Organophosphorus chemistry volume 39

Specialist Periodical Reports Edited by D W Allen, J C Tebby and D Loakes Organophosphorus Chemistry Volume 40 Organophosphorus Chemistry Volume 40 A Specialist Periodical Report Organophosphorus Chemistry Volume 40 A Review of the Literature Published between January 2009 and January 2010 Editors D.W Allen, Sheffield Hallam University, Sheffield, UK J.C Tebby, Staffordshire University, Stoke-on-Trent, UK D Loakes, Laboratory of Molecular Biology, Cambridge, UK Authors P Bałczewski, Polish Academy of Sciences, Lodz, Poland G Keglevich, Budapest University of Technology and Economics, Budapest, Hungary M Migaud, Queens University, Belfast, UK I.L Odinets, Russian Academy of Sciences, Moscow, Russia R Pajkert, University of Bremen, Bremen, Germany G.-V Roăschenthaler, University of Bremen, Bremen, Germany J Skalik, Polish Academy of Sciences, Lodz, Poland R.N Slinn, University of Liverpool, Liverpool, UK F.F Stewart, Idaho National Laboratory, Idaho, US If you buy this title on standing order, you will be given FREE access to the chapters online Please contact sales@rsc.org with proof of purchase to arrange access to be set up Thank you ISBN: 978-1-84973-138-6 ISSN: 0306-0713 DOI: 10.1039/9781849732819 A catalogue record for this book is available from the British Library & The Royal Society of Chemistry 2011 All rights reserved Apart from fair dealing for the purposes of research for non-commercial purposes or for private study, criticism or review, as permitted under the Copyright, Designs and Patents Act 1988 and the Copyright and Related Rights Regulations 2003, this publication may not be reproduced, stored or transmitted, in any form or by any means, without the prior permission in writing of The Royal Society of Chemistry, or in the case of reproduction in accordance with the terms of licences issued by the Copyright Licensing Agency in the UK, or in accordance with the terms of the licences issued by the appropriate Reproduction Rights Organization outside the UK Enquiries concerning reproduction outside the terms stated here should be sent to The Royal Society of Chemistry at the address printed on this page Published by The Royal Society of Chemistry, Thomas Graham House, Science Park, Milton Road, Cambridge CB4 0WF, UK Registered Charity Number 207890 For further information see our web site at www.rsc.org Preface David Allen,a David Loakesb and John Tebbyc DOI: 10.1039/9781849732819-FP005 This is the 40th in a series of volumes which first appeared in 1970 under the editorship of Stuart Trippett and which covered the literature of organophosphorus chemistry published in the period from January 1968 to June 1969, citing some 1370 publications The present volume covers the literature from January 2009 to January 2010, citing more than 2200 publications, continuing our efforts to provide an up to date survey of progress in an area of chemistry that has expanded significantly over the past 40 years Unfortunately, in this volume we have been unable to provide detailed coverage of the tervalent phosphorus acid derivatives area but hope to remedy this with a two-year survey in the next volume.The past year has seen the publication of a significant number of review articles that are cited in the relevant chapters in this volume Of particular note is the publication of a volume reviewing the recent chemistry of heterocyclic phosphorus compounds that relates to a number of areas covered herein (Phosphorus Heterocycles 1, Ed., R K Bansal; from the series Topics in Heterocyclic Chemistry, 20, Ed., R R Gupta, Springer-Verlag, Berlin, Heidelberg, 2009) The use of a wide range of tervalent phosphorus ligands in homogeneous catalysis has continued to be a major driver in the chemistry of both traditional P–C-bonded phosphines and also that of tervalent phosphorus acid derivatives The general synthetic applicability of tertiary phosphines in the nucleophilic catalysis of carbon-carbon bond formation reactions remains an area of great interest, as also does the formation and reactivity of ’frustrated Lewis pair’ systems involving sterically-crowded phosphines and pentafluorophenylboranes Also significant is the continuing interest in the use of phosphonium salts as ionic liquids, with many new applications again being reported New approaches to the Wittig and related reactions also continue to be developed, including the use of water as a solvent In phosphine chalcogenide chemistry, the synthesis of enantioenriched phosphine oxides and the use of phosphine chalcogenides as ligands has continued to attract attention One of the largest areas of growth over the last 40 years is in nucleotides and nucleic acids Since the first DNA structure was published some 55 years ago, there has been a huge increase in the number of nucleic acid structures reported Nucleotides continue to be of significant interest as potential therapeutic agents, and this is reflected in the continuing interest in ProTides, masked phosphate derivatives, as therapeutic prodrugs There has also been much interest in the synthesis of nucleoside phosphoramidites, largely for synthetic incorporation into oligonucleotides, and also in the a Biomedical Research