ChemInformVolume 33, Issue 40 p. 269-269 Reviews Macro- and Spiro-heterocycles Michael Pabel, Michael Pabel Dep. Chem., Aust. Natl. Univ., Canberra, A. C. T. 0200, AustraliaSearch for more papers by this authorS. Bruce Wild, S. Bruce Wild Dep. Chem., Aust. Natl. Univ., Canberra, A. C. T. 0200, AustraliaSearch for more papers by this author Michael Pabel, Michael Pabel Dep. Chem., Aust. Natl. Univ., Canberra, A. C. T. 0200, AustraliaSearch for more papers by this authorS. Bruce Wild, S. Bruce Wild Dep. Chem., Aust. Natl. Univ., Canberra, A. C. T. 0200, AustraliaSearch for more papers by this author First published: 19 May 2010 https://doi.org/10.1002/chin.200240269AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume33, Issue40October 8, 2002Pages 269-269 RelatedInformation

Publisher Summary This chapter covers a wide variety of molecules and hence broad subject headings have been adopted. The inclusion of numerous structural diagrams in the text, however, will assist the reader in locating material of interest. The monocyclic compounds discussed are posphorins, metal complexes of phsophorins, insertion into C-X bonds of halophosphorins, dihydrophosphorins, tetrahydrophosphorins, phosphorinanes, and phosphasugars. Similarly the bi- and tri-cyclic compounds are covered. The chapter outlines the subsections—namely, phospha-anthracenes and –acridines, phosphaphenanthrenes, phosphadamantanes and other tricyclic compounds and derivatives are described. The chlorophosphine complex 419 reacted upon treatment with tri-ethylamine via 420 with diene 421 to give the intermediate 422 that underwent a second Diels-Alder reaction with 421 to furnish the tetracyclic complex 423 is illustrated in the topic of polycyclic compounds. The arsenic compounds are discussed for the monocyclic and heterocyclic structures. The compounds containing antimony and bismuth are briefly presented.

The important chloro-bridged dipalladium(II) resolving agents (R,R)- and (S,S)-cis-di-μ-chlorobis[1-[1-(dimethylamino)-ethyl]-2-naphthalenyl-C,N]dipalladium, (R,R)- and (S,S)-cis-1, undergo facile rearrangements into unequal mixtures of cis and trans diastereomers upon dissolution in chloroform or dichloromethane, although concentration of the solution in each case affords in high yield the pure cis diastereomer of the dinuclear metal complex as the corresponding mono-solvate in a typical second-order asymmetric transformation. When equimolar solutions of (R,R)-cis- and (S,S)-cis-1 CH2Cl2 in dichloromethane are mixed together, however, an equilibrium is rapidly established between the cis and trans diastereomers of the (R∗,R∗)-(±) and (R∗,S∗) forms of 1 and from which solution configurationally homogeneous (R∗,S∗)-trans-1·CH2Cl2 crystallizes in high yield by second-order asymmetric transformation. The crystal and molecular structures of (R,R)-cis-1·CH2Cl2 and (R∗,S∗)-trans-1·CH2Cl2 have been determined. The optical purities of the individual enantiomers of (R∗,R∗)-(±)-1·CH2Cl2 have been determined by reaction with (1R,2S,5R)-menthyldiphenylphosphine or (1S, 2S, 5R)-neomenthyldiphenylphosphine in chloroform-d1 and analysis of the 31P1H NMR spectra of the resulting solutions of the corresponding bridge-split palladium(II)-phosphine epimers.

The first phosphiranium salt, 1-methyl-1-phenylphosphiranium triflate (1), has been isolated in 73% yield from the reaction between 1-phenylphosphirane and methyl triflate in benzene. The crystal and molecular structures of 1 have been determined. The phosphiranium ion in 1 undergoes ring opening with water to give (±)-ethylmethylphenylphosphine oxide, and reacts with primary alcohols to give (±)-alkoxyethylmethylphenylphosphonium ions. Treatment of 1 with dimethyl- or methylphenylacetylene in dichloromethane affords over one week the corresponding substituted phosphirenium salts in high yield. Phosphirenium salts can also be prepared in high yields by reacting a chloroalkylaryl- or chlorodiarylphosphine and an alkyne with thallium(I) triflate in dichloromethane. The crystal and molecular structures of 1,2,3-trimethyl-1-phenylphosphirenium triflate have been determined. The reaction of chloromethylphenylphosphine with thallium(I) triflate in the absence of an alkyne leads to an unstable phosphinophosphonium triflate that undergoes rapid chloride exchange and/or pyramidal inversion at phosphorus under ambient conditions, as determined by variable temperature NMR spectroscopy.

