Reactivity of an Intramolecular Fluorophosphonium Fluoroborate

The reactions of the intramolecular frustrated Lewis pair‐adduct Ph₂PC(p‐Tol)?C(C₆F₅)B(C₆F₅)₂(CNtBu) with XeF₂ gave Ph₂P(F)C(p‐Tol)?C(C₆F₅)B(F)(C₆F₅)₂ ( 3 ). This species reacts with two equivalents of Al(C₆F₅)₃?C₇H₈ producing the salt, [Ph₂P(F)C(p‐Tol)?C(C₆F₅)B(C₆F₅)₂][F(Al(C₆F₅)₃)₂] ( 4 ), whereas reaction with HSiEt₃/B(C₆F₅)₃ gave Ph₂P(F)C(p‐Tol)?C(H)B(C₆F₅)₃ ( 5 ). The photolysis of 3 resulted in aromatization affording the phenanthralene derivative Ph₂P(F)C(p‐Tol(o‐C₆F₄))?CB(F)(C₆F₅)₂ ( 6 ).     

Reactions involving transition metals: XX. A comparison of the reactions of 1,2,3,4,7,7-hexafluorobicyclo[2.2.1]heptadiene,and 2,3-bis(trimethyltin)- and 2,3-dichloro-1,4,5,6,7,7-hexafluorobicyclo[2.2.1]hepta-2,5-dienes with low valent transition metal complexes

1,2,3,4,7,7-Hexafluorobicyclo[2.2.1]heptadiene (1) and 2,3-bis(trimethyltin)-1,4,5,6,7,7-hexafluorobicyclo[2.2.1]hepta-2,5-diene (2) react with [M(Ph₃P)₄] (M = Pt, Pd) to afford air-stable adducts. 2,3-Dichloro-1,4,5,6,7,7-hexafluorobicyclo[2.2.1]hepta-2,5-diene (3) gives only [PtCl₂(PPh₃)₂] with [Pt(Ph₃P)₄], but a low yield of an adduct was obtained with [Pd(PPh₃)₄]. The diene 1 also reacts with Fe(CO)₅ to form the complex [(C₇H₂F₆)Fe(CO)₄], and with [Rh(C₂H₄)₂(acac)] to give [(C₇H₂F₆)Rh(acac)] in which the diene acts as a bidentate ligand. Similar products could not be isolated from the reactions of 2 and 3. A stable adduct, believed to be [{C₇F₆(SnMe₃)₂}Rh(CO)₂(μ-Cl)₂Rh(CO)₂] has been isolated from the reaction between 2 and [Rh(CO)₂Cl]₂. This adduct reacts with PPh₃ to give the bridge-cleavage product [{C₇F₆(SnMe₃)₂}RhCl(CO)(PPh₃)₂]. Reaction of 1 with [Rh(CO)₂Cl]₂ gives an unstable adduct which could not be isolated, and 2 does not react at room temperature. The chloro derivative 3 reacts with [PdCl₂(PhCN)₂] to give the adduct [(C₇F₆Cl₂)PdCl(PhCN)], but 1 and 2 do not react under similar conditions. Stable substitution products [(C₇F₆R₂)M] (R = H, M = Fe(CO)₂(η-C₅H₅); R = SnMe₃, M = Fe(CO)₂(η-C₅H₅), Mn(CO)₅, Ir(CO)₂(PPh₃)₂, Rh(CO)₂(PPh₃)₂; R = Cl, M = Ir(CO)₂(PPh₃)₂, Rh(CO)₂(PPh₃)₂) have been isolated from the reactions of the dienes with carbonylmetal anions. Insertion of the CHCH bond occurs when 1 is heated with [MnMe(CO)₅] to give [{C₇F₆H₂C($\text{O)Me}M}$n(CO)₄], and this, on reaction with either PPh₃ or [Pt(PPh₃)₄], gives [(C₇F₆H₂COMe)Mn(CO)₄PPh₃].     