Centre, Sheffield Hallam University, Sheffield, UK S1 1WB Medical Research Council, Laboratory of Molecular Biology, Hills Road, Cambridge, UK CB2 0QH c Division of Chemistry, Faculty of Sciences, Staffordshire University, Stoke-on-Trent, UK ST4 2DE b Organophosphorus Chem., 2011, 40, v–vi | v  c The Royal Society of Chemistry 2011 synthesis of a broad range of nucleoside pyrophosphate derivatives In the area of nucleic acids there has been further growth in applications, with many aptamers having been selected against a range of targets from small molecules to living cells In addition, many (deoxy)ribozymes have been reported In the field of ribozymes there has been particular emphasis on aptamers with peroxidase or Diels-Alderase activities Nucleic acid nanodevices are another area of particular interest, ranging from defined selfassembly structures to a variety of applications such as logic gates However, the largest area of interest is in the incorporation of modified nucleosides, and whereas previously this has been primarily to investigate duplex stability, now there is a growing emphasis on application The field of quinquevalent phosphorus acids continues to draw much attention, with a large number of publications focusing on aspects of synthesis In particular, there has been a focus on the design of novel ligands for various catalytic reactions However, there is also a growing interest in biological and therapeutic applications, again in the area of prodrug synthesis Novel enantioselective approaches to biologically-active phosphate precursors have been described, and in the area of phosphonic acids, a variety of conjugates, such as peptides and nanoparticles, are described The continued interest in penta- and hexa-coordinated phosphorus compounds is largely due to their potential role in biological processes such as the hydrolysis of RNA and phosphoryl transfer reactions Therefore, considerable attention has been given to the synthesis, chemical transformation, structure and configurational stability of hypervalent organophosphorus compounds During the last year, most research in this area has been focused on the synthesis and structural determination of novel hypervalent phosphorus compounds as well as on the stereochemistry of pentacoordinated chiral spirophosphoranes The role of hypervalent phosphorus compounds in driving several phosphorus-mediated reactions has been studied and a hexacoordinated phosphorus anion has been used as an effective chiral solvating agent in NMR studies There has been an increase in the number of publications addressing phosphazene chemistry which suggests a continuing strong interest in these intriguing materials Prominent is an emphasis on the bioactive and biocompatible nature of these materials, although many other applications also exist Their unique electronic properties and highly flexible backbones, that can be controlled through adroit pendant group attachment, produce numerous materials and structures Novel aspects of the chemistry, structure, and applications of phosphazenes are discussed There has been a marked increase in the use of a combination of physical methods in most chemical studies Included within electronic spectroscopy is the application of the relatively-new technique of photothermal lens spectroscopy (PTLS or TLS), and also a return of applications of X-ray photoelectron spectroscopy (XPS) 31P NMR spin trapping, a recent technique for detecting diamagnetic species, is highlighted as is the synthesis and microwave spectrum of 2-chloroethylphosphine, reported for the first time, and a novel square-wave voltammetric method used for determining organophosphates vi | Organophosphorus Chem., 2011, 40, v–vi CONTENTS Cover A selection of organophosphorus molecules Image reproduced by permission of Dr David Loakes Preface David Allen, David Loakes and John Tebby v Phosphines and related P–C-bonded compounds D W Allen Introduction Phosphines pp-Bonded phosphorus compounds Phosphirenes, phospholes and phosphinines References 1 26 31 35 Phosphine chalcogenides 52 G Keglevich References 70 Organophosphorus Chem., 2011, 40, vii–ix | vii  c The Royal Society of Chemistry 2011 Phosphonium salts and P-ylides 74 Irina L Odinets Introduction Phosphonium salts P-Ylides (phosphoranes) References 74 74 90 100 Nucleotides and nucleic acids: mononucleotides 106 M Migaud Introduction Methodology Mononucleotides Dinucleotides Polyphosphorylated nucleosides References 106 106 108 123 128 134 Nucleotides and nucleic acids; oligo- and polynucleotides 139 David Loakes Introduction Aptamers and (deoxy)ribozymes Oligonucleotide conjugates Nucleic acid structures References 139 163 169 181 186 Quinquevalent phosphorus acids 217 Piotr Ba!czewski and Joanna Skalik Introduction Phosphoric acids and their derivatives Phosphonic acids and their derivatives Phosphinic acids and their derivatives References 217 218 251 282 289 Pentacoordinated and hexacoordinated compounds 297 Romana Pajkert and Gerd-Volker Roăschenthaler Introduction Synthesis and structure determination of novel hypervalent spirophosphoranes 297 298 viii | Organophosphorus Chem., 2011, 40, vii–ix Stereochemistry of pentacoordinated chiral spirophosphoranes