The R(P) diastereomer of (-)-menthylmesitylphosphine, (R(P))-1, has been isolated with high configurational purity at phosphorus by fractional crystallization of an (R(P))-1/(S(P))-1 = 43/57 mixture from acetonitrile containing a trace of sodium acetylacetonate as a proton scavenger or by deboranation of the corresponding borane complex (S(P))-2 with diethylamine, thereby effecting the first resolution of a secondary phosphine chiral at phosphorus. The crystal and molecular structure of (S(P))-2 has been determined. The ready isolation of (S(P))-2 of 97% diastereomeric purity in 66% yield from an equilibrium (R(P))-2/(S(P))-2 = 28/72 mixture in n-hexane by second-order asymmetric transformation and its quantitative and stereospecific conversion under mild conditions into (R(P))-1 of similar purity augurs well for the future of the resolved secondary phosphines in stereoselective syntheses.

Diltihium phenylphosphide reacts with 1,3-dichloropropane or 1,2-dichloroethane to give 1-phenylphosphetane (1) or 1-phenylphosphirane (2), respectively, both of which can be isolated by distillation in vacuo. The phosphetane rapidly polymerizes when neat but is stable in benzene wherefrom the polymer can be selectively and quantitatively separated from 1 by the addition of trans-dichlorobis(diethyl sulfide)palladium(II). Four-membered 1 has a remarkably low-field(31)P NMR chemical shift (13.9 ppm), and 2, a remarkably high-field shift (-236 ppm). The crystal and molecular structures of the potential cyclotrimerization precursor complexes fac-[Mo(CO)(3)(1)(3)] (7), fac-[Mo(CO)(3)(2)(3)] (8), and [(eta(5)-C5H5)Fe-(2)(3)]PF6 (9) have been determined. Both molybdenum complexes have C-3 symmetry in the solid state, and the iron complex has C-1 symmetry. An interesting feature of the three structures is that the phenyl groups of the small phosphorus heterocycles in each case are arranged in groups of three syn or anti to the auxiliary ligands.

The title compound, [Fe(C5H5)(C8H9P)(C20H20P2)]PF6, was obtained by spontaneous resolution of the racemate from acetone/diethyl ether solution. The cationic piano-stool iron(II) complex exhibits pseudo-octahedral coordination geometry, with Fe-P distances of 2.189(3) and 2.178 (4) Angstrom for the bidentate ligand, and 2.170 (3) Angstrom for the phosphirane ligand, The bond parameters for the phosphirane ligand are in good agreement with those found for related complexes.

(+/-)-Chlorophenylisopropylphosphine has been resolved in a palladium(II) complex containing the phosphine and ortho-metalated (R)-1-[1-(dimethylamino)ethyl]naphthalene; the configurationally homogeneous (R,Rp) diastereomer of the complex crystallises from the reaction mixture by typical second-order asymmetric transformation in overall 82% yield. The absolute configuration of the complex was determined by X-ray crystallography. The pure (R,Rp) diastereomer of the complex reacts quantitatively with methanol in the presence of triethylamine to give the corresponding methoxyphosphine complex with complete stereoselectivity and inversion at phosphorus. All attempts at liberating optically active chlorophosphine from the palladium complex were unsuccessful.