Syntheses,Characterizations, and Crystal Structures of β‐Diketiminato Compounds of Pentafluorophenyl Group 12 Derivatives,HC{[C(Me)N(C6H3‐2, 6‐i‐Pr2)]2}MC6F5 (M = Zn,Cd)

The reactions of H₂C[C(Me)N(C₆H₃‐2, 6‐i‐Pr₂)]₂ ((DPP)₂NacNacH) and Zn(C₆F₅)₂ · 2 EtCN or Cd(C₆F₅)₂ · 2 MeCN in a molar ratio of approximately 1:1 selectively gave the derivatives (DPP)₂NacNacMC₆F₅ (M = Zn, Cd) in excellent yields. No reaction was observed between (DPP)₂NacNacH and Hg(C₆F₅)₂ under similar conditions. Reactions with Hg(C₆F₅)OCOMe yielded the products of dismutation, Hg(C₆F₅)₂ and Hg(OCOMe)₂. (DPP)₂NacNacZnC₆F₅ crystallises as a 1:1 adduct with THF with two independent molecules per unit cell (triclinic, P1 (no. 2)). The zinc atom is tetrahedrally surrounded by the chelating ligand, the pentafluorophenyl group and one THF molecule. A similar situation is found in the 1:1 adduct of (DPP)₂NacNacCdC₆F₅ and DMF (monoclinic, P2₁/n (no. 14)), while in the donor‐free compound (CDCl₃ and H₂O co‐crystallize) the cadmium atom is nearly ideally trigonal planar co‐ordinated (orthorhombic, Pbnm (no. 62)).     

Synthesis and reactivity of alkynyl-linked phosphonium borates

The phosphine tBu₂PC?CH ( 1 ) was reacted with B(C₆F₅) to give the zwitterionic species tBu₂P(H)C?CB(C₆F₅)₃ ( 2 ). The analogous species tBu₂P(Me)C?CB(C₆F₅)₃ ( 3 ), tBu₂P(H)C?CB(Cl)(C₆F₅)₂ ( 4 ), tBu₂P(H)C?CB(H)(C₆F₅)₂ ( 5 ), and tBu₂P(Me)C?CB(H)(C₆F₅) ₂ ( 6 ) were also prepared. The salt [tBu₂P(H)C?CB(C₆F₅)₂(THF)][B(C₆F₅)₄] ( 7 ) was prepared through abstraction of hydride by [Ph₃C][B(C₆F₅)₄]. Species 5 reacted with the imine tBuN?CHPh to give the borane–amine adduct tBu₂PC?CB[tBuN(H)CH₂Ph](C₆F₅)₂ ( 8 ). The related phosphine Mes₂PC?CH ( 9 ; Mes=C₆H₂Me₃) was used to prepare [tBu₃PH][Mes₂PC?CB(C₆F₅)₃] ( 10 ) and generate Mes₂PC?CB(C₆F₅)₂. The adduct Mes₂PC?CB(NCMe)(C₆F₅)₂ ( 11 ) was isolated. Reaction of Mes₂PC?CB(C₆F₅)₂ with H₂ gave the zwitterionic product (C₆F₅)₂(H)BC(H)?C[P(H)Mes₂][(C₆F₅)₂BC?CP(H)Mes₂] ( 12 ). Reaction of tBu₂PC?CB(C₆F₅)₂, a phosphine–borane generated in situ from 5 , with 1‐hexene gave the species [tBu₂PC?CB(C₆F₅)₂](CH₂CHnBu)[tBu₂PC?CB(C₆F₅)₂] ( 13 ) and subsequent reaction with methanol or hexene resulted in the formation of [tBu₂P(H)C?CB(C₆F₅)₂](CH₂CHnBu)[tBu₂PC?CB(C₆F₅)₂](OMe) ( 14 ) or the macrocycle {[tBu₂PC?CB(C₆F₅)₂](CH₂CH₂nBu)}₂ ( 15 ), respectively. In a related fashion, the reaction of 13 with THF afforded the macrocycle [tBu₂PC?CB(C₆F₅)₂](CH₂CHnBu)[tBu₂PC?CB(C₆F₅)₂][O(CH₂)₄] ( 16 ), although treatment of tBu₂PC?CB(C₆F₅)₂ with THF lead to the formation of {[tBu₂PC?CB(C₆F₅)₂][O(CH₂)₄]}₂ ( 17 ). In a related example, the reaction of Mes₂PC?CB(C₆F₅)₂ with PhC?CH gave {[Mes₂PC?CB(C₆F₅)₂](CH?CPh)}₂ ( 18 ). Compound 5 reacted with AlX₃ (X=Cl, Br) to give addition to the alkynyl unit, affording (C₆F₅)₂BC(H)?C[P(H)tBu₂](AlX₃) (X=Cl 19 , Br 20 ). In a similar fashion, 5 reacted with [Zn(C₆F₅)₂] ? C₇H₈, [Al(C₆F₅)₃] ? C₇H₈, or HB(C₆F₅)₂ to give (C₆F₅)₃BC(H)?C[P(H)tBu₂][Zn(C₆F₅)] ( 21 ), (C₆F₅)₃BC(H)?C[P(H)tBu₂][Al(C₆F₅)₂] ( 22 ), or [(C₆F₅)₂B]₂HC?CH[P(H)tBu₂] ( 23 ), respectively. The implications of this reactivity are discussed.     