Hypervalent phosphorus compounds in chemical processess Application of hypervalent phosphorus compounds in NMR studies References 304 307 313 315 Phosphazenes 316 Frederick 316 316 321 327 342 347 F Stewart Introduction Biomaterials Material applications Novel phosphazene materials Phosphazene co-polymers Instrumental and theoretical aspects of polymer formation and structure Acknowledgments References Physical methods Robert N Slinn Introduction Theoretical and computational chemistry methods Nuclear magnetic resonance spectroscopy Electron paramagnetic (spin) resonance spectroscopy Vibrational and rotational spectroscopy Electronic spectroscopy X-ray diffraction (XRD) structural studies Electrochemical methods Thermal methods and thermochemistry 10 Mass spectrometry techniques References 351 351 356 356 356 362 370 371 374 377 380 381 381 382 Organophosphorus Chem., 2011, 40, vii–ix | ix New a-aminophosphonates, such as (53), have been synthesized and characterized by IR, along with 1H, 13C and 31P NMR spectroscopy,74 and a unique spectroscopic and DFT study has been carried out on synthesized 3-quinolyl-a-aminophosphonates (54) and (55).75 Besides (54) and (55) as main products, monoester phosphonate by-products were also obtained All the quinoline-based a-aminophosphonates were characterized by IR spectroscopy and the results compared with those obtained by NMR studies Combining the experimental IR, 1H and 13C NMR spectra with DFT calculations, the most intense IR bands of diesters (54) and (55) and their derivatives, along with their 1H and 13C NMR resonances, were thus assigned Polyphosphoesters, synthesized via a new and modified inverse phase transfer catalysis polycondensation reaction, have been characterized using IR and 1H, 13C and 31P NMR spectroscopy.76 The polyphosphonate structure of the polymers was confirmed by the IR absorption peaks at 1480-1470 and 1020-1030 cm À (P–Cphenyl), 1250-1240 cm À (P=O), and 1150 and 930 cm À (P-O-Cphenyl) However in the 1200-1300 and 900-1000 cm À regions, there were modifications to the characteristic bands due to P=O and P(O)-O-Cphenyl groups The IR band attributed to the P(O)-OCphenyl group occurred at 960 cm À compared with 920-940 cm À 1corresponding to other polyphosphonates The thermal behaviour of two new cyclotriphosphates, SrKP3O9.3H2O and SrKP3O9, has been studied between 25 and 8001C by IR spectroscopy, XRD, and TGA and DTA thermal analyses.77 SrKP3O9.3H2O leads, between 250 and 3501C, to the corresponding anhydrous phase, SrKP3O9 The vibrational spectrum of SrKP3O9.3H2O was examined and interpreted in the domain of the stretching vibrations of the P3O9 rings, on the basis of the crystalline structure of its isotypic compounds, SrMIP3O9.3H2O (MI=NH4 ỵ , Rb ỵ and Tl ỵ ), and in light of the calculation of the twelve fundamental IR valency frequencies for Cs symmetry As reported earlier,15 the FTIR, Raman and surface-enhanced Raman scattering (SERS) spectra of phenyl phosphate disodium salt were recorded, and the Hartree-Fock calculated vibrational wavenumbers compared with experimental values SERS spectra indicated that the molecule is adsorbed on the silver surface with the benzene ring in a tilted orientation and that the phenyl ring and the phosphate group interact with the silver surface SERS spectra have also been recorded for phosphonate derivatives of N-heterocyclic aromatic compounds, namely ImMeP (56), (ImMe)2P (57), BAThMeP (58), BzAThMeP (59), and (PyMe)2P (60), immobilized on a silver electrode surface, and compared to the Raman spectra of the corresponding solid species.78 The changes in wavenumber, broadness, and enhancement of N-heterocyclic aromatic ring bands upon adsorption are consistent with the adsorption mainly occurring through the N lone-pair of electrons, with the ring arranged in a largely edge-on manner for ImMeP and BzAThMeP, or in aslightly-inclined orientation to the silver electrode surface at an intermediate angle from the surface normal for (ImMe)2P, BAThMeP, and (PyMe)2P A strong enhancement of an approximate 1500 cm À SERS signal for ImMeP and (PyMe)2P is also observed, attributed to the formation of a localized C=C bond which is accompanied by a decrease in the ring-surface p-electrons overlap In addition, in BzAThMeP more-intense 372 | Organophosphorus Chem., 2011, 40, 356–386 SERS bands due to the benzene ring are observed than for the thiazole ring, suggesting a preferential adsorption of benzene Some phosphonate unit interaction is also suggested but with moderate strength between biomolecules The strength of the P=O coordination to the silver electrode is found to be highest for ImMeP and lowest for BzAThMeP For all the biomolecules, the contribution of the structural components to their ability to interact with their receptors correlated with the SERS patterns HO HN N O OH P HO N S H N N OH N PO3H2 N H (56) ImMeP (57) (ImMe)2P N H PO3H2 (58) BAThMeP HO O OH P HN OH S N N PO3H2 N (59) BzAThMeP (60) (PyMe)2P As mentioned earlier,19CPMD simulations were carried out at 300K on deprotonated phosphorylated serine (p-ser-H) À , and the resultant extracted spectrum correlates with the experimental IR spectrum obtained by the recently-developed