Reaktionen koordinierter Liganden. XVI. Struktur von Lithiumphosphido-Komplexen cis-Mo(CO)4(PRR′Li)2(R,R′  H,Alkyl, Aryl) in Lösung – eine 31P- und 7Li-NMR-spektroskopische Studie

Reactions of Coordinated Ligands. XVI. Structure of the Lithiumphosphido Complexes cis-Mo(CO)₄(PRR′Li)₂ (R, R′ ? H, Alkyl, Aryl) in Solution – a ³¹P and ⁷Li N.M.R. Study Complexes of the lithiumorganophosphides cis-Mo(CO)₄(PRR′Li)₂ (R, R′ ? H, Alkyl, Aryl) may be assigned to a ionic type (solvated) of structure [cis-Mo(CO)₄(PRR′)₂Li]^?Li⁺ in solution. According to ⁷Li and ³¹P NMR measurements at low temperatures the anion comprises a four membered MoP₂Li ring system. The temperature dependence of the ⁷Li and ³¹P NMR spectra may be explained by an intermolecular Li exchange and inversion of configuration at the phosphorus atoms.     

Synthesis and X-ray crystal structures of [Ph2PMe2][(η-C5H4Bu)2Li] and [(η-C5H4Bu)2Yb(Cl)CH2P(Me)Ph2]

The interaction of [(η⁵-C₅H₄Bu^t)₂YbCl · LiCl] with one equivalent of Li[(CH₂) (CH₂)PPh₂] in tetrahydrofuran gave [Ph₂PMe₂][(η⁵-C₅H₄Bu^t)₂Li] (1) and [(η⁵-C₅H₄Bu^t)₂Yb(Cl)CH₂P(Me)Ph₂] (2) in 10% and 30% yields, respectively. 1 could also be prepared in 70% yield from the reaction of [Ph₂PMe₂][CF₃SO₃] with two equivalents of (C₅H₄Bu^t)Li. Both compounds have been fully characterized by analytical, spectroscopic and X-ray diffraction methods. The solid state structure of 1 reveals a sandwich structure for the [(η⁵-C₅H₄Bu^t)₂Li]⁻ anion.     

Diphosphine Compounds,Part III: UV/Visible Spectroscopy and Novel Routes to Functionalized Diphosphine-M(CO)6 Complexes (M = W,Mo, or Cr)

Reaction of coordinated (diphenylphosphino)methane and ketones or aldehydes have been characterized by ³¹P{H¹}-NMR, ¹H{³¹P}-NMR, and UV/vis spectroscopy in dichloromethane. Group VI metals hexacarbonyl [M(CO)₆ where M = Cr, Mo, and W] reacted with (diphenylphosphino)methane, [(Ph₂P)₂CH₂], to give [(OC)₄M{(Ph₂P)₂CH₂}] depending upon the reaction conditions. Condensation of [(CO)₄M{(Ph₂P)₂CH₂}] with different ketones or aldehydes forms [(CO)₄M{(Ph₂P)₂C = CR₁R₂}]. Complexes of the types [(OC)₄M{(Ph₂P)₂C = CR₁R₂}] reacted with hydrazine in a Michael addition to give [(CO)₄M{(Ph₂P)₂CHC(R₁R₂)NHNH₂}](1.3a–e), which condensed with different ketones and aldehydes to give complex of the type [(CO)₄M{(Ph₂P)₂CHC(R₁R₂)NHN = C(R₃)] (1.4a–e). The structures of the complexes are discussed on the basis of elemental analysis (EA), IR,¹H-NMR, ³¹P-NMR spectroscopic data, and FAB mass spectra. The UV/vis spectra show two absorption bands with the low energy band moving to lower energy with increasing substitution on the (diphenylphosphino) methane (dppm) (a bathochromic effect).     

