Organophosphorus chemistry vol 40

Specialist Periodical Reports Edited by D W Allen, J C Tebby and D Loakes Organophosphorus Chemistry Volume 41 Organophosphorus Chemistry Volume 41 A Specialist Periodical Report Organophosphorus Chemistry Volume 41 A Review of the Literature Published between January 2010 and January 2011 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, Ło´dz´, Poland and Jan Długosz University in Cz˛estochowa, Poland H Groombridge, Defence Science and Technology Laboratory, Salisbury, UK G Keglevich, Budapest University of Technology and Economics, Budapest, Hungary M Migaud, The Queen’s University of Belfast, UK I L Odinets, Russian Academy of Sciences, Moscow, Russia R Pajkert, Jacobs University Bremen GmbH, Germany G.-V Roăschenthaler, Jacobs University Bremen GmbH, Germany J Skalik, Polish Academy of Sciences, Ło´dz´, Poland R N Slinn, University of Liverpool, UK F F Stewart, Idaho National Laboratory, Idaho Falls, ID, USA 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: 978-1-84973-377-9 ISSN: 0306-0713 DOI: 10.1039/9781849734875 A catalogue record for this book is available from the British Library & The Royal Society of Chemistry 2012 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: 10.1039/9781849734875-FP005 This volume, No 41 in the series, covers the literature of organophosphorus chemistry published in the period from January 2010 to January 2011, and continues our efforts in recent years to provide an up to date survey of progress in this topic which continues to generate a vast amount of research Papers from the 18th International Conference on Phosphorus Chemistry, held in Wroc"aw, Poland in 2010 have now appeared in issue of volume 186 of Phosphorus, Sulfur, Silicon, (2011) With regret, we note the death of Pascal Le Floch early in 2010 In recognition of his many contributions to the chemistry of organophosphorus compounds, a special edition of the journal Comptes Rendus Chimie (2010, 13,(8–9), 889) has been published, containing almost 40 papers dedicated to his memory The use of a wide range of tervalent phosphorus ligands in homogeneous catalysis continues to be a major driver in the chemistry of both traditional P–C-bonded phosphines and also that of tervalent phosphorus acid derivatives Noteworthy is the growing application of tertiary phosphines as nucleophilic catalysts in the reactions of electrophilic unsaturated systems, leading to new synthetic approaches Interest has also continued in a growing series of reactions of sterically-crowded arylphosphine-arylboranes (Frustrated Lewis Pair (FLP) systems) leading to the activation of small molecules such as dihydrogen and carbon dioxide The use of phosphonium salts as ionic liquids has also continued to expand, with many new applications being reported and the Wittig and related reactions have continued to be widely employed in synthesis In phosphine chalcogenide chemistry, it is interesting to note the growing interest in the chemistry of secondary phosphine chalcogenides and their use as ligands in catalytic systems The chapter on tervalent phosphorus acid derivatives covers a two year period between January 2009 and December 2010 The emphasis is on the synthesis, novel uses and applications of tervalent phosphorus acid derivatives, and a major aspect of this area of chemistry is the use of derived ligands as precursors to catalysts for a range of synthetic transformations During this period the first P-chirogenic aminophosphane-phosphinite ligand, supported on the upper rim of a calix[4]arene moiety, has been reported The synthesis of rhenium complexes with phosphites, phosphonites and phosphinites has been discussed, along with the coordination chemistry of perfluoroalkylated phosphorus(III) ligands with palladium, platinum, rhodium and iridium Nucleotides and oligonucleotides continue to be a source of much research, and 2010 has seen a strong emphasis on the chemistry of cyclic a Biomedical Research Centre, Sheffield Hallam University, Sheffield, S1 1WB, UK Medical Research Council, Laboratory of Molecular Biology, Hills Road Cambridge, CB2 0QH, UK Email: d.w.allen@shu.ac.uk c Division of Chemistry, Faculty of Sciences, Staffordshire University, Stoke-on-Trent, ST4 2DE, UK b Organophosphorus Chem., 2012, 41, v–vii | v  c The Royal Society of Chemistry 2012 nucleotides and of dinucleotides, particularly highlighted by the development of solid phase methodologies allowing for synthetic divergence both in terms of phosphorus functionality and nucleosidic diversity As such, a large number of novel nucleosidic polyphosphate and phosphonate analogues have been reported In the field of nucleic acids, the main growth areas have been in nucleic structure determination, aptamers and (deoxy)ribozymes and nanotechnology As structure-based drug design has become one of the dominant means of identifying new therapeutic agents, so the number of nucleic acid-protein structures has expanded to meet this need During this period there have been more nucleic acid-protein structures than for nucleic acids alone, as has been the case in previous years In the field of aptamers, once again there has been an increase in interest, perhaps again driven by therapeutic nucleic acid drug design and for diagnostic assays of clinical targets One of the main growth areas of nanotechnology has been in single molecule studies, largely aimed at an understanding of nucleic acid-protein interactions There have also been many reports describing novel nucleic acid nanostructures, with the ability to control nucleic acids, and these growth areas suggest a new direction in nucleic acid chemistry as we learn more about how these biomolecules interact Coverage of pentavalent phosphorus acid compounds reflects the literature concerning phosphoric, phosphonic and phosphinic acids and their derivatives, highlighting some of the most important developments The area of phosphoric and phosphonic acids has seen growth in the chemistry of novel chiral phosphoric acids which have been applied to many reactions such as epoxidation of olefins, the Baeyer-Villiger oxidation, aldol-type reactions, pinacol