Planar N‐Heterocyclic Carbene Diarylborenium Ions: Synthesis by Cationic Borylation and Reactivity with Lewis Bases

The NHC–borane adduct (IBn)BH₃ ( 1 ) (NHC= N‐heterocyclic carbene; IBn=1,3‐dibenzylimidazol‐2ylidene) reacts with [Ph₃C][B(C₆F₅)₄] through sequential hydride abstraction and dehydrogenative cationic borylation(s) to give singly or doubly ring closed NHC–borenium salts 2 and 3 . The planar doubly ring closed product [C₃H₂(NCH₂C₆H₄)₂B][B(C₆F₅)₄] is resistant to quaternization at boron by Et₂O coordination, but forms classical Lewis acid–base adducts with the stronger donors Ph₃P, Et₃PO, or 1,4‐diazabicyclo[2.2.2]octane (DABCO). Treatment of 3 with tBu₃P selectively yields the unusual oligomeric borenium salt trans‐[(C₃H₂(NCH₂C₆H₄)₂B)₂(C₃H₂(NCHC₆H₄)₂B)][B(C₆F₅)₄] ( 7 ).     

Photochemical and thermal reactions of η5-cyclopentadienyltetracarbonylvanadium and bis(pentafluorophenyl)acetylene

The photolysis of (η⁵-C₅H₅)V(CO)₄ in the presence of one or two equivalents of bis(pentafluorophenyl)acetylene yields (η⁵-C₅H₅)V(CO)₂(C₆F₅CCC₆F₅). One carbon monoxide ligand in this acetylene adduct can be photochemically displaced by triphenylphosphine to yield (η⁵-C₅H₅)V(CO)[P(C₆H₅)₃](C₆F₅CCC₆F₅). This complex is also obtained by the photolysis of (η⁵-C₅H₅)V(CO)₃P(C₆H₅)₃ in the presence of bis(pentafluorophenyl)acetylene. In vacuo, melt-phase thermolysis of (η⁵-C₅H₅)V(CO)₂(C₆F₅CCC₆F₅) and bis(pentafluorophenyl)acetylene produces (η⁵-C₅H₅)V(CO)(C₆F₅CCC₆F₅)₂. This diacetylenic complex as well as the perfluorinated organic compounds 2,3,5,6-tetrakis(pentafluorophenyl)-1,4-benzoquinone, 2,3,4,5-tetrakis(pentafluorophenyl)cyclopentadienone and 2,3,4,5,6,7-hexakis(pentafluorophenyl)cycloheptatrienone are also obtained from thermal reactions of (η⁵-C₅H₅)V(CO)₄ and bis(pentafluorophenyl)acetylene in solution. Photolysis of (η⁵-C₅H₅)V(CO)(C₆F₅CCC₆F₅)₂ in the presence of carbon monoxide produces (η⁵-C₅H₅)V(CO)₂(C₆F₅CCC₆F₅). The photochemical and thermal reactions of bis(pentafluorophenyl)acetylene and (η⁵-C₅H₅)V(CO)₄ are compared and contrasted with similar reactions of diphenylacetylene and (η⁵-C₅H₅)V(CO)₄.     

1,1‐Hydroboration and a Borane Adduct of Diphenyldiazomethane: A Potential Prelude to FLP‐N2 Chemistry

Diphenyldiazomethane reacts with HB(C₆F₅)₂ and B(C₆F₅)₃, resulting in 1,1‐hydroboration and adduct formation, respectively. The hydroboration proceeds via a concerted reaction involving initial formation of the Lewis adduct Ph₂CN₂BH(C₆F₅)₂. The highly sensitive adduct Ph₂CN₂(B(C₆F₅)₃) liberates N₂ and generates Ph₂CB(C₆F₅)₃. DFT computations reveal that formation of Ph₂CN₂B(C₆F₅)₃ from carbene, N₂, and borane is thermodynamically favourable, suggesting steric frustration could preclude carbene–borane adduct formation and affect FLP‐N₂ capture.     