InfraRed Multiple Photon Dissociation (IRMPD) technique, which was first described in this chapter in Volume 39 5.2 Rotational (microwave) spectroscopy The synthesis and microwave spectrum of 2-chloroethylphosphine has been reported for the first time.79 Microwave spectroscopy was carried out at room temperature and at À 201C in the 22–80 GHz spectral interval The experimental study was combined with quantum chemical calculations at the MP2/6-311 ỵ ỵ (3df,3pd) and B3LYP/6-311 ỵ ỵ (3df,3pd) levels of theory The spectra of two rotameric forms were assigned, both with an anti-periplanar arrangement for the Cl-C-C-P chain of atoms but with different orientation of the phosphine group One conformer was found to be 5.2 kJ/mol more stable than the other by relative intensity measurements The spectra of the first excited states of the C-C torsional vibration of both rotamers were assigned The torsional frequency was determined to be around 63 cm À for both conformers, again using relative intensity measurements The quantum chemical calculations produced rotational and centrifugal distortion constants that are in satisfactory agreement with observations, but they failed to correctly predict low-frequency fundamental frequencies Calculations predicted three additional high-energy conformers with a synclinal orientation of the Cl-C-C-P link of atoms and with a different orientation of the phosphine group, but a search for these forms was unsuccessful Organophosphorus Chem., 2011, 40, 356–386 | 373 Electronic spectroscopy 6.1 Absorption spectroscopy 6.1.1 UV-visible spectroscopy UV-visible spectroscopy is again used primarily as a complementary analytical technique to the other methods available (IR, NMR, XRD, mass spectrometry, etc) for the characterization of organophosphorus compounds Some applications have been mentioned earlier such as a combined experimental and theoretical study on two new Fe(III) complexes (5) and (6).10 TDDFT calculations were carried out to interpret the bands observed in the UV-visible spectra, which were consistent with the calculations demonstrating low-spin octahedral geometry The spectrum of complex (5) in acetonitrile showed one intense absorption band at 352 nm, assigned to intra-ligand n À p* transitions and, compared to the free ligand band at 331 nm, this red shift indicated a change in the electronic environment of the ligand due to complexation The complex (5) also showed a low energy band at 503 nm attributed to ligand-to-metal charge transfer (LMCT) absorptions due to the phosphine-Fe ỵ (3d) transition with some contribution from the coordinated chloride The UV-visible spectrum of the complex (6) in acetonitrile exhibited one intense band at 228 nm and a shoulder at 297 nm was attributed to the intra-ligand p À p* and n À p* transitions, respectively Compared to the free ligand bands at 220 and 294 nm, these shifts are again consistent with a change in the electronic environment of the ligand due to complex formation In addition to the ligandcentred bands, the complex (6) also showed two other bands at 403 nm and 526 nm which may again be attributed to LMCT absorptions The absorption bands of the phosphino-pyridine complex (6) are found to be similar to those obtained for other pyridine-based low-spin Fe(III) complexes The electronic spectra of three new Cu(I) complexes with tricyclohexylphosphine (PCy3) and different diimine ligands have also been recorded and all display yellow MLCT emissions in the solid state at room temperature with absorption maxima (lmax) at 558, 564 and 582 nm, which are similarly shifted to 605, 628 and 643 nm, respectively, in dichloromethane solution.80 The quantitative analysis of bis-(4-carboxyphenyl)-phenylphosphine oxide has been carried out from absorbance measurements at, lmax 302 nm in pyridine solution.81 Other studies involving UV-visible spectroscopy include kinetic investigations 6.1.2 Circular Dichroism (CD) Spectroscopy The molecular structure and absolute configuration at three stereogenic axes of bis-phenylene (ortho and meta) BINOL-based phosphoramidites, and their solution conformations have been studied by transparent spectral region optical rotation (OR), IR, electronic (ECD) and vibrational (VCD) circular dichroism spectroscopy, and the results were compared with ab initio DFT calculations with good agreement.82 As mentioned earlier,14 the solvent-induced stereochemical behaviour of a bile acid-based biphenyl phosphite (BADHP) has been studied theoretically using DFT methods and related to experimental CD spectroscopy results Also, the stereochemistry of chiral pentacoordinate spirophosphoranes (61) has been correlated with solid-state CD and 1H NMR spectroscopy.54 Two sets of diastereoisomers separately derived from L- or D-valine and L- or D-leucine were synthesized, isolated and characterized in 374 | Organophosphorus Chem., 2011, 40, 356–386 the solid state by XRD and CD spectroscopy, and in solution by 1H NMR spectroscopy 6.1.3 (Photo)Thermal lens spectrometry Photothermal Lens spectrometry (PTLS or TLS) is a relatively-new spectroscopic technique coming within the classification of photothermal spectroscopy (PTS), a distinct group of high-sensitivity techniques used