rearrangements, Mannich-type reactions, transacetalisation reactions, glycosylation reactions, asymmetric addition reactions, amination and, arylation reactions, reductions and acetalisation reactions Syntheses of useful fluorescent phosphates and application of fluorescent techniques have led to new fluorescent assays for serine and threonine protein phosphatases, enzyme inhibitors and HIV and HCV phosphate and phosphonate based inhibitors A number of publications describe hetero-[3ỵ2] and [4ỵ2] Diels-Alder reactions of unsaturated phosphonates with various dienophiles and heterodienophiles, mostly nitrogen, leading to heterocycles in excellent diastereo- and enantioselectivities, as well as a number of multicomponent reactions involving unsaturated phosphonates, leading to a variety of heterocycles in one step processes There has been further evidence of the role of hypervalent phosphorus in both organophosphorus reactions and biological processes Spirophosphoranes, acyclic and monocyclic compounds have been synthesised Antiapicophilic spirophosphoranes bearing novel bulky fluorinated ligands as well as their stereochemical behaviour and structural properties have been reported Potential biological activity of some spirophosphoranes and synthetic routes to those possessing amino fragments in the structure have been also investigated Regioselective catalytic addition of a H-spirophosphorane to various alkynes and a cascade reaction of a dioxaphosphole derivative with activated carbonyl compounds leading to caged bicyclic spirophosphoranes have been discussed The absolute configuration of vi | Organophosphorus Chem., 2012, 41, v–vii chiral spirophosphoranes in solution as well as the structure, energetics and stereomutation of other phosphoranes have been studied Tetracyclic hexacoordinated compounds bearing a transannular N–P bond have been synthesised and the application of chiral phosphates as NMR solvating agents has been studied In the phosphazene field there has been an increasing interest in biomedically related materials They have been produced with amphiphilic character that can be used to achieve high levels of biocompatibility There has been developments in the control and prediction of specific properties for use as immunoadjuvants, medical composites, and drug delivery agents Other aspects have involved new compounds for a variety of applications, such as electrolytes, lubricants, and composites More often seen is the inclusion of phosphazenes in other types of materials including optically active chromophores, inorganic composites and metal complexes Thus, the unique properties and chemistries of phosphazenes continue to be developed in an ever-expanding manner, enabling the creation of a broader range of new materials Central to the uniqueness of phosphazenes is the core of these structures involving cyclic or linear backbone systems Organophosphorus chemistry is particularly suitable for study by physical methods Theoretical and computational chemistry have continued to expand They include ab initio, density functional theory, semi-empirical and empirical calculations, and molecular mechanics and molecular dynamics NMR, IR and UV-visible spectroscopy, mass spectrometry, X-ray diffraction analysis and elemental analysis complete the suite of methods available for the characterization of novel compounds X-ray crystallography of an aliphatic diazaphosphorinane shows it to involve the first example of a P¼O bond in the equatorial position of the ring There have been further examples of the use of isotopically-labelled monomethylphosphate and -thiophosphate in studies of the stereochemical outcome of phosphoryl transfer reactions Electronic circular dichroism (ECD) has been re-evaluated for its potential to determine directly the absolute configurations of isotopically labelled chiral phosphates There have been new analytical uses of fluorescence spectrophotometry, and also extensions to a novel three-dimensional gas chromatography (GC3) system Organophosphorus Chem., 2012, 41, v–vii | vii CONTENTS Cover A selection of organophosphorus molecules Image reproduced by permission of Dr David Loakes Preface v David Allen, David Loakes and John Tebby Phosphines and related P–C-bonded compounds D W Allen Introduction Phosphines pp-Bonded phosphorus compounds Phosphirenes, phospholes and phosphinines References 1 28 32 36 Tervalent phosphorus acid derivatives H J Groombridge Introduction Halogenophosphorus compounds Tervalent phosphorus esters Tervalent phosphorus amides References 56 Phosphine chalcogenides G Keglevich References 89 56 56 58 71 77 109 Organophosphorus Chem., 2012, 41, ix–xi | ix  c The Royal Society of Chemistry 2012 Nuclear Double Resonance (ENDOR) spectroscopy investigation has been performed on a series of Cr(I) carbonyl complexes [Cr(CO)4L] ỵ (L=Ph2PN(R)PPh2 and Ph2P(R)PPh2) that are used as pre-catalysts for the selective oligomerization of ethene.58 The spectra of the complexes were recorded in frozen dichloromethane at 140 K for EPR and 10 K for ENDOR spectroscopy R Me R Me N+ O– (32) R = Me (DMPO), (EtO)2(O)P (DEPMPO), Me R = R* (CYPMPO), R* = Me Ph2(O)P (DPPMPO) N O O– (33) R = Me (DMPOX), O P O O (EtO)2(O)P (DEPMPOX), R = R* (CYPMPOX), Ph2(O)P (DPPMPOX) Vibrational and rotational spectroscopy 5.1 Vibrational (IR and Raman) spectroscopy The use of IR (and to a lesser extent Raman) spectroscopy, as a complementary technique to the other physical and computational methods for characterization, is unlimited and some applications have been reported earlier Thus, the novel N-phosphinyl ureas (5),10 the first generation dendron G’v1 built from a cyclotriphosphazene core,11 phenylphosphonic acid and phenylthiophosphonic acid,13 the 2H-1,4,2diazaphosphole (15) and 1,3,5-oxazaphosphol-3-ene complexes (16),33 and the novel phosphoramidates,44 have been characterized using IR, UV, MS, and NMR spectroscopy Also, the different orientations of P¼O versus C¼O in the P(O)NHC(O) skeleton in the phosphorus(V)-nitrogen compounds (21) and (22) have been discussed.53 Thus, by using HF and DFT, NMR, X-ray data and the IR spectra of (21) and (22), this revealed that the acyclic