Interaction of 1,3,2,4‐Benzodithiadiazines with Aromatic Phosphines and Phosphites

Although an interaction between hydrocarbon and fluorocarbon 1,3,2,4‐benzodithiadiazines ( 1 ) and P(C₆H₅)₃ continuously produces chiral 1,2,3‐benzodithiadiazol‐2‐yl iminophosporanes ( 2 ; in this work, 5,7‐difluoro derivative 2a ) via 1:1 condensation, an interaction between 1 and other PR₃ reagents gives different products. With R  OC₆H₅ and both hydrocarbon and fluorocarbon 1 , only X=P(OC₆H₅)₃ (X = S, O) were identified in the complex reaction mixtures by ¹³С and ³¹Р NMR and GC‐MS. With R = C₆F₅, no interaction with the archetypal 1 was observed but catalytic addition of atmospheric water to the heterocycle afforded 2‐amino‐N‐sulfinylbenzenesulfenamide ( 4 ). With electrophilic B(C₆F₅)₃ instead of nucleophilic P(C₆F₅)₃, only adduct H₃N→B(C₆F₅)₃ and a new polymorph of C₆F₅B(OH)₂ were isolated and identified by X‐ray diffraction (XRD). A molecular structure of 2a was confirmed by XRD, and the π‐stacked orientation of one of phenyl groups and heterocyclic moiety was observed. This structure is in general agreement with that calculated at the RI‐MP2 level of theory, as well as at three different levels of DFT theory with the PBE and B3LYP functionals. Mild thermolysis of 2a in a dilute decane solution gave persistent 5,7‐difluoro‐1,2,3‐benzodithiazolyl ( 3a ) identified by EPR in combination with DFT calculations.     

Pentafluorphenylverbindungen des Phosphors

Pentafluorophenyl Compounds of Phosphorus The preparation of compounds of the type R(C₆F₅)PX (R = CH₃, C₂H₅, t-C₄H₉ and C₆H₅: X = F, Cl, Br and N(C₂H₅)₂) is described. These derivatives are converted to trifluorophosphoranes, R(C₆F₅)PF₃, and phosphinic acid fluorides, R(C₆H₅)P(:O)F. The n.m.r. spectra are discussed.     

Organonickel(II) Complexes with Anionic N-Donor Ligands. Hydration of coordinated nitriles at a nickel(II) site

The hydroxo complex (Bu₄N)₂[Ni₂(C₆F₅)₄(μ-OH)₂]reacts with 2,3,4,5,6-pentafluoro benzenamine (C₆F₅-NH₂), 1,3-diaryltriaz-1-enes (ArNH? N=N? Ar, Ar = Ph, 4-MeC₆H₄, 4-MeOC₆H₄), 7-aza-1H-indole (= 1H-pyrrolo[2.3-b]pyridine; Hazind), N-phenylpyridin-2-amine(pyNHPh), and N-phenylpyridine-2-carboxamide (py-CONHPh) at room temperature in acetone to give the binuclear complexes (Bu₄N)₂[Ni₂(C₆F₅)₄(μ-C₆F₅NH)₂] ( 1 ) and (Bu₄N)₂[{Ni(C₆F₅)₂} 2(μ-OH)(μ-azind)] ( 2 ) and the mononuclear complexes Bu₄N[Ni(C₆F₅)2(ArN₃Ar)] ( 3 – 5 ), Bu₄N[Ni(C₆F₅)₂(pyNPh)] ( 6 ), and Bu₄N[Ni(C₆F₅)₂(pyCONPh)] ( 7 ). The hydroxo.complex (Bu₄N)₂[{Ni(C₆F₅)2-(μ-OH)}₂] promotes the nucleophilic addition of water to pyridine-2-carbonitrile, 2-aminoacetonitrile, and 2-(dimethylamino)acetonitrile, and complexes 8 – 10 containing pyridine-2-carboxamidato, 2-aminoacetamidato and 2-(dimethylamino)acetamidato ligands are formed. Analytical (C, H, N) and spectroscopic (IR, ¹H and ¹⁹F-NMR, and FAB-MS) data were used for structural assignments. A single-crystal X-ray diffraction study of (Bu₄N)₂[{Ni(C₆F₅)₂}₂(μ-OH)(μ-azind)] ( 2 ) established the binuclear nature of the anion; the two Ni-atoms are bridged by an OH group and a 7-aza-7H-indol-7-yl group, but the central Ni? O? Ni? N? C? N ring is not planar, the dihedral angle between the Ni? O? Ni and Ni? N? C? N? Ni planes being 84.4°.     