for the analysis of chemicals and materials Following the discovery of the ‘photothermal lens effect’ (Gordon et al, 1964), TLS was the first of these techniques used in chemical analysis For an analyte with less than unit fluorescence quantum yield, the electromagnetic energy absorbed, and not lost by subsequent emission, results in an increase in energy of the sample This increase is usually randomized, resulting in sample heating and the photothermal spectroscopy signal is thus derived from this As a direct comparison, photothermal spectroscopy techniques have sensitivities far greater than those obtained with conventional absorption spectrophotometry since PTS is an indirect technique for measuring optical absorption Specifically, the TLS technique measures the thermal blooming that occurs when a laser beam heats a transparent sample and is typically applied to measuring minute quantities of substances in homogeneous gas and liquid solutions A recent application of thermal lens spectrometry has been in the bioanalytical determination of organophosphorus pesticides (OPs) based on inhibition of acetylcholinesterase (AChE) determined in a flow injection system (FIA) by TLS Since thio-forms of OPs exhibit low in vitro potency towards AChE, in order to achieve satisfactory detection limits such thio compounds have to be oxidised to their oxo-form using chloroperoxidase (CPO) enzyme in citrate buffer and an ionic liquid (IL) is required as co-solvent to increase the sensitivity of detection Thus, the effects of selected ionic liquids on the efficiency of CPO oxidation of methyl-parathion (62) to methyl-paraoxon (63) were studied to determine the most suitable IL and experimental conditions (IL concentration) needed to achieve not only efficient oxidation of thio OP compounds, but also highest possible sensitivity of the FIA-TLS AChE assay.83 Photothermal enhancement factors of 3.5 times and corresponding improvements of sensitivity in the determination by the FIA-TLS method are predicted in 30% ionic liquids R ∗ H N ∗ O H N ∗ R CPO+ O2N S P OH O O P O ( 61) (62) R = L- or D-valine and L- or D-leucine O Me Me H202/KCl IL/citrate O2N O O P O O Me Me (63) 6.2 Fluorescence and luminescence spectroscopy The structural and fluorescence properties of three novel phenolphthalein bridged cyclo-triphosphazatrienes have been reported.84 The new compounds (64)–(66) were characterized by mass spectrometry, FT-IR, 1H, 31P NMR, UV-visible, and fluorescence spectroscopy It was observed that (64) and (65) show weak absorption at 260-280 nm, whereas the trimer (66) shows a more intense absorption at 275 nm The compounds (65) and (66) feature strong fluorescence at 400 nm upon excitation at 240 nm, whereas the monomer (64) shows weaker fluorescence at 320 nm The more bridged Organophosphorus Chem., 2011, 40, 356–386 | 375 phenolphthalein groups show the higher intensity of the absorption bands in the UV-visible spectra O O Cl2P N Cl2P N P O N Cl O Cl P N Cl2P N Cl P Cl N n (64 - 66) n = - HO R OH N PPh2 (67) R = H (dppq) or R = Me (mdppq) HOOC N+ O CH2PO3H- (68) A modular route to chromophoric diphosphines, and their use in the preparation of luminescent metallopolymers of Pt and Pd, has been reported.85 Also, two novel mixed-ligand Cu(I) complexes [Cu(NP)(DPEphos] ỵ , containing DPEphos (bis[2-(diphenylphosphino)phenyl]ether) and dppq or mdppq ligands (67), have been synthesized and characterized by XRD, electrochemical and photophysical measurements.86 It was shown that luminescent heteroleptic Cu(I) complexes based on asymmetrical iminephosphine ligands, such as mddq, exhibit improved electrochemical and photochemical stability compared to analogous complexes based on diimine or diphosphine ligands Lanthanide imidodiphosphinate (pip) complexes, Ln(pip)3, (Ln=Ce, Nd, Tb, and Ho) have been synthesized, structurally characterized by XRD, and their electroluminescent properties investigated for organic light emitting diode (OLED) applications.87 Also the synthesis, crystal structure and luminescence properties of seven novel lanthanide(III) squarato-aminophosphonates Ln(HL2), containing the H4L2 ligand (68), have been described.88 The Eu, Tb and Nd compounds exhibit strong luminescence in red light, green light, and near-IR regions, respectively Similarly, two new zinc phosphonates have been synthesized, characterized, and display purple and yellow-green emissions, respectively.89 A trivalent neodymium (Nd3 ỵ ) complex, Nd(PM)3(TP)2, has been synthesized and its optical properties studied by introducing Judd-Ofelt theory to calculate the radiative transition rate and radiative decay time of the 4F3/2 - 4IJ0 transitions in this complex.90 Strong emissions in the near-IR (NIR) region are due to the efficient energy transfer from ligands to the central metal ion The potential application of this complex in NIR electroluminescence was studied on several devices and the maximum NIR irradiance obtained was 2.1 mW/m2 at 16.5 V 6.3 Photoelectron spectroscopy 6.3.1 UV photoelectron spectroscopy (UPS) Ethynyl- and allenylphosphine-boranes, along with methyl-, vinyl-, allyl-, and propargylphosphine-boranes, have been investigated using UV photoelectron 376 | Organophosphorus Chem., 