compound (22), containing P¼O and C¼O in an anti position, is involved in a stronger N–H O¼P hydrogen bond in the crystal network The IR/Raman and DFT analysis of new octathiotetraphosphetane ammonium salts and a Cu(I) complex has been reported.59 The spectral analysis reveals clear features, characteristic for a P4S84À anion, which are present in the IR and Raman spectra of all the compounds obtained The FT-Raman spectra of 10 generations of P-containing dendrimers containing P¼S and P¼O bonds with terminal benzaldehyde and P-Cl groups have been recorded and analyzed.60 The influence of encirclement on the band frequencies and intensity was studied Lines in the Raman difference spectrum G’2(O) – G’2(S) have characteristic EPR-like form The strong line at 1602 cmÀ1 shows marked changes in intensity for -CH¼O or -CH¼N substituents in the aromatic ring Analysis of difference spectra assigned the following characteristic lines, P¼S stretching vibrations for the bonds in the core, repeating unit, and terminal group Also, the FT-IR and FT-Raman spectra of a dendron G0 built from a cyclotriphosphazene core with five terminal carbamate and one ester groups have been recorded alongside DFT theoretical calculations.61 Finally, a pattern for calculating 398 | Organophosphorus Chem., 2012, 41, 385–411 the vibrational spectra of organophosphorus compounds within the framework of the DFT/B3LYP method has been described with Sarin and Soman molecules as examples.62 5.2 Rotational (microwave) spectroscopy In Volume 40, the synthesis and microwave spectrum of 2-chloroethylphosphine was reported for the first time.63 In continuing work, chloromethylphosphine, (ClCH2PH2) has been studied by microwave spectroscopy at À30 1C in the 22–80 GHz spectral interval.64 The experimental study was accompanied by quantum chemical calculations at the MP2/aug-cc-pVQZ and B3LYP/aug-cc-pVTZ levels The spectra of the ground, as well as of several vibrationally-excited states of the 35ClCH2PH2 and 37ClCH2PH2 isotopologues of two rotameric forms, (34a) and (34b), were assigned These have different orientations of the phosphino group Whereas (34a) has a symmetry plane, consisting of the Cl-C-P link of atoms, in (34b) the phosphino group is rotated out of this symmetry plane (34a) was found to be 4.3 kJ/mol more stable than (34b) by relative intensity measurements The rotational and quartic centrifugal distortion constants calculated using the MP2/aug-ccpVQZ procedure are in very good agreement with their experimental counterparts, but poorer agreement was found for the B3LYP/aug-cc-pVTZ calculations Both computational procedures predict energy differences between (34a) and (34b) close to the experimental energy difference It was suggested that (34a) is the preferred form because it is stabilized by weak intramolecular H-bonding between the Cl atom and the H atoms of the phosphino group Repulsion between the lone electron pair of the P atom and the Cl atom also stabilizes (34a) relative to (34b) H H C P H Cl H (34a) H H H C Cl P H (34b) Electronic spectroscopy 6.1 Absorption spectroscopy 6.1.1 UV-visible spectroscopy UV-visible spectroscopy is used primarily as a complementary analytical technique to the other methods available (IR, NMR, XRD, mass spectrometry) for characterization, and some applications have been mentioned earlier.7,19,33,39 Thus, in the Tc2X4(PMe3)4 (X=Cl, Br) complexes,7 the UV-visible spectra were recorded and show a series of low-intensity bands in the range of 10,000–26,000 cmÀ1 Quantum-chemical calculations predicted that the lowest energy band corresponds to the d*-s* transition, and the difference between calculated and experimental values was 228 cmÀ1 (X=Cl) and 866 cmÀ1 (X=Br) The next bands are attributed to d*-p*, d-s*, and d-p* transitions Also, in Organophosphorus Chem., 2012, 41, 385–411 | 399 the acylated asymmetric dithienophospholes,19 DFT calculations were used to explore the extent of delocalization in the molecular orbitals as suggested by the bathochromic shifts in their UV-visible absorption and fluorescence emission spectra In the 2H-1,4,2-diazaphosphole complex (15),33 the UV-visible absorption spectrum shows a low-energy transition at 404 nm assigned to a metal-diazaphosphole (ligand) charge transfer (MLCT) process A more intense p-p* absorption appears at lmax=296 nm Another broad visible band appears at lmax=539 nm, assigned either to one or more nearly degenerate d-d transitions of Fe(II), or to a MLCT (dp-p*) process occurring from the Fe centre to the acceptor-substituted cyclopendadienyl ring The UV-visible spectra of (16) show one lmaxB240 nm and shoulders at lmaxB466 nm Finally, in addition to NMR and theoretical studies, a kinetic study on new P ylides was undertaken by UV spectrophotometry for the effects of solvent, structure of reactants (different R groups in the dialkyl acetylenedicarboxylates), and also concentration of reactants on the rate of reactions.39 The proposed mechanism was confirmed from the results using a steady-state approximation, and the first step (k2) of the reaction was recognized as ratedetermining step 6.1.2 Elecronic circular dichroism (ECD) spectroscopy It is known that isotopically-labelled monomethyl [16O, 17O, 18O]-phosphate (MePi*) and [16O, 17O, 18O]-thiophosphate (TPi*) are very useful for distinguishing the stereochemical outcome of phosphoryl transfer reactions Now, the use of conventional 31P NMR spectroscopy for the stereochemical analysis of the required derivatives involves complex chemical and enzymatic transformations, resulting in low method sensitivity, and so the use of electronic circular dichroism (ECD) for the direct absolute configuration of MePi* is very desirable However, unfortunately ECD has been found to be unreliable for analysis of MePi* due to a very weak signal To investigate these findings further, the technique has been revisited, reevaluating its potential to determine directly the absolute configurations of the isotopically chiral phosphates MePi* (S-35) and TPi* (R-36a) and (S-36b) using ECD, NMR, mass spectrometry, and Time-dependent DFT (TDDFT) calculations.65 The synthesis for, and improved