Disproportionation reactions between alkyl and fluoroalkyl radicals. V. Perfluoro-n-propyl and ethyl radicals revisited

A redetermination of the disproportionation/combination ratio for n–C₃F₇ and C₂H₅ radicals gives a value of Δ(n–C₃F₇, C₂H₅) = 0.13 ± 0.01, independent of the temperature. The radicals were produced by the photolysis of n–C₃F₇COC₂H₅. The previous determinations of this ratio are discussed and are found to be largely incorrect. The values for Δ(CF₃, C₂H₅) and Δ(C₂F₅, C₂H₅) are also re-evaluated, and the recommended values are 0.10 ± 0.02 and 0.12 ± 0.02, respectively. Systems involving perfluoroalkyl and ethyl radicals are complicated due to rapid perfluororadical addition to the ethylene formed in the disproportionation process. The extent of this reaction, and its consequences, are discussed and evaluated. The role of the propionyl (C₂H₅CO) radical in the room temperature photolysis is also assessed. However, it is found that the Δ values determined by the intercept method used in this work are not affected by the secondary reactions that occur. It is concluded that high cross-combination ratios are general to perfluoroalkyl-alkyl radical interactions. For C₃F₇ and C₂H₅ radicals the ratio is 2.7–2.8. Above 100°C ratios exceed 3 due to secondary reactions.     

Optisch aktive übergangsmetall-komplexe XX. Optisch aktive cyclopentadienyl-perfluoropropyl-kobalt-komplexe mit zweizähnigen schiff-basen

In the reaction of C₅H₅ Co(C₃F₇)(CO)I with the Schiff base NN′, derived from S-(-)-?-phenylethylamine and pyridine carbaldehyde-2, the salt [C₅H₅Co(C₃F₇)NN′]⁺ I^? (Ia,b) is formed, which can be transformed to [C₅H₅ Co(C₃F₇)NN′]⁺ PF₆^? (IIa,b). The sodium salt Na⁺ [NN″]^? of the Schiff base, derived from S-(-)-α-phenylethylamine and pyrrol carbaldehyde-2, in the reaction with C₅H₅ C0(C₃F₇)(CO)I yields the neutral complex C₅H₅ Co(C₃F₇)NN″ (IIIa,b). The diastereoisomeric pairs IIa,b and IIIa,b are separated by fractional crystallisation and chromatography respectively into the optically pure components which differ in their ¹H NMR spectra. The IR, UV, CD, mass spectra and optical rotations of the new compounds IIa, IIb, IIIa and IIIb are compared.     

Molecular Structures of Mononuclear Rhodium Complexes Containing the Polydentate Ligand Tri(1‐cyclohepta‐2,4,6‐trienyl)phosphane,P(C7H7)3. Classification according to the 31P Chemical Shifts

The olefinic phosphane P(C₇H₇)₃ ( 5 ) behaves as a tetradentate tripod ligand in [RhCl{P(η²‐C₇H₇)₃}] ( 6 ), using all 3 cyclohepta‐2,4,6‐trienyl substituents as η²‐coordinating side‐arms. Nucleophilic displacement of the one‐electron chloro ligand by halides or pseudohalides to give [RhX{P(η²‐C₇H₇)₃}] (X = Br ( 7a ), I ( 7b ), N₃ ( 7c ), NCO ( 7d )) leaves the basket‐like framework [Rh{P(η²‐C₇H₇)₃}] intact. Reactions of 6 with three‐electron ligands result in decomplexation of one cyclohepta‐2,4,6‐trienyl ring and formation of [Rh(L³){P(C₇H₇)(η²‐C₇H₇)₂}] (L³ = acetylacetonate ( 8 ), 2‐carboethoxy cyclopentanonate ( 8a )), reactions of 6 with five‐electron ligands such as η⁵‐C₅H₅ cause decomplexation of two olefinic side‐arms to give [Rh(L⁵){P(C₇H₇)₂(η²‐C₇H₇)}] (L⁵ = η⁵‐C₅H₅ (Cp) ( 9 ), η⁵‐C₅H₄^tBu ( 9a )). The last remaining chelate ring in 9 is opened by pressure‐carbonylation to give the adduct [Rh(Cp)(CO){P(C₇H₇)₃}] ( 10 ) or by oxidative addition of halogens to form [Rh(Cp)X₂{P(C₇H₇)₃}] (X = Br, I). The full set of ¹H, ¹³C, ³¹P, and ¹⁰³Rh NMR data is given for the prototype complexes 7a , 8 , 9 , and 10 , and the molecular geometries of the [Rh{P(C₇H₇)₃}] fragments are compared on the basis of the X‐ray structural determinations of 6 , 8 , 8a , 9 , 9a , and 10 . The chemical shifts δ(³¹P) provide a reliable parameter for the prediction of the molecular structures of the rhodium complexes in solution.     