Structural,Theoretical, and Spectroscopic Study of Mercury(II) Complexes of two New Unsymmetric Phosphorus Ylides

Abstract

The reaction of Ph₂PCH₂PPh₂ (dppm) with 4-methylphenacyl bromide and 2-(bromoacetyl)naphthalene in chloroform produce the new phosphonium salts [Ph₂PCH₂PPh₂CH₂C(O)C₆H₄Me]Br (1) and [Ph₂PCH₂PPh₂CH₂C(O)C₁₀H₇]Br (2). Further, by reaction of the monophosphonium salts of dppm with the strong base Et₃N the corresponding bidentate phosphorus ylides, Ph₂PCH₂P(Ph)₂ = C(H)C(O)C₆H₄Me (3) and Ph₂PCH₂P(Ph)₂ = C(H)C(O)C₁₀H₇ (4) were obtained. The reaction of these ligands with mercury(II) halides in dry methanol led to the formation of the mononuclear complexes {HgX ₂[(Ph₂PCH₂PPh₂C(H)C(O)C₆H₄Me)]} [X = Cl (5), Br (6), and I (7)] and {HgX ₂[(Ph₂PCH₂PPh₂C(H)C(O)C₁₀H₇)]} [X = Cl (8), Br (9), and I (10)]. Characterization of the obtained compounds was performed by elemental analysis, IR, ¹H, ³¹P, and ¹³C NMR spectra. The structure of compounds 3 and 10 are unequivocally determined by single crystal X-ray diffraction techniques. X-ray analysis of 10 reveals the presence of mononuclear complex containing Hg atom in a distorted tetrahedral environment. In all complexes, the title ylides are coordinated through the ylidic carbon and the phosphine phosphorus. Computational studies on ligand 4 and complexes 8, 9, and 10 at DFT (B3LYP) level of theory are also reported. It was shown that the formation of P,C-coordinated 1+1 complex 10 is energetically more favored than corresponding P,P-coordinated 1+2 product.

[Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the following free supplemental files: Additional figures]     

2-Phosphinothioyl- and 2-phosphinoylethylcyclopentadienyl zirconium and titanium complexes. Crystal structure of [η5:η1-C5H4CH2CH2P(O)Ph2]TiCl3

The intracomplex conversion of (2-diphenylphosphanoethyl)cyclopentadienyl zirconium and titanium complexes into the corresponding 2-phosphinothioyl and 2-phosphinoyl derivatives, viz., (η⁵-C₅H₅)[η ⁵-C₅H₄CH₂CH₂P(S)Ph₂]ZrCl₂, [η⁵-C₅H₄CH₂CH₂P(S)Ph₂]ZrCl₃, [η⁵:η¹C₅H₄CH₂CH₂P(O)Ph₂]ZrCl₃·THF, and [η⁵:η ¹-C₅H₄CH₂CH₂P(O)Ph₂]TiCl₃ (7), was performed. The NMR spectroscopy data revealed the following order of the coordination ability of the functional groups with respect to the Zr center: Ph₂P=O > Ph₂P > Ph₂P=S. An analogous order was found for the monodentate ligands (Ph₃P=O > Ph₃P > Ph₃P=S) with respect to (η⁵-C₅H₅)ZrCl₃. The molecular structure of complex 7 was established by X-ray diffraction analysis. Coordination of the Ph₂P=O group to the titanium atom was found retained both in the crystalline state and solution.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 116–122, January, 2005.     

Synthesis and structure of the platinum complexes [Bu4N]+[PtBr5(DMSO)]?, [Ph4P]+[PtBr5(DMSO)]?, and [Ph3(n-Am)P]+[PtBr5(DMSO)]?

The complexes [Bu₄N]₂⁺[PtBr₆]²⁻ (I), [Ph₄P]₂⁺[PtBr₆]²⁻ (II), and [Ph₃(n-Am)P]₂⁺ (III) are synthesized by the reactions of tetrabutylammonium bromide, tetraphenylphosphonium bromide, and triphenyl(n-amyl)-tetraphenylphosphonium bromide, respectively, with potassium hexabromoplatinate (mole ratio 2: 1). After recrystallization from dimethyl sulfoxide, complexes I, II, and III transform into [Bu₄N]⁺[PtBr₅(DMSO)]⁻ (IV), [Ph₄P]⁺[PtBr₅(DMSO)]⁻ (V), and [Ph₃(n-Am)P]⁺[PtBr₅(DMSO)]⁻ (VI). According to the X-ray diffraction data, the cations of complexes IV–VI have a slightly distorted tetrahedral structure. The N-C and P-C bond lengths are 1.492(7)–1.533(6) and 1.782(10)–1.805(10) ?, respectively. The platinum atoms in the mononuclear anions are hexacoordinated. The dimethyl sulfoxide ligands are coordinated with the Pt atom through the sulfur atom (Pt-S 2.3280(18)–2.3389(11) ?). The Pt-Br bond lengths are 2.4330(6)–2.4724(6) ?.     