purification of, MePi* and TPi*, together with a complete characterization including 17O NMR and mass spectrometry data, and re-investigation of their ECD spectra have been reported Altogether, the TDDFT calculations, together with a stereochemical analysis based on NMR and the mass spectrometry data, support the conclusion that the experimental ECD results for MePi* and TPi* may be reliable in order of magnitude O 18 O 17 O O P OCH3 (35, MePi*) 18 O S O P 17 O (36a, (R)-TPi*) 400 | Organophosphorus Chem., 2012, 41, 385–411 18 O 17 O P S (36b, (S)-TPi*) 6.2 Fluorescence and luminescence spectroscopy A new fast and simple method has been developed for the quantitative determination of total organophosphorus pesticide (OP) residues in both flour and soil by using fluorescence spectrophotometry.66 The enhanced fluorescence intensity of neutral red indicator in a pH 4.6 buffer medium, with sodium dodecylbenzene sulfonic acid, is reduced on addition of the OP in direct proportion to the concentration of OP added The linear range of the assay method is 0.024–0.40 mg/L Similarly, a rapid fluorospectrophotometric method based on proportional reduction in the enhanced intensity of titan yellow in a pH 6.6 phosphate buffer, with Tween-80, has been developed for the determination of residual amounts of the OP Phoxim in millet and soil.67 Fluorescence measurements were taken at wavelengths lex 412 and lem 460 nm In the characterization of Au(I)-Ag(I) phosphine-alkynyl clusters (37) – (40), their luminescence behaviour has been studied.68 Compounds (38) and (39) exhibited orange-red phosphorescence with quantitive quantum efficiency in both aerated and degassed CH2Cl2, implying O2-independent phosphorescence due to efficient protection of the emitting chromophore centre by the organic ligands Complex (39) exhibits reasonable two-photon absorption (TPA) property with a cross section of sB45GM (800 nm), comparable to the value of commercially available TPA dyes such as Coumarin 151 Computational studies were performed to correlate the structural and photophysical features of the complexes studied The metal-centred triplet emission within the heterometallic core is suggested to play a key role in the observed phosphorescence The luminescence spectrum of (37) in CH2Cl2 shows dual phosphorescence maximized at 575 nm (the P1 band) and 770 nm (the P2 band) Both P1 and P2 bands possess identical excitation spectra, i.e., the same ground-state origin, and the same relaxation dynamics throughout the temperature range of 298–200 K The dual emission of (37) arises from fast structural fluctuation upon excitation, perhaps forming two geometry isomers which exhibit distinctly different P1 and P2 bands The scrambling dynamics might require large-amplitude motion and thus is hampered in rigid media, as evidenced by the single emission for (37a) (610 nm) and (37b) (570 nm) observed in the solid The luminescence of two new 3D zinc phosphonates (41) and (42) has also been measured.69 [Au8Ag6(C2Ph)12(PPh2-C2-C2-PPh2)2](PF6)2 [Au10Ag8(C2Ph)16(PPh2-C2-C6H4-C2-PPh2)2](CF3SO3)2 (37a orange, 37b yellow) (38) [Au12Ag10(C2Ph)20(PPh2-C2-(C6H4)2-C2-PPh2)2](CF3SO3)2 (39) [Au14Ag12(C2Ph)24(PPh2-C2-(C6H4)3-C2-PPh2)2](CF3SO3)2 (40) [(H3N(CH2)4NH3) Zn2((O3PCH2)2NCH2PO3H)(Cl)] (41) [(H3N(CH2)4NH3)Zn3(O3P(CH2)2PO3)2] (42) Organophosphorus Chem., 2012, 41, 385–411 | 401 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.42,45,53 Thus, N-2,4-dichorobenzoyl phosphoric triamides were synthesized and characterized by multinuclear NMR and IR spectroscopy, and X-ray crystallography, with one indicating polymorphism,42 and polymorphism was again seen in (20a, b) from NMR and XRD studies.45 The different orientations of P¼O versus C¼O in the P(O)NHC(O) skeleton in two new phosphorus(V)-nitrogen compounds, (21) and (22) were also discussed earlier.53 From single crystal XRD analysis, the P atoms have a distorted tetrahedral configuration, with the bond angles in the range of 101.291 [N(2)–P(1)–N(3)] to 114.741 [O(1)–P(1)–N(1)] for cyclic amide (21), and 103.861 [N(3)–P(1)–N(1)] to 115.991 [O(1)–P(1)–N(3)] for amide (22) The phosphoryl and carbonyl groups adopt an anti position in amide (22), whereas in cyclic amide (21) they are in a gauche situation The single-crystal X-ray structure of the diphosphene, DmpP¼PDmp (Dmp=2,6-Mes2C6H3), previously reported to have a relatively-short P¼P bond distance of 1.985 A˚ at room temperature, has been re-examined at variable temperatures.70 Its XRD analyses at 100 K allow for resolution of disorder of the two P atoms (unresolvable by room temperature XRD), and for determination of a more conventional P¼P bond length of 2.029 A˚ Single crystals of the closely-related DxpP¼PDxp (Dxp=2,6(2,6-Me2C6H3)2C6H3) show similar disorder in one of two crystallographically-independent molecules in the unit cell, and a value of 2.0276 A˚ is found for the non-disordered P¼P bonds at 100 K A new diphosphene Ar P¼PAr (Ar =2,6-Mes2-4-OMe-C6H3) has been prepared and its structure has also been examined The P¼P bond length was 2.0326 A˚ and relatively free of the effects of disorder The first thermally stable, neutral, electrophilic phosphinidene complexes of vanadium, [CpV(CO)3{Z1-P-(NR2)}] (R=iPr and Cy), have been prepared.71 The molecules were characterized by multinuclear NMR spectroscopy and also by single-crystal XRD for R=Cy Its structure exhibits a piano stool geometry closely related to that of CpV(CO)4 with an Z1-phosphinidene ligand replacing CO in one of the basal coordination sites of the vanadium atom (V(1)-P(1)=2.300 A˚) 1-Electron oxidation of phosphaalkene (43) gave stable phosphinyl radical cation (44).72 In the solid state, cation (44) adopts a V-shaped geometry with a N2-P1-C1 angle of 107.31 The P1-C1 (1.81 A˚) and P1-N2 (1.68 A˚) bond lengths in cation (44) are significantly longer and shorter, respectively, than the corresponding ones in phosphaalkene (43) (1.74 and 1.77 A˚) These two bond distances are at the lower ends of the ranges for P–C and P–N single bonds, respectively Moreover, the N1-C1 bond distance in cation (44) (1.32 A˚) is shorter than that in phosphaalkene (43) (1.38 A˚), indicating