical study of 31P, 31P coupling constants in cyclotriphosphazenes

Several scalar coupling constants (mainly 31P, 31P) were calculated for 10 cyclotriphosphazenes and compared with experimental results when available. Although the experimental values cannot be reproduced, the calculated values are proportional to the experimental values. Some difficult cases, such as 19F, 19F couplings, are discussed.     

New P,N-Cyclic Ligands

Abstract

The anions of P,N-cyclic metaphosphimic acids (MPm^n-, n = =3, 4…) interact with cations as conformationally labile multidentate ligands. They belong to the cyclophosphazane class and can be obtained from chloroderivatives (NPCl₂)_n associated with a related class of P,N-compounds (cyclophosphazenes. Besides halogens, a great variety of organic radicals can act as substituents in the cyclophospnazenes. An additional introduction of donating atoms or groups in these radicals results in new multidentate ligands. Like the MPm^n- they demonstrate a cation binding ability. Thus P,N-cyclic ligands can contain endocyclic functional groups POO- which are inherent to common MPm^n- or various exo-cyclic groups, e.g. -COO^?, -PR₂O^?, -PROO^?, -NR₂etc., linked to the cycle via side chains. Furthermore, miscellaneous phosphazane-phosphazene structures as well as those with an additional heteroatom can be designed. We have obtained the first examples of P,N-cyclic chelantes of some structural types. These are bicycles based on MPm^n- cross-linked by organic bridges. Such ligands can take a sandwich configuration. Neutral and acido-ligands of cyclo-pendante type involving groups -COO^?, -PPh₂O and >O as well as a ligand with endocyclic sulfur have been obtained too. Selective or universal chelantes, extragents, coloured ligands and other reagents can be synthesized depending on a ligand structure design, the nature of organic fragments linked to the cycle and the type of functional groups.     

Variable coordination behaviour of pyrazole-containing N,P and N,P(O) ligands towards palladium(II)

Three bidentate, mixed-donor ligands based on a triphenylphosphine unit bearing a pyrazole group in the ortho-position of one phenyl ring have been synthesised; the N,P ligand [2-(3-pyrazolyl)phenyl]diphenylphosphine pzphos has been synthesised and transformed into new N,P(O) and N,P(S) derivatives, [2-(3-pyrazolyl)phenyl]diphenylphosphine oxide pzphos(O) and [2-(3-pyrazolyl)phenyl]diphenylphosphine sulfide pzphos(S), respectively. The coordination chemistry of pzphos and pzphos(O) towards palladium(II) has been investigated. Depending on the ligand to metal molar ratio employed in the reactions of palladium(II) with pzphos, either the 1 : 1 chelate [Pd(pzphos)Cl2] 1a or the 2 : 1 N,P chelate [Pd(pzphos)2]Cl2 1b was obtained. 1b contains two six-membered chelate rings in which the chlorides have been displaced from the inner coordination sphere of palladium. Exchange of the chloride anions in 1b for perchlorate anions was achieved using AgClO4 to give [Pd(pzphos)2][ClO4]2 1c. Reaction of pzphos(O) under the same conditions forms the 2 : 1 adduct [Pd(pzphos(O))2Cl2] 2b regardless of the metal to ligand ratio or the order of addition of reactants. Unlike the N,P chelate 1b, the N,P(O) ligands in complex 2b bind in a monodentate fashion through the N-donor atoms of the pyrazole rings. Abstraction of the chloro ligands in compound 2b using AgClO4 gave the 2 : 1 N,P(O) chelate [Pd{pzphos(O)}2][ClO4]2 2c, in which entropically unfavourable 7-membered chelate rings are formed. X-Ray diffraction has been used to confirm the solid-state structures of the pzphos(O) ligand and the complexes 1b, 1c, 2b and 2c.     

Sterically Congested Phosphite Ligands: Synthesis,crystallographic characterization,and observation of unprecedented eight-Bond 31P,31P coupling in the 31P-NMR spectra

The synthesis and characterization of 2-{1-{3,5-bis(1,1-dimethylethyl)-2-{[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy}phenyl}ethyl}-4,6-bis(1,1-dimethylethyl)phenyl diphenyl phosphite ( 6 ) is described. In the ³¹P-NMR spectrum (¹H-decoupled) of 6 , an unprecedented eight-bond P,P coupling of J = 72.8 Hz is observed. In the X-ray crystal structure of 6 , an intramolecular P–P distance of 3.67 Å is found, which is within the sum of the van-der-Waals radii of the P-atoms. The observed intramolecular P–P distance suggests that a through-space coupling mechanism is operative. The solid-state conformation of 6 is compared to the conformation obtained by semi-empirical MO geometry optimizations (PM3 method). The calculated geometry suggests that the solid-state structure is near a true energy minimum, but that crystal-packing forces decrease the intramolecular P–P distance in the solid state. In the absence of crystal-packing forces, however, the collisional and vibrational energy available in solution may lead to the population of states with a shortened intramolecular P–P distance in 6 . The proximity of the P-atoms in 6 is due to restricted conformational freedom resulting from steric congestion within the molecule. The free energy of activation (ΔG* = 10.2 and 10.8 kcal/mol for unequal populations of exchanging conformers) for ring inversion of the dibenzo[d,f][1,3,2]dioxaphosphepin ring in 6 is determined by variable-temperature ³¹P-NMR spectroscopy. Semi-empirical MO calculation on model compounds suggest that the structure of the transition state for ring inversion has the two aryl rings and O-atoms in a common plane, with the P-atom lying above this plane.     

EPR-Untersuchungen an Nitrosyl-Eisen-Chelaten des Typs [FeNO(S,S)(P,P)]

EPR Investigations on Nitrosyl Iron Chelates of the Type [FeNO(S, S)(P, P)] The EPR powder spectra of [FeNO(mnt)(diphos)] and {FeNO(mnt)[P(C₆H₅)₃]₂} (mnt = maleonitriledithiolate, diphos = tetraphenylethylenediphosphine), diamagnetically diluted in the corresponding cobalt chelates, are reported. The nitrosyl iron chelate {FeNO(mnt)[P(C₆H₅)₃]₂} could, However, be only isolated in the host chelate. According to the EPR parameters obtained for [FeNO(mnt)(diphos)] the MO of the unpaired electron consists of the metal d_z2 and the corresponding ligand orbitals. The g tensor components and the ligand hyperfine structure coupling constants found for {FeNO(mnt)[P(C₆H₅)₃]₂} are more in agreement with an MO for the unpaired electron consisting of the metal d_yz and the corresponding ligand orbitals. Large structural deviations are responsible for this difference.