Determination of Spin-Spin Coupling Constants J(PP) on the Basis of 13C and 31p NMR Data

Abstract

The diphosphine dioxides Ph₂P (O) CH₂P (O)Ph₂.(I, Ph₂P(O)CH₂CH₂P(O)Ph₂ (II), Ph₂P(O)CH=CHP(O)Ph₂-cis (III), -trans (IV), [Ph₂P(O)] C=CH (V), [Ph₂P(O) 1₂C=PPh₃ (VI), and also non-symmetric Ph₂(P)OCH=CHP(O)PhEt-trans (VII), Et²P(O)CH=CHP(O)PhEt-trans (VIII), have been studied in CH²C1₂ and CHCl₃ solutions by means of ¹³C and ³¹P NMR.     

ZUR KENNTNIS DES NATRIUMDIPHENYLPHOSPHINOFORMIATS Ph2PCOONa1

Abstract

Ph ₂ PCOONa 2, hergestellt dutch Reaktion von Ph₂PNa mit CO₂, wird in protischen Medien rasch unter Bildung von Ph₂PH and CO₂ hydrolysiert. Die Hydrolyse verlauft in Natronlauge sehr viel langsamer and es bilden sich zusätzlich geringe Mengen Ph₂P(O)O^? und HCOO^?, Aus 2 and stöchiometrischen Mengen RI bilden sich tertiäre Phosphine Ph₂PR (R[dbnd]Me, Et) während mit überschüssigem MeI das Phosphoniumsalz [Ph₂PMe₂]I erhalten wird. Ph₂PCOOMe, Ph₂PCOOSiMe₃ bzw. Ph₂PCSSNa wurden durch Umsetzung von 2 mit (MeO)₂SO₂, Me₃SiCl bzw. CS₂ synthetisiert. Ph₂P(O)ONa and Ph₂P(S)SNa entstanden bei der Reaktion von 2 mit O₂ oder S₈ in Benzol.

Concerning Sodiumdiphenylphosphinoformiate Ph2PCOONa¹.

Ph₂PCOONa 2, prepared from Ph₂PNa and CO₂, is readily hydrolyzed in protic media with formation of Ph ₂ PH and CO₂. Hydrolysis is much slower in NaOH and small quantities of Ph₂P(O)O^? and HCOO^? are additionally formed. Reactions of 2 with RI in stoichiometrical amounts gave tertiary phosphines Ph₂PR (R[dbnd]Me, Et) while the phosphonium compound [Ph₂PMe₂]I resulted from 2 and MeI in excess. Ph₂PCOOMe, Ph₂PCOOSiMe₃ or Ph₂PCSSNa were obtained from 2 and (MeO)₂SO₂, Me₃SiCl or CS₂. Ph₂P(O)ONa and Ph₂P(S)SNa were isolated when 2 was reacted with O₂ or S₈ in benzene.     

New Organophosphorus Proligands and Amide Precursors: Crystal and Molecular Structures of Ph2P(X)NH(C6H3Pri 2-2,6) (X = O,S) and (OPPh2)(O2SMe)N(C6H3Pri 2-2,6)

The new organophosphorus proligand (OPPh₂)(O₂SMe)NR (R = C₆H₃Prⁱ ₂–2,6) (3) was prepared as a white crystalline solid by reacting the lithiated compound Li[Ph₂P(O)NR] with MeSO₂Cl in a 1:1 molar ratio. The precursor Ph₂P(O)NHR (1), as well as its thio analogue Ph₂P(S)NHR (2), were obtained in the reaction between the lithiated amine RNHLi and the corresponding organophosphorus chloride. All compounds were characterized by multinuclear (¹H, ¹³C, and ³¹P) NMR spectroscopy. The molecular structures of 1–3 were established by single-crystal X-ray diffraction. A zigzag polymeric chain is formed in the crystals of 1 and 2 by hydrogen N–H···X (X = O, S) bonding, while the crystal of 3 contains discrete monomeric units with a syn–syn conformation of the O?P(C)₂–N–S(C)(?O)₂ skeleton.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

DIPHOSPHINE COMPOUNDS: PART I. NOVEL BIOLOGICALLY ACTIVE 1,1′bis-AND/OR 1,2-cis-(DIPHENYLPHOSPHINO-)ETHENE AND THEIR COMPLEXES [M(CO)n{Ph2P(CHn)nPPh2}] & [Cu(Cl)2{Ph2P(CHn)nPPh2}], (M = W,Mo, Crn = 1,2….n)