a double bond Collectively, these data are in agreement with those expected for a phosphinyl radical bearing a cationic substituent 402 | Organophosphorus Chem., 2012, 41, 385–411 Dipp N+ Ph3C+ (C6F5)4B– N Dipp P P N (C6F5)4B– (43) N (44) The electronic and steric properties of the chalcogenides of the aminomethylphosphines (2), (3), and (4) were mentioned earlier.8 Diphenyl[2-(2pyridylaminomethyl)phenyl]phosphine oxide (45), has been prepared and analyzed.73 It crystallizes with two crystallographically-independent molecules in the asymmetric unit The aminopyridine units and the benzene ring bonded to the phosphine oxide P atom form dihedral angles of 88.58 and 82.471 in the two molecules The crystal structure displays strong N–H O and weak C–H O hydrogen bonds along the b axis and C–H p aromatic intra- and intermolecular interactions It has also been observed that bis(2methoxyphenyl)(phenyl)phosphine selenide crystallizes with two distinct orientations for the methoxy groups.74 The Se¼P bond is 2.1170 A˚ and cone angle is 176.01 Intra- and intermolecular C–H Se interactions occur in the crystal A series of phosphonium salts with pentafluorobenzyl substituents (46) and (47), have been prepared and investigated in the crystal by XRD and also in solution by NMR.75 The solid state structures of salts (46) and (47) reveal the presence of anion-p as well as CH-anion interactions The two attractive, yet competitive, forces seem to act together and a directing effect of the CH interaction on the relative position between anion and p-system is observed The search for anion-p interactions in solution failed and only CH-anion interactions proved to be important in solution F F F F Ph F X – Ph P+ P+ P O F N F Ph F F N BPh4– F H (46, X = Br or I) (45) H H N O P O O Ph2P O Cl O H PPh2 N H Cl (48, M = Fe, Co, Zn) O N O H (49) OEt EtO N P NH H3C NH O P OEt OEt (50) O H3C O O EtO M (47) (51) Organophosphorus Chem., 2012, 41, 385–411 | 403 The reactivity of the diphosphinite ligand, 9,9-(Ph2POCH2)2-fluorene, and the formation and XRD analysis of its Ni, Pd, Pt, Fe, Co and Zn complexes, including the first structurally-characterized diphosphinate metal chelates (48), have been reported.76 In complexes (48), the diphosphinate ligand and the metal centre (Fe, Co and Zn) form 10-membered metallocycles Examination of the [amino(imino)methyl] phosphonate (49), reveals that it exists as a zwitterion: the N atom of the imino group is protonated and the phosphonic acid group is deprotonated.77 The molecular geometry about the central C atom of this zwitterionic species was found to be strictly planar with the sum of the three angles about C being precisely 3601 In the crystal, the molecules are interlinked by O–H O and N–H O hydrogen-bonding interactions, forming a three-dimensional supramolecular network structure Some new stable phosphorus ylides have been prepared and X-ray crystallographic data and theoretical study shows that there is a conjugation between the C¼P and C¼O bonds in phosphorous ylide (50).78 This compound crystallizes in the triclinic system, space group (P1), with unit cell parameters: a=8.7522 A˚, b=8.8513 A˚, c=18.3469 A˚, a=99.12201, b=90.9541, g=118.7921, Z=2, and V=1222.72 A˚ In N,N’-dicyclohexylN 0 ,N 0 -dimethylphosphoric triamide (51)79 both cyclohexyl groups adopt chair conformations with the NH unit in an equatorial position The P atom adopts a slightly distorted tetrahedral environment In the (CH3)2NP(O) unit, the O–P–N–C torsion angles, showing the orientations of the methyl groups with respect to the P¼O group, are À166.6 and 34.61 The O atom of the P¼O group acts as a double hydrogen-bond acceptor and is involved in two different intermolecular N–H OP hydrogen bonds, building rings that are further linked into chains running parallel to the b axis Electrochemical methods 8.1 Voltammetry The uses of cyclic voltammetry (CV) were mentioned earlier during the characterizations of the electron-rich metal-metal triple-bonded Tc2X4(PMe3)4 complexes,7 and the Ru-phosphine and heterobimetallic complexes (12).28 In the case of the Tc2X4(PMe3)4 complexes, the cyclic voltammograms exhibit two reversible waves and indicate that Tc2Br4(PMe3)4 exhibits more positive oxidation potentials than Tc2Cl4(PMe3)4 This phenomenon is ascribed to stronger metal (d) to halide (d) back-bonding in the bromo complex Further analysis indicates that Tc(II) dinuclear species containing p-acidic phosphines are more difficult to oxidize, and a correlation between oxidation potential and phosphine acidity was established Also, cyclic voltammetry studies have demonstrated that the redox properties of the bimetallic complexes (12) rely on the nature of the metal centre of the {M(acac)2} moiety (M=Co, Ni, and Zn) The dinuclear framework of the ruthenium-cobalt derivative should be stable and inert as the complex undergoes a fully-reversible rutheniumcentred oxidation, while an irreversible cobalt-centred process was detected Indeed, a fully-reversible ruthenium-centred process was observed for M=Ni and M=Zn as the only redox process in the explored potential window On this basis, the dependence of the redox properties of the complex on the metal bonded to the dmoPTA-NCH3 atoms was shown 404 | Organophosphorus Chem., 2012, 41, 385–411 The OP methidathion, a non-systemic organophosphorous insecticide and acaricide, has been studied at the hanging mercury drop electrode under cathodic stripping mode by means of cyclic and square-wave voltammetry (SWV).80 Its electrode reaction was analyzed in the light of recent theory of cathodic stripping processes of insoluble salts of SWV Its complex electrode mechanism is described by an electrode reaction of a second order, complicated by adsorption of methidathion molecules on the electrode surface involving lateral interactions between each other Moreover, under specific experimental conditions, the electrode mechanism can be additionally complicated by multilayer formation on the electrode surface, as well as by a chemical transformation following the cathodic stripping process of the methidathion-mercury salt Following the mechanistic study of the electrode