The trivalent fluorophosphine (+/-)-PFPh(i-Pr), (+/-)-1, has been prepared by halogen exchange of the corresponding chlorophosphine with sodium fluoride in hot sulfolane. The neat fluorophosphine rapidly decomposes by equilibrium redox disproportionation into PF(3)Ph(i-Pr) and (R,R)/(R,S)-Ph(i-Pr)PPPh(i-Pr), but in benzene, (+/-)-1 has considerable thermodynamic stability. The resolution of (+/-)-1 was achieved by a fractional crystallization of the diastereomers (R,R(P))- and (R,S(P))-chloro[1-[1-(dimethylamino)ethyl]-2-naphthalenyl-C,N](fluorophenylisopropylphosphine)palladium(II), (R,R(P))- and (R,S(P))-5, whereby the less soluble (R,R(P)) diastereomer selectively crystallized in 64% yield in a typical second-order asymmetric transformation. Optically pure (S)-(-)-1, -210 (c 0.59, C(6)H(6)), was liberated from (R,R(P))-5 with (R,S)-1,2-phenylenebis(methylphenylphosphine). The optically active phosphine in benzene racemizes over 6 h without significant redox disproportionation. The methoxyphosphine (+/-)-P(OMe)Ph(i-Pr), (+/-)-9, was also resolved by the method of metal complexation. Thus, fractional crystallization of (R,R(P))- and (R,S(P))-chloro[1-[1-(dimethylamino)ethyl]-2-naphthalenyl-C,N](methoxyphenylisopropylphosphine)palladium(II), (R,R(P))- and (R,S(P))-8, followed by liberation of the respective optically active methoxyphosphines from the separated diastereomers with 1,2-bis(diphenylphosphino)ethane, gave (R)-(+)- and (S)-(-)-9 of 92% and 96% ee, respectively. The barrier to unimolecular inversion for (+/-)-9 was determined to be >82.9 +/- 0.5 kJ mol(-)(1) by variable temperature (1)H NMR spectroscopy. The substitution of fluoride in (R,R(P))-5 by methoxide proceeds with predominant inversion of the configuration at phosphorus to give (R,R(P))- and (R,S(P))-8 with (R,S(P))/(R,R(P)) = (1)/(5). The crystal structures of (R,R(P))-5 and (R,R(P))-8 have been determined: (R,R(P))-5 (C(23)H(28)ClFNPPd) crystallizes in the orthorhombic space group P2(1)2(1)2(1) with a = 9.967(2) Å, b = 10.998(4) Å, c = 21.324(3) Å, Z = 4, and R = 0.031; (R,R(P))-8 (C(24)H(31)ClNOPPd) crystallizes in the space group P2(1)2(1)2(1) with a = 10.444(3) Å, b = 12.146(3) Å, c = 19.047(2) Å, Z = 4, and R = 0.026.

The complexes (R*,R*)-(+/-)-[(eta(5)-C5H5){1,2-C6H4(PMePh)(2)}FeL]PF6, where L = 1-phenyl-phosphetane, -phospholane, -phosphorinane, and -phosphepane, have been prepared in high yields from the corresponding phenylphosphine complex by treatment with the appropriate alpha,omega-dibromoalkanes and potassium tert-butoxide. The 1-phenylarsetane complex was obtained by deprotonation of the corresponding complex of (+/-)-(3-chloropropyl)phenylarsine. The 1-phenylphosphirane, the 1-phenylphosphetane, and the 1-phenylarsetane complexes were also prepared by direct reactions of the free ligands with (R*,R*)-(+/-)-[(eta(5)-C5H5){1,2-C6H4(PMePh)(2)}FeMeCN]PF6. The molecular structures of (R*,R*)-(+/-)-[(eta(5)-C5H5){1,2-C6H4(PMePh)(2)}Fe(PhPCH(2)CH(2)CH(2))]PF6 and (R*,R*)-(+/-)-[(eta(5)-C5H5){1,2-C6H6(PMePh)(2)}-Fe(PhAsCH(2)CH(2)CH(2))]PF6 have been determined by X-ray crystallography. The phosphetane complex crystallized in a solvated form with two independent cations of slightly different geometries in each unit cell; the four-membered phosphetane rings are puckered with the angles between the C-P-C and C-C-C planes being 18(2) and 24(2)degrees for the respective cations. The four-membered ring of the arsetane complex is also puckered with the corresponding angle being 25(1)degrees.