Bulky Polyfluorinated Terphenyldiphenylboranes: Water Tolerant Lewis Acids

Protocols for the synthesis of the bulky polyfluorinated triarylboranes 2,6-(C₆F₅)₂C₆F₃B(C₆F₅)₂ ( 1 ), 2,6-(C₆F₅)₂C₆F₃B[3,5-(CF₃)₂C₆H₃] ( 2 ), 2,4,6-(C₆F₅)₃C₆H₂B(C₆F₅)₂ ( 3 ), 2,4,6-(C₆F₅)₃C₆H₂B[3,5-(CF₃)₂C₆H₃] ( 4 ) were developed. All boranes are water tolerant and according to the Gutmann-Beckett method, 1 – 3 display Lewis acidities larger than that of the prominent B(C₆F₅)₃.     

Frustrated Lewis Pair Chemistry of Chiral (+)‐Camphor‐Based Aminoboranes

Dimethylamino‐(+)‐camphorenamine reacted with an equimolar amount of Piers’ borane, HB(C₆F₅)₂, to give the corresponding iminium–hydroborate zwitterionic salt. Being in equilibrium with the parent enamine–HB(C₆F₅)₂ N–B pair, this salt was able to split hydrogen heterolytically, hydrogenating the iminium group in the molecule. Detailed studies revealed that the hydrogen splitting in this reaction proceeded through an intermolecular pathway leading to a bornylamine–HB(C₆F₅)₂ adduct. When the starting enamine is present in excess over HB(C₆F₅)₂, the produced bornylamine–HB(C₆F₅)₂ adduct breaks up, eliminating free bornylamine and forming the initial camphorenamine– HB(C₆F₅)₂ pair. This results in hydrogenation of the camphorenamine framework in a catalytic fashion.     

A Silylene–Borane Lewis Pair as a Tool for Trapping a Water Molecule: Silanol Formation and Dehydrogenation

The Lewis acid B(C₆F₅)₃ and the cyclic silane (Ar^N₂Si)₃ ( 1 ) (Ar^N=o-(CH₃)₂NCH₂C₆H₄) are useful precursors to access the silylene(II)–borane adduct Ar^N₂Si-B(C₆F₅)₃ ( 2 ). Treatment of 2 with water led to coordination and gave the Lewis pair (Ar^N₂H₂O)Si-B(C₆F₅)₃ ( 3 ) that exhibits a hydrogen-bond-stabilized silanol unit. It can be converted into the siloxane [(HAr^N)₂SiOB(C₆F₅)₃]₂O ( 6 ) by dehydrogenation in the presence of a base. Heteronuclear NMR spectroscopic data to characterize the compounds were supported by quantum-chemical calculations.     

Aminophosphane. XI. Einige Reaktionen des N-Diphenylphosphino-triphenyl-phosphazens

N-Diphenylphosphino-triphenylphosphazene possesses a highly reactive (C₆H₅)₂P group. At room temperature CH₃J adds to give (C₆H₅)₃P?N?P(C₆H₅)₂CH ₃J whilst phenylbromide did not react under similar conditions. The phosphorous halides (C₆H₅)₂PX(X = Cl, Br)add in a 1:1 mole ratio to yield (C₆H₅)₃P?N?P(C₆H₅)₂? PC₆H₅)₂X; this addition is also the preferred reaction with C₆H₅PCl₂, but PCl₃ is in part dehalogenated by (C₆H₅)₃P?N? P(C₆H₅)₂, and PSCl₃ desulfurized. The chalcogens O, S, Se, Te readily add to the P(III) atom of the base and this is also the case with BH₃. CS₂ forms the betaine (C₆H₅)₃ · · P?N? P(C₆H₅)₂? C(S)S. The IR and NMR spectra of the new compounds are discussed.     