reaction, a method for quantitative determination of methidathion was proposed applying SWV 8.2 Electrochemical sensors and biosensors A film bulk acoustic resonator (FBAR) modied with a self-assembled Cu2ỵ/11-MUA bilayer has been manufactured as a possible sensor for nerve gas detection.81 The resonance frequency of the FBAR decreases due to the adsorption of organophosphorus compounds onto the Cu2ỵ/11-MUA bilayer The sensor was able to detect DMMP concentration as low as 100 ppb On the basis of these results, it is expected that the Cu2ỵ/11-MUA modied FBAR could be further developed as a handheld sensor for early alarm of nerve agents The simple fabrication and small size make this an appropriate candidate for fabrication of sensor arrays Thermal methods and thermochemistry Thermal methods including differential thermal analysis (DTA), thermogravimetric analysis (TG/TGA) and differential scanning calorimetry (DSC) have been used mainly in the analysis and characterization of polymers, particularly for the characterization and thermal properties of cyclotriphosphazenes and polyphosphazenes when in combination with spectroscopic and structural studies, as mentioned earlier.11,35,36 A kinetic investigation has been carried out on the thermal decomposition of N,Ndimethyl-N ,N -diphenylphosphorodihydrazide and diphenyl amidophosphate compounds by TG, DTA and DSC techniques under nonisothermal conditions.82 Also, the thermal properties and flammability of a series of polyphosphoramides have been investigated using DSC, TGA and microscale combustion calorimetry (MCC).83 10 Mass spectrometry techniques Mass spectrometry is also included in the next section where it is used as a detector for identifying the eluents from gas and liquid chromatographic separations (GC-MS and LC-MS) As with the other methods (IR, UVvisible, NMR and XRD), mass spectrometry (MS) is a complementary technique used for the characterization of organic compounds and many applications have been mentioned earlier including the characterization of free radical spin adducts using 31P NMR spectroscopy and mass spectrometry.25 Organophosphorus Chem., 2012, 41, 385–411 | 405 A detailed study of the fragmentation of enriched a-aminophosphonate diastereoisomers by chemical ionization (CI) and fast atom bombardment (FAB) mass spectrometry (MS) has been reported.84 Complete characterization of the different MS fragmentation pathways is represented and this required the use of tandem (MS/MS) experiments and high resolution accurate mass measurements All the a-aminophosphonates gave prominent [MH] ỵ ions, and their fragmentations mainly showed a loss of dimethyl phosphite to give the corresponding iminium ions as base peaks for a-aminophosphonates bearing methylbenzyl and 2,2-dimethylbutyl fragments The loss of the chiral fragment from the iminium ions bearing the (S)-1-(1naphthyl)ethyl group gave rise to a base peak due to aryl cations All the fragment ions were confirmed by high-resolution mass spectrometry A ‘green’ synthesis of a-hydroxy phosphonates and their characterizations by IR, NMR, and EI-MS has been reported,85 and also a comparison of the isomeric a-amino acyl adenylates and amino acid phosphoramidates of adenosine by electrospray ionization tandem mass spectrometry (ESI-MSn).86 In the ESI-MS/MS of a-amino acyl adenylates, the novel rearrangement ion [cAMP-H]À observed as the most intense signal was formed through a pentacoordinate phosphorus intermediate with a six-membered ring by nucleophilic attack of the -OH group on the P atom In contrast, for the amino acid phosphoramidate of adenosine, the P atom could be attacked not only by the carboxylic group to form the cyclic aminoacyl phosphoramidates (CAPAs), but also by the N atom on the nucleobase leading to intramolecular phosphoryl group migration It was found that the sodium ion having multidentate binding ability played an essential role in this characteristic rearrangement The proposed mechanisms were supported by a MS/MS study, deuterium-labelled experiments, high-resolution tandem mass spectrometry and moderate calculations at the B3LYP/6-31G* level The characteristic fragmentation patterns of a-amino acyl phosphates and amino acid phosphoramidates allows identification of stereoisomers when either the phosphorylation is at the N-terminus or C-terminus Finally, a novel strategy for determination of the elemental composition of organic compounds by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS), based on isotopic peak ratios, has been reported.87 Using -phosphoadenosine -phosphosulfate and CTU guanamine as standard organic compounds, isotopic peaks derived from 15N-, 34 S-, and 18O-substituted forms were separated from 13C-substituted species Furthermore, these isotopic peaks were quantitatively detected and closely matched the natural abundance of each element which led to determining the elemental composition This approach would be particularly amenable to the metabolomics research field 11 Chromatography and related separation techniques 11.1 Gas chromatography and gas chromatography-mass spectrometry (GC-MS) GC and GC-MS methods reported include the rapid detection of dimethyl phosphite by GC,88 the first direct determination of seven underivatized alkyl methylphosphonic acids by flame ionization (FID) GC,89 and the 406 | Organophosphorus Chem., 2012, 41, 385–411 rapid determination of tris(2-chloroethyl) phosphate extracted from PVC articles by GC-MS.90 The increasing selectivity in a three-dimensional (three capillary columns in-series) gas chromatography (GC3) system, over a two column GC x GC system, and in which one of the three columns has an ionic liquid stationary phase, has been applied to a triflate ionic liquid stationary phase column with a high selectivity for phosphonated compounds (dimethyl methylphosphonate, diethyl methylphosphonate and diisopropyl methylphosphonate) Using all three separation dimensions, the 2D separation fingerprint of a diesel sample was simultaneously obtained along with selective information regarding the phosphonated compounds in the diesel samples in the additional dimension.91 11.2 (High performance) liquid