2011, 40, 356–386 spectroscopy and DFT/B3LYP calculations so as to define the variation in electronic effects between the free phosphines and corresponding phosphine-boranes.91 Complexation led to only minor changes for the a,bunsaturated compounds since similar structures are found for the conformers of the complexes and phosphines The P-C bond shortenened in all cases due to charge transfer from phosphorus to boron on complexation Except for the allenyl derivative, the order of the relative stability remained the same in phosphines and phosphine-boranes and the rotational barriers are also comparable The calculated complexation energies, between 80-100 kJ/mol, are in agreement with flash vacuum thermolysis experiments The photoelectron spectra can be easily described in the case of a,b-unsaturated compounds since the direct conjugation between the lone electron pair and the p-bond has to be exchanged to a hyperconjugation between the sP À B bond and the unsaturated moiety In the case of b,g-unsaturated derivatives, the observed hyperconjugation in phosphines disappears on complexation and no interaction with the phosphorus atom could be observed 6.3.2 X-ray photoelectron spectroscopy (XPS) X-ray photoelectron spectroscopy has been used to study the effect of X-rays (at 1253.6 eV) on the surface composition of poly{bis(trifluoroethoxy)phosphazene}.92 The X-ray source was used for modification of the surface as well as for generation of photoelectrons and increases in exposure time and irradiation dose over criticality led to changes in elemental composition of the surface and surface properties of poly{bis(trifluoroethoxy)phosphazene} X-ray diffraction (XRD) structural studies Solid-state structural analyses for the characterization of organophosphorus compounds include XRD studies As with IR/Raman, UV, NMR spectroscopy and Mass Spectrometry, XRD is a complementary technique for full structure elucidation The applications below are selective overall and other applications have already been mentioned earlier.4,29,32,35,52 Monoaurated [Mes*{AuCl}P=PMes*] and diaurated [Mes*{AuCl}P= P{AuCl}Mes*] adducts of the hindered diphosphene (Mes*P=PMes*), where Mes*=2,4,6-tri-tert-butylphenyl, have been synthesized and characterized by XRD, IR/Raman, UV-visible, and multinuclear NMR spectroscopy, as well as by DFT calculations.93 The crystallographic and Raman spectroscopic data provide evidence that the P=P bond grows shorter and increases in strength upon auration, and DFT calculations on model compounds support this finding The compounds allow a systematic analysis of the impact of Lewis acids on the P=P bond The structure of sodium 3,5-diphenyl-2,4-diazaphospholide has been characterized by XRD study as a one-dimensional coordination polymer, [Na(dme){P(CPh)2N2}]n.94 The first 1,2-bis(diphenyl phosphino)-1,2-diphenylhydrazine ligand, [Ph2PN(Ph)N(Ph)PPh2], and its square- planar Ni(II), Pd(II) and Pt(II) complexes, have also been characterized by XRD.95 In the ligand, the P-N-N-P chain has a cis configuration, the two N atoms in a planar environment with the angles adding to 359.81 around N1 and N2, and the P-N and N-N distances are in the range comparable to related diphenylphosphino-1,2-diarylhydrazines In the compound 1,1,2,2tetrakis(diisopropylamino)diphosphane,96 the distance between the P atoms Organophosphorus Chem., 2011, 40, 356–386 | 377 (2.2988/2.3013 A1 major/minor occupancy components, respectively) is found to be one of the longest reported for uncoordinated diphosphanes The molecule is disordered over two positions with site-occupation factors of 0.6447 and 0.3553 The structure adopts the syn-periplanar conformation in the solid state with a N-P-P-N torsion angle of 14.71 A new triaryl phosphine complex [HgCl2(PPh2Bz)2], with a larger P-Hg-P angle, longer Hg-Cl, and shorter Hg-P bond, has been synthesized and analysed by XRD.97 A comparison of the sensitive bond parameters with similar compounds, together with Gaussian calculations, show that the s-donating abilities of triaryl phosphine ligands toward HgCl2 decrease in the order: PEt3 W PPh2Bz W P(2-thienyl)3 W dppf W PPh3 A series of trityl-supported P(III) and P(V) complexes have been synthesized and characterized through single-crystal XRD, NMR, IR and mass spectrometry Comparison of their structural features reveal that the P-C bond length decreases as the phosphorus oxidation state increases from ỵ to ỵ arising from less electronic repulsion As a result, the 31P NMR chemical shifts become shifted downfield.98 Five vicinal bis(alkyl-triarylphosphonium salts) (69) derived from o-bis(diphenyl-phosphino)benzene (o-dppb) have been prepared and their formal electrostatic and possible van der Waals strain compared through the P ỵ P ỵ distances in the crystal.99 Their stereochemistry in the crystal state and stereodynamics in solution result from a complex interplay between electrostatic, steric and covalent effects which were also studied by DFT calculations According to XRD analysis, while the conformations of the dimethyl dication (69, R=Me) is C2 symmetric, the conformation of alka-1, n-diyl-diphosphonium salts (n=1, 2, 3) is pseudo-Cs symmetric The compound 4-carboxybutyl-triphenylphosphonium