Interaction of [Ph₂PC(═CH₂)PPh₂] (A)^1–3 and/or [Ph₂P (CH═CH) PPh₂](B) ligands in different molar ratio with hexacarbonyl metals M(CO)₆ gives [M(CO) _n Ph₂PC(═CH₂)PPh₂] and/or [M(CO) _n Ph₂P (CH═CH)PPh₂ where M═ Cr, Mo or W, n = 2 and/or 4]. The carbon diphosphine complexes of type (A) which form four heteromemebered rings and/or type (B) form five heteromembered rings which reacts (addition reaction) with some different amines (methyl amine, dimethyl amine), phenyl hydrazine and/or some of amino acids (glycine, alanine, aspartic acid, serene). The structures of A and/or B complexes and their amino derivatives have been characterized by using elemental analysis, IR spectra, ¹HNMR,¹H-³¹P-NMR, and mass spectra. Ligands and their complexes were screened in vitro to investigate the biological activities (antibacterial and antifungi). Interestingly, complexes are having strong and remarkable activities increases than the free ligands.     

Synthesis and Structures of 3,5-disubstituted 1,2,4-triazole Head Units and Incorporation of 3,5-dibenzoyl-1,2,4-triazolate into New [2 + 2] Schiff-Base Macrocyclic Complexes

The synthesis and characterization of sodium 3,5-diacetyl-1,2,4-triazolate (4 ^Me ) and sodium 3,5-dibenzoyl-1,2,4-triazolate (4 ^Ph ), both of which can be used as head unit building blocks in Schiff-base reactions, are reported. The crystal structures of sodium 3,5-diacetyl-1,2,4-triazolate, as [4 ^Me (H₂O)]_∞, and sodium 3,5-dibenzoyl-1,2,4-triazolate, as [4 ^Ph (CH₃OH)₂]₂, have been determined. The former is a helical polymer whilst the latter is a methanol-bridged dimer. The lead(II) templated cyclization reaction of sodium 3,5-dibenzoyl-1,2,4-triazolate (4 ^Ph ) with 1,3-diaminopropane or 1,4-diaminobutane, respectively, leads to the formation of two new [2 + 2] Schiff-base macrocycles as their lead(II) complexes, [Pb₂ L ^3Ph (μ-OH)]ClO₄ (5) and [Pb₂ L ^4Ph (μ-OH)]ClO₄ (6), respectively. Transmetallation of 5 with nickel(II) ions yields a novel, structurally characterized, dinickel(II) macrocyclic complex, [Ni₂ L ^3Ph (NCS)₂] (7), which features double triazolate bridging of the two five-coordinate nickel(II) ions.     

Formation of carbonylrhenium cryptates with alkali metal cations: Coordination chemistry studies of [Ph2P(E)NP(E)Ph2], E = O,S, Se towards ReBr(CO)5

Reaction of ReBr(CO)₅ with Li[Ph₂P(O)NP(O)Ph₂] afforded the cryptate Li[Re₂(CO)₆{μ-Ph₂P(O)NP(O)Ph₂-κ²O,O’}₃]; whereas K[Ph₂P(O)NP(O)Ph₂] reacted with ReBr(CO)₅ to give K[Re₂(CO)₆{μ-Ph₂P(O)NP(O)Ph₂-κ²O,O′}{Ph₂P(O)NP(O)Ph₂-κ²O,O′}₂]. Other chalcogen ligands’ salts M[Ph₂P(E)NP(E)Ph₂], E = Se and S, M = K and Li gave dirhenium carbonyls with bromido and Ph₂P(E)NP(E)Ph₂, E = Se or S bridges upon reaction with ReBr(CO)₅.     

Synthese und Eigenschaften von [Ph2(Carb)P]AlCl4 (Carb = 2,3‐Dihydro‐1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐yliden) – ein stabiler Carben‐Komplex des dreiwertigen Phosphors [1]

Synthesis and Properties of [Ph₂(Carb)P]AlCl₄ (Carb = 2,3‐Dihydro‐1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene) – a Stable Carbene Complex of Trivalent Phosphorus [1] 2,3‐Dihydro‐1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene ( 7 , Carb) reacts with chlorodiphenylphosphane to give the cationic phosphane [Ph₂(Carb)P]Cl ( 10 ) which is transferred to the more stable salt [Ph₂(Carb)]AlCl₄ ( 13 ) on treatment with AlCl₃. The cationic phosphane selenide [Ph₂(Carb)PSe]AlCl₄ ( 14 ) is obtained from 13 and selenium. Spectroscopic and structural data indicate [Ph₂(Carb)P]⁺ to be a cationic analogue of Ph₃P. The X‐ray structure of 13 is reported.     