chromatography and LC-MS The analytical and semi-preparative HPLC enantioseparation of novel pyridazin-3(2H)-one derivatives with a-aminophosphonate moiety (52), has been performed using immobilized polysaccharide chiral stationary phases.92 The synthesis and characterization of differently- substituted cyclic phosphazenes has also been reported.93 The mixtures of compounds formed in the reactions were characterized using liquid chromatography/ electrospray ionisation time- of-flight mass spectrometry Every substituted cyclic phosphazene contained four to five by-products in addition to the main product Chromatographic separation of these mixtures allowed a characterization based on polarities Based on the calculation of molecular formulae, structures for all the products were suggested It could be shown using high-resolution mass spectrometry that side products with a different side-chain ratio, with remaining chlorine atoms or hydroxyl groups, or even spiro or ansa products, were formed O N N Cl O S NH CH P OR2 OR2 R1 (52) 11.3 Capillary electrophoresis A novel method has been patented for the separation of 2-(2,4,5trichlorophenoxy)propionic acid enantiomers by capillary electrophoresis.94 12 Kinetics A kinetic study on new P ylides by UV spectrophotometry was mentioned earlier.39 Also, the 31P NMR spectroscopy kinetic study of the tandem cleavage of phosphonate esters by bromotrimethylsilane was mentioned earlier.52 Both 1H and 31P NMR methods were used to access rate constants and activation parameters for each of the consecutive second-order Organophosphorus Chem., 2012, 41, 385–411 | 407 silylation reactions involved in the overall transformation Computational optimisation of the rate constants obtained from the initial, linear phase of each reaction allowed an excellent fit with the experimental data for the entire course of the reaction The value of 31P NMR spectroscopy for kinetic studies was highlighted with the associated advantages of uncluttered spectra and short relaxation times facilitating accurate determination of the concentrations of the species involved Two additional kinetics studies are noteworthy, the kinetics and mechanism of pyridinolysis of dimethyl phosphinic and thiophosphinic chlorides in acetonitrile,95 and the hydrolysis and aminolysis of esters of 2-S-phosphoryl acetates.96 References M Lehmann, A Schulz and A Villinger, Struct Chem., 2011, 22, 35 S A Hayes, R J F Berger, N W Mitzel, J Bader and B Hoge, Chem Er J., 2011, 17, 3968 L S Khaikin, O E Grikina and N F Stepanov, Russ J Phys Chem., 2010, 84, 1745 K A Chernyshev and L B Krivdin, Russ J Org Chem., 2010, 46, 785 A V Belyakov, A N Khranov and V A Naumov, J Mol Struct., 2010, 978, A V Belyakov, A N Khranov and V A Naumov, Russ J Gen Chem., 2010, 80, 2249 F Poineau, P M Forster, T K Todorova, L Gagliardi, A P Sattelberger and K R Czerwinski, Inorg Chem., 2010, 49, 6646 R Starosta, B Bazanow and W Barszczewski, Dalton Trans., 2010, 39, 7547 S V Federov, L B Krivdin, Y Y Rusakov, N A Chernysheva and V L Mikhailenko, Magn Reson Chem., 2010, 48, S48 10 K Gholivand and N Dorosti, Monatsh Chem., 2011, 142, 183 11 V L Furer, I I Vandyukova, A E Vandyukov, S Fuchs, J P Majoral, A M Caminade and V I Kovalenko, J Mol Struct., 2011, 987, 144 12 J Liu, D Chen, G Zhang, Y Zhang, H Zhang, S Mi and G Shen, THEOCHEM, 2010, 948, 71 13 W Foerner and H M Badawi, Z Naturforsch B, 2010, 65, 357 14 T Chen and X.-S Tan, Fenzi Kexue Xuebao, 2010, 26, 334 (Chem Abs., 2011, 154, 335533) 15 K Gholivand and H R Mahzouni, Polyhedron, 2011, 30, 61 16 S G Kozlova and I V Drebushchak, J Struct Chem., 2010, 51, 166 17 K Hemelsoet, F Van Durme, V Van Speybroeck, M.-F Reyniers and M Waroquier, J Phys Chem A, 2010, 114, 2864 18 H Tavakol, G Gaimech, S Ghammamy and G R Bebahani, Phosphorus, Sulfur, Silicon Relat Elem., 2010, 185, 2464 19 T J Gordon, L D Szabo, T Linder, C P Berlinguette and T Baumgartner, Comptes Rendus Chimie, 2010, 13, 971 20 W.-Y Shi, S Jiang, J Zeng, Y Chu and Z Lv, Jisuanji Yu Yingyong Huaxue, 2010, 27, 1660 (Chem Abs., 2011, 154, 539796) 21 R T Santiago, F A La Porta, M V J Rocha, T C Ramalho, M P Freitas and E F F da Cunha, Lett Org Chem., 2010, 7, 552 22 M Smiechowski, Chem Phys Lett., 2010, 50, 123 23 M G Cory, D E Taylor, S W Bunte, K Runge, J L Vasey and D S Burns, J Phys Chem A, 2011, 115, 1946 24 Q Yang, J.-R Zhu, Q Sun, J.-R Cui, R.-T Li and Z.-M Ge, J Chin Pharm Sci., 2010, 19, 24 408 | Organophosphorus Chem., 2012, 41, 385–411 25 L Zoia and D S Argyropoulos, Eur J Mass Spectrom., 2010, 16, 175 26 R B Guevara, D T Barnard, A K Mowles, H M Weaver, R A Quick, W F Lebbos, K M Biggs and J E Williams, J Undergrad Chem Res., 2010, 9, 77 27 L Rigamonti, M Rusconi, C Manassero, M Manassero and A Pasini, Inorg Chim Acta, 2010, 363, 3498 28 A Mena-Cruz, P Lorenzo-Luis, V Passarelli, A Romerosa and M SerranoRuiz, Dalton Trans., 2011, 40, 3237 29 K B Dillon, P Gemmell, T G Hibbert and B Y Xue, Heteroat Chem., 2010, 21, 156 30 Y.-Y Carpenter, N Burford, M D Lumsden and R McDonald, Inorg Chem., 2011, 50, 3342 31 R Pomeckoa, Z Asfari, V Hubscher-Bruder, M Bochenska and F ArnaudNeu, Supramol Chem., 2010, 22, 275 32 M P Duffy, Y Lin, F Ho and F Mathey, Organometallics, 2010, 29, 5757 33 R Streubel, J M Perez, H Helten, J Daniels and M Nieger, Dalton Trans., 2010, 39, 11445 34 M V Escarcega-Bobadilla, E Teuma, A M Masdeu-Bulto and M Gomez, Tetrahedron, 2011, 67, 421 35 A S Borisov, P Hazendonk and P G Hayes, J Inorg Organomet Polym., 2010, 20, 395 36 M Isiklan, N Asmafiliz, E E Ozalp, E E Ilter, Z Kilic, B Cosut, S Yesilot, A Kilic, A Ozturk, T Hokelek, L Y Koc Bilir, L Acik and E Akyuz, Inorg Chem., 2010, 49, 7057 37 Z Kilic, A Okumus, S Demiriz, S Bilge, A Ozturk, N Caylak and T Hokelek, J Incl Phenom Macrocycl Chem., 2009, 65, 269 38 S J Sabounchei, P Shahriary, Z B Nojini, H R Khavasi, C Arici and H Dal, Heteroat Chem., 2010, 21, 475 39 M Zakarianezhad, S M Habibi-Khorassani, A Ebrahimi, M T Maghsoodlou and H Ghasempour, Heteroat Chem., 2010, 21, 462 40 S Eroeksuez, O Dogan and P P Garner, Tetrahedron: Asymmetry, 2010, 21, 2535 41 S J Sabounchei, K S Noorani, F Hejazi and S Samiee, Asian J Chem., 2010, 22, 6859 42 K Gholivand, N Oroujzadeh and Z Shariatinia, Heteroat Chem., 2010, 21, 168 43 K Schober, E Hartmann, H Zhang and R M Gschwind, Angew Chem., Int Ed., 2010, 49, 2794 44 X Chen, J Yuan, S Zhang, L Qu and Y Zhao, Phosphorus, Sulfur, Silicon Relat Elem., 2010, 185, 274 45 K Gholivand, F Afshar, Z Shariatinia and K Zare, Struct Chem., 2010, 21, 629 46 A K Panda, Asian J Chem., 2010, 22, 2811 47 N Aliouane, J.