(S,S)-[PtCl2{1,2-C6H4(PMePh)(2)}], (S,S)-1, reacts with 1 equiv of silver nitrate in acetone to give the corresponding chloro-bridged diplatinum complex, which, when treated with (+/-)-methylphenylphosphine in the presence of trifluoromethanesulfonic acid, affords, following metathesis of intermediate salts with ammonium hexafluorophosphate, the complex [PtCl{1,2-C6H4(PMePh)(2)}(PHMePh)]PF6, 2, as a diastereomeric pair, epimeric at the secondary phosphine-P stereocenter with (S,S),(S)/(S,S),(R) = 2/1 in dichloromethane-d(2). Recrystallization of this mixture from dichloromethane-diethyl ether gives colorless prisms of (S,S),(S)-[PtCl{1,2-C6H4(PMePh)(2)}(PHMePh)]PF6.CH2Cl2, (S,S),(S)-2.CH2Cl2, having [alpha](589) +56 (c 1, CH2Cl2). The crystal structure of the configurationally homogeneous secondary phosphine complex has been determined. Crystal data for C28H31Cl3F6P4Pt: triclinic, P1, a=8.816(1) Angstrom, b=9.122(1) Angstrom, c=10.556(1) Angstrom, alpha=93.50(1)degrees beta=97.81(1)degrees, delta=94.76(1)degrees Z = 1, and R=0.024. Pure (S,S),(S)-2.CH2Cl2 is stable in dichloromethane solution, but epimerization at the secondary phosphine-P stereocenter occurs rapidly in the presence of traces of chloride or water to give an equilibrium mixture of the two epimers with (S,S),(S)/(S,S),(R) = 2/1 at 23 degrees C. All attempts at displacing resolved (+/-)-PHMePh from (S,S),(S)-2.CH2Cl2 were unsuccessful. Indeed, simple secondary phosphines of this type, although possessing a considerable barrier to unimolecular inversion, viz. E(inv) > 97.5 +/- 0.5 kJ mol(-1), undergo facile intermolecular proton exchange in the presence of traces of acids or cationic secondary phosphine complexes, for example, (S,S),(S)-2.CH2Cl2. Nevertheless, isotopic exchange experiments between (+/-)-PHMePh and (+/-)-PDEtPh revealed negligible proton exchange between the phosphines in highly purified acetonitrile containing sodium acetylacetonate as a proton scavenger, thus indicating that the optical resolution of a simple secondary phosphine of the type (+/-)-PHR(1)R(2) may be feasible under mildly basic conditions.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTStereochemistry and Stability of Free and Coordinated Secondary Phosphines. Crystal and Molecular Structure of [S-[(R*,R*),(R*)]]-(+)589-[PtCl{1,2-C6H4(PMePh)2}(PHMePh)]PF6.cntdot.CH2Cl2Armin Bader, Trevor Nullmeyers, Michael Pabel, Geoffrey Salem, Anthony C. Willis, and S. Bruce WildCite this: Inorg. Chem. 1995, 34, 1, 384–389Publication Date (Print):January 1, 1995Publication History Published online1 May 2002Published inissue 1 January 1995https://pubs.acs.org/doi/10.1021/ic00105a058https://doi.org/10.1021/ic00105a058research-articleACS PublicationsRequest reuse permissionsArticle Views177Altmetric-Citations33LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-AlertscloseSupporting Info (2)»Supporting Information Supporting Information Get e-Alerts

The phosphorus centers in [Cu{1,2-C6H4(PH2)(2)}(2)]CF3SO3 are readily methylated by methyl iodide in the presence of 4 or 8 equiv potassium tert-butoxide to give 1,2-phenylenebis (methylphosphine) or 1,2-phenylenebis(dimethylphosphine), respectively, after displacement from the metal with cyanide. Under similar conditions with 8 equiv of base, 1,4-dibromobutane and 1,5-dibromopentane react to give respectively 1,2-phenylenebis (phospholane) and 1,2-phenylenebis (phosphorinane). 1,3-Dibromopropane, however, reacts with the complex under the basic conditions to give a variety of phosphines after displacement from the metal, including (R*,R*)-(+/-)/(R*,S*)-2,3,4,5-tetrahydro-1H-1,5-benzodiphosphepine, (R*,S*)-2,3,4,5-tetrahydro-1,5-bis(prop-1-enyl)-1H-1,5-benzodiphosphepine, (R*,S*)-2,3,4,5-tetrahydro-1,5-bis(prop-2-enyl)-1H-1,5-benzodiphosphepine, and the putative cage and macrocyclic dimers of 1,2-phenylenebis (phosphetane). The crystal structure of anti-[Ni{(R*,S*)-2,3,4,5-tetrahydro-1,5 bis(prop-1-enyl)-1H-1,5-benzodiphosphepine}(2)](ClO4)(2) . CH2Cl2 has been determined. Crystal data: monoclinic, C2/c, a = 27.119(3) Angstrom, b = 10.908(1) Angstrom, c = 15.590(2) Angstrom, beta = 123.81(1)degrees, Z = 4, and R = 0.047. The coordination geometry around the nickel is square-planar in the centrosymmetrical cation of the complex.

1-Phenylphosphirane reacts with methyl triflate to give 1-methyl-1-phenylphosphiranium triflate, which reacts with acetylenes to give the corresponding phosphirenium salts.

A single diastereoisomer of (-)-menthylmesitylphosphine has been isolated in 94% purity, thereby effecting the first resolution of a free secondary phosphine chiral at phosphorus.