Synthesis and Structure of Phosphorus-Containing Complexes [Ph4P]

Complexes [Ph₄P] ₂ ⁺ [Hg₄I₁₀]²⁻ (I) and [[Ph₄P] ₂ ⁺ [BiI₅(Me₂S=O)]²⁻ (II) are synthesized by the reactions of tetraphenylphosphonium Ph₄PI with mercury diiodide in acetone and with bismuth triiodide in dimethyl sulfoxide, respectively. According to X-ray diffraction analysis, structural units of these complexes are tetraphenylphosphonium cations and tetra- and mononuclear anions, respectively. The phosphorus atoms in the tetraphenylphosphonium cations have a distorted tetrahedral coordination. In the central fragment of the centrosymmetric anion [Hg₄I₁₀]²⁻, the distances between the terminal mercury atoms and iodine atoms are 3.503(2) Å. The mercury atoms in the central and terminal fragments of compound I have distorted tetrahedral and trigonal coordinations, respectively. The bismuth atom in the mononuclear octahedral anion of complex II contains a dimethyl sulfoxide molecule along with five iodine atoms in the coordination sphere. __________ Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 10, 2005, pp. 791–795. Original Russian Text Copyright ? 2005 by Sharutin, Egorova, Sharutina, Dorofeeva, Molokov, Fukin.     

Complex-forming and selectivity properties of substituted tetraphenylethylenediphosphine dioxides with respect to alkali metal cations

The complex-forming reactivity of mono- and disubstituted ethylenediphosphine dioxides of the general formula Ph₂P(O)CH₂C(R¹R²)P(O)Ph₂, and of a tetraphosphorylated monopodand, ortho-bis[4,5-bis(diphenylphosphinyl)-pentoxy]benzene, relative to alkali metal cations have been determined conductometrically in THF-CHCl₃ medium (4:1). Introduction of alkyl substituants in the ethylene bridge of tetraphenylethylenediphosphine dioxide increases its Li/Na selectivity; maximum Li/Na selectivity equal to 40 is observed for the dimethyl-substituted tetraphenylethylenediphosphine dioxide derivative. Among the ligands examined herein the hexadentate tetraphosphoryl-containing monopodand ortho-bis[4,5-bis(diphenylphosphinyl)pentoxy]benzene was found to be the most effective complex-forming agent with respect to lithium (log=6.0), with a high Li/Na selectivity value equal to 40. The syntheses of 1,1-dimethyltetraphenylethylenediphosphine dioxide and of ortho-bis[4,5-bis(diphenylphosphinyl)pentoxy]benzene are described.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 873–877, April, 1990.The authors wish to thank Z. N. Vostroknutovii for carrying out the stability constant measurements in anhydrous acetonitrile.     

Mixed ligand transition metal complexes of tertiary phosphines and 5-phenyl-l,3,4-oxadiazole-2-thione

Transition metal complexes containing two types of ligands: 5-phenyl-1,3,4-oxadiazole-2-thione ion (L) and tertiary phosphines, have been prepared. The complexes, [ML₂A₂] [M = Pd or Pt; A = PPh₃ or Ph₂PCH₂CH₂P(O)Ph₂] and [ML₂B] (M = Co, Ni, Pd or Pt; B = Ph₂PCH₂PPh₂ or Ph₂PCH₂CH₂PPh₂), were characterized by elemental analysis, molar conductance, i.r., u.v.–vis., ³¹P-n.m.r., magnetic susceptibility measurements and mass spectra.     