Optisch aktive übergangsmetall-komplexe : XVIII. Über die reaktion von C5H5Co(CO)(C3F7)j mit isonitrilen

In the reaction of C₅H₅Co(CO)(C₃F₇)I with isonitriles in the molár ratio $\text{1}\text{1}$ the brown complexes C₅H₅Co(CNR)(C₃F₇)I are formed. The fluorine atoms of the α-CF₂ groups are diastereotopic because of the asymmetric center at the Co atom. With (—)-α-phenylethylisonitrile a pair of diastereoisomers is obtained which could not be separated.C₅H₅Co(CO)(C₃F₇)I and C₅H₅Co(CNR)(C₃F₇)I react with excess isonitrile with the formation of benzene soluble, yellow salts [C₅H₅Co(CNR)₂(C₃F₇)]⁺I^?, which can be transformed into the corresponding PF^?₆ salts. The new compounds were characterised by C, H, N, Co analyses, molecular weight determinations, IR, ¹H NMR, ¹⁹F NMR, ¹³C NMR, ESCA and mass spectra.     

Fluorinated tropylium ions in the mass spectra of some polyfluoroaromatic compounds

The most prominent ion in the mass spectra of C₆F₅CH₂X (X ? H, Br, CH:CH₂, COCl, and CH₂C₆F₅) is C₇F₅H₂⁺, formulated as the pentafluorotropylium cation. This ion is also found, in an amount comparable to the parent ion, in the spectrum of (C₆F₅)₂CH₂. The heptafluorotropylium cation is found similarly in the spectrum of C₆F₅CF₃. The mass spectra of (C₆F₅)₂CHBr and [(C₆H₅)₂CH]₂ exhibit an ion C₁₃F₁₀H⁺ as the base peak, which is probably a pentafluorophenylpentafluorotropylium cation. The alcohol (C₆F₅)₂CHOH shows loss of C₆F₅, followed by 2H, as a major breakdown pathway. The mode of formation, and the subsequent fragmentation, of the major ions in these spectra, are discussed.     

Halfsandwich Carbonylmetal Complexes of Vanadium,Chromium, and Manganese Containing Tri(1‐cyclohepta‐2, 4, 6‐trienyl)phosphane,P(C7H7)3

The photo‐induced substitution of a CO ligand has been used to prepare the halfsandwich complexes (η³‐C₃H₅)V(CO)₄[P(C₇H₇)₃] ( 1 ), (η⁵‐C₅H₅)V(CO)₃[P(C₇H₇)₃] ( 2 ), (η⁷‐C₇H₇)V(CO)₂[P(C₇H₇)₃] ( 3 ), (η⁶‐C₆H₃Me₃)Cr(CO)₂[P(C₇H₇)₃] ( 4 ), and (η⁵‐C₅H₅)Mn(CO)₂[P(C₇H₇)₃] ( 7 ), in which the olefinic phosphane is coordinated as a conventional two‐electron ligand through the lone pair of electrons at phosphorus. Some analogues, which are permethylated at the aromatic ring ( 2* , 4* , 7* ), were included for comparison. Subsequent photo‐elimination of another CO group from 4 or 7 converts the olefinic phosphane into a chelating four‐electron ligand, leading to (η⁶‐C₆H₃Me₃)Cr(CO)[P(C₇H₇)₂(η²‐C₇H₇)] ( 5 ) and (η⁵‐C₅H₅)Mn(CO)[P(C₇H₇)₂(η²‐C₇H₇)] ( 8 ), respectively. The η²‐coordinated double bond in 5 and 8 can be displaced by trimethylphosphite to give (η⁶‐C₆H₃Me₃)Cr(CO)[P(C₇H₇)₃][P(OMe)₃] ( 6 ) and (η⁵‐C₅H₅)Mn(CO)[P(C₇H₇)₃][P(OMe)₃] ( 9 ). The ³¹P and ¹³C NMR spectra of all complexes are discussed, and X‐ray structure analyses for 2 and 8 are presented. Prolonged irradiation of 7 and 8 led to a di(cycloheptatrienyl)phosphido‐bridged dimer, {(η⁵‐C₅H₅)Mn(CO)[P(C₇H₇)₂]}₂( 10 ).