bromide has also been characterized by using XRD and quantum chemical calculations.100 In tris(4-tert-butylphenyl) phosphine oxide, the P=O bond length is 1.4866 A1 and the P-C bond lengths range from 1.804 to 1.808 A1 The molecule is located on a crystallographic mirror plane and the methyl groups of one tert-butyl group are disordered over two sites in a 0.776 : 0.224 ratio.101 A photochemical synthesis of l5-phosphinolines has been reported and the structures of two phosphinolines (70) and (71) established by single-crystal XRD.102 The XRD and NMR spectra data indicate the superposition of ylidic and aromatic structures for phosphinolines +Ph2 XP Me Me P +Ph2 (69) X = TfO- or BF4- P P O O Ph Ph Ph (70) (71) A novel cyclotetraphosphate, (2-NH2-5-ClC5H4N)4P4O12.6H2O, has been synthesized and characterized by single crystal XRD.103 The compound crystallizes in an orthorhombic unit cell Pccn and the structure can be described as inorganic layers stacked along the a-direction and held together through N-H .O hydrogen bonds, originating from the organic cations, giving rise to three-dimensional H-bonded assemblies In addition, 378 | Organophosphorus Chem., 2011, 40, 356–386 there is electrostatic, van der Waal forces and Cl Cl interaction so as to increase the cohesion of the 3D-network A new library of a-aminophosphonates, R1NH-CH(R)-P(O)(OiPr)2, has been synthesized and characterized by IR, 1H and 31P NMR spectroscopy, and the crystal and molecular structures of p-XC6H4-NH-CH(p-XC6H4)-P(O)(OiPr)2 (X=H, Br, MeO) established by single crystal XRD.104 The synthesis, crystal structure and biological activities of N-(4-cyanopyrazole-3-yl)- a-(3,5-difluorophenyl)-O, O-diisopropyl-a-aminophosphonate has been reported.105 From XRD, the compound crystallizes in monoclinic, space group C2/c The results demonstrate that the dihedral angle between the pyrazole and benzene rings is 105.51 and there is a full delocalized pyrazole system with sp2 hydridization of N(3) The crystal structure is stabilized by two intermolecular hydrogen bonds of N(1)-H(1) .O(3) and N(3)-H(3A) .N(4) The phosphoramidate ester (72) has also been synthesized and characterized, spectroscopically and by single crystal XRD.106 In the crystal, (72) is constructed of a centrosymmetric dimer unit composed of a pair of p-p stacking diastereoisomers It has a noteworthy feature in the framework and such units are linked by two equal intermolecular P=O H-N hydrogen bonds Me O N O Me O O P O NH O H C C O CH2CH3 Me (72) The synthesis, and characterization by multinuclear NMR and single crystal XRD, of the first heterodimetallic PCP-pincer-carbodiphosphorane complex, [PdAu(Cl)2(C(dppm)2)]Cl, has also been reported.107 Both metals are attached to the C atom of the carbodiphosphorane functionality and are connected via a very short d8-d10 pseudo-closed shell interaction, with PdAu distance=2.8900 A1, which significantly modifies the ligand backbone conformation The absolute configurations and coordination properties of the P-chiral cycloadducts, from the chiral organo-Pt complex-promoted asymmetric Diels-Alder reaction of 3,4-dimethyl-1-phenylphosphole and 3-diphenylphosphinofuran, have been established by X-ray analysis.108 The novel [Na(18-crown-6)(H2O)2] ỵ HO3 À PCH=CHPh.18-crown- 6.H2O3 PCH=CHPh] has been prepared and its crystal and molecular structures studied by X-ray structural analysis.109 In this structure, the complex cation [Na(18-crown-6)(H2O)2] ỵ is of the guest-host type The coordination polyhedron of its Na ỵ cation is a slightly-screwed hexagonal bipyramid with the base consisting of all O atoms of 18-crown-6 ligand and with two opposite apexes at two O atoms of two ligand water molecules In the crystal structure, the alternating complex cations and 18-crown-6 molecules as well as the molecules of acid and its anion HO3–PCH=CHPh form, by means of hydrogen bonds, infinite chains of two different types Organophosphorus Chem., 2011, 40, 356–386 | 379 Other applications of XRD in characterization involve three novel bisphosphonates bearing an acridine moiety,110 a new acetyl phosphorylamidate,111 and the first example of a hexaacoordinate phosphorus compound with two S - P bonds.112 The stereochemistry in pentacoordinate spirophosphoranes has also been determined using XRD and spectroscopic analysis.113 Electrochemical methods 8.1 Voltammetry The use of cyclic voltammetry (CV) has been mentioned earlier during the characterization of the two mononuclear Fe(III) complexes (5), and (6).10 An acetonitrile solution was used with 0.1 M TBAP as the supporting electrolyte It was shown that (5) exhibits a one-electron redox process at E1/ III - FeIV ỵ e redox system, and the 2=0.316 V attributed to the Fe process is chemically as well as electrochemically irreversible as indicated by iPc/iPa 6¼ and an extremely high DEp value of 632 mV In addition there is another oxidation peak at 1.072 V attributed to the irreversible ligand oxidation Similarly complex (6) also exhibits an irreversible redox couple for FeIII/FeIV oxidation at E1/2=0.106 V with DEp=212 mV along with the ligand oxidation peak at 1.159 V A novel square-wave voltammetry (SWV) method has been developed for the detection of