Electronic Structure of Monodithiolated Iron?Oxotungsten Heterometallic Complexes: Integer‐Spin Fe?W Assembly

Fe? W heterometallic complexes, in which an FeX₂ (X=Cl, SPh) moiety is attached to monodithiolene oxotungsten through a sulfide bridge, that is, [Ph₄P]₂[Cl₂Fe(S)₂WOS₂] ( 1 ), [Ph₄P]₂[Cl₂Fe(S)₂WOS₂(DMED)] ( 2 , DMED=dimethylethylenedicarboxylate), [Ph₄P]₂[Cl₂Fe(S)₂WO(tdt)] ( 3 , tdt=toluenedithiolate), [Ph₄P]₂[(SPh)₂Fe(S)₂WO(tdt)] ( 4 ), and [Ph₄P]₂[Cl₂Fe(S)₂WO(edt)] ( 5 , edt=ethanedithiolate), are reported. Mössbauer and EPR spectroscopy, magnetism, electrochemistry, and electronic structural analysis based on DFT and TD‐DFT calculations show the transfer of electron from the iron center to the tungsten center, thus resulting in a ferromagnetically coupled Fe^IIIW^V unit, along with antiferromagnetic intermolecular interactions, from the starting Fe^II and W^VI compounds. A net spin of a S=3 ground state, which arises from ferromagnetically coupled Fe^III and W^V atoms, displays a rare X‐band EPR in normal mode at g≈7 in the solid state.     

The 1H, 13C and 31P NMR spectra of EZ pairs of some phosphorus substituted alkenes

The olefins Ph₂P(X)CH?CHR [X=lone pair, O, S, Ch₃I; R?Ch₃, ph, P(X)ph₂] have been prepared and their ¹H, ¹³C and ³¹P NMR spectra measured. trans ³J[P(IV)C] (range 18.3–25.7 Hz) is greater than cis ³J[P(IV)C] (range 6.9–11 Hz) but this relationship does not hold for P(III) compounds. In the ³¹P spectra the E isomer absorbs to higher field than the Z isomer for P(III) and P(IV) compounds. The ¹H data are in accord with previous results; average substituent shielding coefficients for ph₂P(X) substituted alkenes are reported.     

SYNTHESIS AND CHARACTERIZATION OF THE FIRST BORANE ADDUCTS AND BORON CATIONS OF SOME N-ALKYL AND N-AMINOTRIPHENYLPHOSPHORANIMINES

Abstract

The first borane adducts of N-alkyl and N-aminotriphenylphosphoranimines, Ph₃P[dbnd]N—R, were prepared by two different general synthetic methods. The first method involved displacement of THF (tetrahydofuran) from THF-borane by the free imines, and the second employed the reaction of LiBH₄ with iminium bromides, Ph₃P[dbnd]N(R)HBr, in diethyl ether. Imine boranes, Ph₃P[dbnd]N(R)BH₃, were synthesized where R [dbnd] methyl, ethyl, n-propyl, isopropyl, isobutyl, t-butyl. dimethylamino, phenylamino, and methyl, phenylamino as the nitrogen attached groups. Symmetrical boron cations, (Ph₃P[dbnd]NR)₂, BH₂ ⁺, where R = methyl, ethyl, and n-propyl, were synthesized by displacement of iodide from in-situ generated iodoborane adducts, Ph₃P[dbnd]N(R)BH₂I, by the free imines. An attempt to form an unsymmetrical boron cation from (CH₃)₃ NBH₂I and Ph, P[dbnd]N(n-C₃H₇) resulted only in a mixture of the corresponding symmetrical boron cations. Physical, chemical and spectral properties of the borane adducts and boron cations, namely thermal and hydrolytic stabilities, infrared and NMR data are presented. Oxidative and reductive stabilities of the boron cations were studied. The borane adducts can be chlorinated with either HCI or Ph₃CCI. Relative base strengths of some imines were determined by following the exchange of BH₃ between borane adducts of (CH₃)₃ N or 4- (CH₃)C₅H₄ N and the imines via NMR.     

Cyclic Phosphorus(V) Compounds: Phosphazanes and Anhydrides

Abstract

³¹P n.m.r. has been extensively used to study the preparation and reactions of cyclic phosphorus-(V) compounds containing P-N-P and P-O-P linkages. Michaelis “Oxyphosphazobenzolchlorid”,[C₆H₅NPOCl]_n has been shown by ³¹P n.m.r. and mass spectroscopy to be the trimer (n=3), not the dimer as proposed by Michaelis. The competing reactions of aniline hydrochloride and POCl₃ to form the dimer (two isomers cis- and trans-) and the trimer have been elucidated. With PSCl₃ only the dimer [C₆H₅NPSCl]₂ is formed (both isomers).