-J Helesbeux, T Douadi, M A Khan, G Bouet, S Chafaa and O Duval, Phosphorus, Sulfur, Silicon Relat Elem., 2011, 186, 354 48 H Maki, Y Ueda and H Nariai, J Phys Chem B, 2011, 115, 3571 49 P Thirumurugan, A Nandakumar, N S Priya, D Muralidaran and P T Perumal, Tetrahedron Lett., 2010, 51, 5708 50 W Zhou, X Huang and X Ju, Wuhan Gongcheng Daxue Xuebao, 2010, 32, 28 (Chem Abs., 2011, 154, 459874) 51 A.-M Caminade, R Laurent, C.-O Turrin, C Rebout, B Delavaux-Nicot, A Ouali, M Zablocka and J.-P Majoral, Comptes Rendus Chimie, 2010, 13, 1006 52 A C Conibear, K A Lobb and P T Kaye, Tetrahedron, 2010, 66, 8446 Organophosphorus Chem., 2012, 41, 385–411 | 409 53 A Tarahhomi, M Pourayoubi, A L Rheingold and J A Golen, Struct Chem., 2011, 22, 201 54 K Gholivand, N Oroujzadeh and Z Shariatinia, J Chem Sci., 2010, 122, 549 55 A E Wroblewski and J Drozd, Tetrahedron: Asymmetry, 2011, 22, 200 56 Z Dominguez, J Hernandez, L Silva-Gutierrez, M Salas-Reyes, M Sanchez and G Merino, Phosphorus, Sulfur, Silicon Relat Elem., 2010, 185, 772 57 A Nakajima, E Matsuda, Y Ueda and K Tajima, Can J Chem., 2010, 88, 556 58 L E McDyre, T Hamilton, D M Murphy, K J Cavell, W F Gabrielli, M J Hanton and D M Smith, Dalton Trans., 2010, 39, 7792 59 E K Badeeva, E V Platova, E S Batyeva, L I Kursheva, E E Zvereva, A E Vandyukov, S A Katsyuba, V I Kovalenko and O G Sinyashin, Heteroat Chem., 2011, 22, 24 60 V L Furer, A E Vandyukov, J P Majoral, A M Caminade and V I Kovalenko, Spectrochim Acta, Part A, 2010, 76, 276 61 V L Furer, I I Vandyukova, A E Vandyukov, S Fuchs, J P Majoral, A M Caminade and V I Kovalenko, Vib Spectrosc., 2010, 54, 21 62 M D Elkin, S I Tatarinov and E Y Stepanovich, J Appl Spectrosc., 2010, 77, 479 63 H Mollendal, A Konovalov and J.-C Guillemin, J Phys Chem A, 2009, 113, 12904 64 H Mollendal, A Konovalov and J.-C Guillemin, J Phys Chem A, 2010, 114, 10612 65 J.-J Pan, B A Kashemirov, J Lee, C E McKenna, F J Devlin and P J Stephens, Bioorg Chem., 2010, 38, 66 D.-X Cheng, Y.-P Zhao and M Gao, Fenxi Shiyanshi, 2010, 29, 45 (Chem Abs., 2010, 153, 397206) 67 D.-X Cheng, G.-Q Zuo, Y.-P Zhao and M Gao, Lihua Jianyan, Huaxue Fence, 2010, 46, 1129 (Chem Abs., 2011, 154, 300762) 68 I O Koshevoy, C.-L Lin, A J Karttunen, J Janis, M Haukka, S P Tunik, P.-T Chou and T A Pakkanen, Inorg Chem., 2011, 50, 2395 69 R Fu, S Hu and X Wu, J Solid State Chem., 2011, 184, 159 70 J D Protasiewicz, M P Washington, V B Gudimetla, J L Payton and M C Simpson, Inorg Chim Acta, 2010, 364, 39 71 T W Graham, K A Udachin, M Z Zgierski and Arthur J Carty, Organometallics, 2011, 30, 1382 72 O Back, M A Celik, G Frenking, M Melaimi, B Donnadieu and G Bertrand, J Am Chem Soc., 2010, 132, 10262 73 S Hernandez-Ortega, F Cuenu Cabeza and A Cabrera-Ortiz, Acta Crystallogr., Sect E: Struct Rep Online, 2010, E66, o1181 74 A Muller, Acta Crystallogr., Sect E: Struct Rep Online, 2011, E67, o89 75 M Mueller, M Albrecht, J Sackmann, A Hoffmann, F Dierkes, A Valkonen and K Rissanen, Dalton Trans., 2010, 39, 11329 76 C Li, R Pattacini and P Braunstein, Inorg Chim Acta, 2010, 363, 4337 77 T.-H Yang, W Zhuang, W Wei, Y.-B Yang and Q Chen, Acta Crystallogr., Sect E: Struct Rep Online, 2010, E66, o2326 78 M Rostamizadeh, M T Maghsoodlou, S M Habibi-Khorassani, N Hazeri, S S Sajadikhah, F R Charati, M A Kazemian, B W Skelton and M Makha, Heteroat Chem., 2011, 22, 36 79 F Sabbaghi, M Pourayoubi, F K Ahmadabad, Z Azarkamanzad and A A Ebrahimi Valmoozi, Acta Crystallogr., Sect E: Struct Rep Online, 2011, E67, o502 80 V Mirceski, D Guziejewski, S Skrzypek and W Ciesielski, Croatica Chemica Acta, 2010, 83, 121 410 | Organophosphorus Chem., 2012, 41, 385–411 81 D Chena, Y Xua, J Wang and L Zhang, Sensors and Actuators, B, 2010, 150, 483 82 M R Sovizi and K Anbaz, J Therm Anal Calorim., 2010, 99, 593 83 Q Tai, Y Hu, R K K Yuen, L Song and H Lu, J Mater Chem., 2011, 21, 6621 84 G D Tibhe, V Labastida-Galvan and M Ordonez, Rapid Commun Mass Spectrom., 2011, 25, 951 85 P G Mandhane, R S Joshi, D R Nagargoje and C H Gill, Tetrahedron Lett., 2010, 51, 1490 86 X Gao, Z.-P Zeng, P Xu, G Tang, Y Liu and Y Zhao, Rapid Commun Mass Spectrom., 2011, 25, 291 87 D Miura, Y Tsuji, K Takahashi, H Wariishi and K Saito, Anal Chem., 2010, 82, 5887 88 Z Zhang, C Wang, S Xu and S Li, Faming Zhuanil Shenqing CN 101,819,188 (China), 2010, (Chem Abs., 2010, 153, 44702) 89 I Po"ec, A Kie"czewska, L Konopski, G Oleksa, H Nowacka Krukowska and J Legocki, Cent Eur J Chem., 2010, 8, 1251 90 S Xu, B Wu, L Yuan and J Xia, Fenxi Ceshi Xuebao, 2010, 29, 978 (Chem Abs., 2011, 154, 425045) 91 W C Siegler, J A Crank, D W Armstrong and R E Synovec, J Chromatogr., 2010, 1217, 3144 92 Y.-P Zhang, X.-Y Zhang, J Zhou, B.-A Song, P S Bhadury, D.-Y Hu and S Yang, J Sep Sci., 2011, 34, 402 93 K Veldboer, T Schuermann, M Vogel, H.-D Wiemhoefer and U Karst, Rapid Commun Mass Spectrom., 2011, 25, 147 94 Q Zhang, M Zhao, W Liu and C Wang, Faming Zhuanli Shenqing Gongkai Shuomingshu CN 101,726,529 (China), 2010, (Chem Abs., 2010, 153, 133694) 95 N K Dey, K K Adhikary, C K Kim and H W Lee, Bull Korean Chem Soc., 2010, 31, 3856 96 M Trmcic and D R W Hodgson, Beil J Org Chem., 2010, 6, 732 Organophosphorus Chem., 2012, 41, 385–411 | 411 ... methods and thermochemistry 10 Mass spectrometry techniques 11 Chromatography and related separation techniques 12 Kinetics References 385 385 390 397 398 399 402 404 405 405 406 407 408 Organophosphorus. . .Organophosphorus Chemistry Volume 41 A Specialist Periodical Report Organophosphorus Chemistry Volume 41 A Review of the Literature Published between... these structures involving cyclic or linear backbone systems Organophosphorus chemistry is particularly suitable for study by physical methods Theoretical and computational chemistry have continued