organophosphorus pesticides (OPs) by inhibition of cholinesterase (ChE) from earthworm.114 Two immiscible phases are employed where the organic phase (isooctane) contains substrate and the aqueous phase contains enzyme Water-insoluble indophenol acetate is hydrolyzed by ChE at the interface of the two phases to produce watersoluble indophenol which then spontaneously passes into aqueous solution giving a change in electrochemical signal Methyl parathion in isooctane inhibits the ChE activity at the interface and a corresponding inhibition relationship was given in the concentration range of 50 ng/ml–100 mg/ml, as an example 8.2 Electrochemical sensors and biosensors A sensitive and selective electrochemical analysis of the OPs methyl parathion (MPT) and 4-nitrophenol (PNP) has been carried out using a new type p-NiTSPc/p-PPD coated carbon fibre microelectrode (CFME),115 and tricresyl phosphate has been determined in aqueous samples and air using a copper nanoparticles and carbon nanotubes-based electrochemical sensor.116 Similarly, dimethyl methylphosphonate (DMMP) and ethanol vapours have been determined using a high-performance nanocomposite material based on functionalized carbon nanotubes and polymers coated on a surface acoustic wave (SAW) device.117 8.3 Other electroanalytical applications An automated potentiometric titration method has been described for N-(phosphonomethyl) iminodiacetic acid118 and a theoretical method has been developed to successfully predict the oxidation potentials of a number of amines and thus a range of organophosphorus compounds in CH3CN 380 | Organophosphorus Chem., 2011, 40, 356–386 with a precision of about 0.08 V.119 With these theoretical values, a scale of reliable oxidation potentials was constructed for the first time for organophosphorus compounds, useful for selecting suitable organophosphorus reagents for electrochemistry reactions On the basis of these oxidation potential values, substituent effects on the oxidation potential values for various types of organophosphorus compounds were also studied Thermal methods and thermochemistry Thermal methods including differential thermal analysis (DTA), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) have been used mainly in the analysis of polymers, particularly the characterization and thermal properties of cyclotriphosphazenes and polyphosphazenes, as mentioned earlier, when in combination with spectroscopic and structural studies Other applications include the characterization and thermal stabilities of a novel polyphosphamide with enhanced P-N content,120 of phosphaphenanthrene-containing polyacetylenes,121 metal cyclodiphosph(V)azane complexes,122 spirocyclophosphazenes,123 and a new bis-iminophosphorane.124 10 Mass spectrometry techniques As with the other physical methods this is a complementary technique for the characterization of organophosphorus compounds The electron ionization (EI) mass spectrometry reactions of dimethylphenyl phosphine have been studied by tandem mass spectrometry (MSn) using deuterium labelling, and the results compared to those for dimethylaniline and dimethylphenyl arsine to examine the effects of heavy main group heteroatoms on the reactions of radical cations of the pnictogen derivatives C4H5E(CH 3)2 for E=N, P and As.125 An electrospray ionization (ESI) mass spectrometric study has been performed on the interactions between crown ethers and tetramethyl- ammonium- and phosphonium cations.126 Bisphosphonates have been studied by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) with different matrices to study the formation and fragmentation of the protonated, cationized (MNa ỵ and MK ỵ ) and deprotonated bisphosphonates.127 Some in-source fragmentations were observed both in positive and negative ion modes The fragmentation patterns obtained in the post-source decay mode were also discussed In contrast to previous ESI-MSn studies, some new fragmentation pathways were deduced and the effects of alkali metal ions on the fragmentation shown The results summarized data previously recorded by ESI-MSn and could be used for the characterization of bisphosphonates as alkali metal complexes in biological mixtures The effect of the structure of alkoxy radicals on the fragmentation of dialkyl alkylphosphonates has also been studied.128 Polyphosphoesters have been characterized by FT ion cyclotron resonance (FT-ICR) mass spectrometry.129 FT-ICR mass spectrometry, together with collision-induced dissociation (CID) and electron capture dissociation (ECD), has been used to characterize poly[1,4-bis(hydroxyethyl)terephthalate-alt-ethyloxyphosphate] and its degradation products Three degradation pathways : hydrolysis of the phosphate–[1,4-bis(hydroxyethyl)terephthalate] bonds, hydrolysis of the phosphate-ethoxy bonds, and hydrolysis of the ethyl-terephthalate bonds, were Organophosphorus Chem., 2011, 40, 356–386 | 381 elucidated The dominant degradation reactions were those that involved the phosphate groups.This work constitutes the first application of mass spectrometry to the characterization of polyphosphoesters 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recent chemistry of heterocyclic phosphorus compounds that relates