Perfluorocycloalkyl(aryl) diazenes from heptafluoronitrosocyclobutane and nonafluoronitrosocyclopentane

The perfluoronitrosocycloalkanes, heptafluoronitrosocyclobutane and nonafluoronitrosocyclopentane, are convenient precursors to a family of new perfluorocycloalkyl(aryl) diazenes. With aniline and o-aminobenzamide, $\text{CF}{}_2\text{(CF}{}_2\text{)}{}_{\mathrm{x}}\text{C}$FNN$\text{C(CH)}{}_4\text{C}$H and $\text{CF}{}_2\text{(CF}{}_2\text{)}{}_{\mathrm{x}}\text{C}$FNN$\text{C(CH)}{}_4\text{C}$C(O)NH₂ (x = 2,3) are formed. Additionally, heptafluoronitrosocyclobutane gives $\text{CF}{}_2\text{(CF}{}_2\text{)}{}_2\text{C}$FNN$\text{CCFCFCHCFC}$F and $\text{CF}{}_2\text{(CF}{}_2\text{)}{}_2\text{C}$FNN$\text{C(CH)}{}_4\text{C}$NH₂ with 2,3,5,6-tetrafluoroaniline and o-phenylenediamine     

Heterocyclic and acyclic derivatives of F-N-isopropylacetimidoyl chloride

$\text{F}$-N-Isopropylacetimidoyl chloride, CF₃CClNCF(CF₃)₂, has been used as a precursor for a variety of heterocyclic and acyclic compounds. Reaction with azide ion yields a mixture of the imidoyl azide, CF₃(N₃)CNCF(CF₃)₂, and the 1,5-tetrazole, CF₃$\text{CNNN}$CF(CF₃)₂. Hexafluoropropylideniminolithium produces as a minor product the conjugated diimine, (CF₃)₂CNC(CF₃)NCF(CF₃)₂, from nucleophilic attack at the imidoyl chlorine and as a major product the triimine, (CF₃)₂CNC(CF₃)NC(CF₃)₂NC(CF₃)₂, from further attack at the isopropyl fluorine. A thio-amide, CF₃C(S)NHCH(CF₃)₂, and a Δ³-1,2,4-dithiazoline, $\text{SSC(CF}{}_3\text{)NC}$(CF₃)₂, are produced upon reaction of hyrogen sulfide with the imidoyl chloride. Pathways are proposed for each of the reactions.     

Some partially fluorinated cyclic and acyclic compounds of sulphur (II) and (IV) and partially fluorinated cyclic compounds of phosphorus (III) and (V)

Sulfinyl fluoride and N-(F-isoprophyl)iminosulfur difluoride form the compounds, O$\text{SN(CH}{}_3\text{)CH}{}_2\text{CH}{}_2\text{N}$(CH₃) and i-C₃F₇N$\text{SN(CH}{}_3\text{CH}{}_2\text{CH}{}_2\text{N}$(CH₃ with symdimethylethylenediamine (1). In contrast, CF₃C(O)NSF₂ and (R_f)₂SF₂ (R_f = CF₃, i-C₃F₇ form only acyclic compounds, CF₃C(O)N(CH₃)CH₂CH₂N(CH₃)C(O)CF₃ and R_fSN(CH₃)CH₂CH₂N(CH₃)SR_f with (1). With PF₃, PF₅ and OPF₃, cyclic compounds $\text{N(CH}{}_3\text{)CH}{}_2\text{CH}{}_2\text{N(CH}{}_3\text{)P}$F, $\text{N(CH}{}_3\text{)CH}{}_2\text{CH}{}_2\text{N(CH}{}_3\text{)P}$F₃, and $\text{N(CH}{}_3\text{)CH}{}_2\text{CH}{}_2\text{N(CH}{}_3\text{)P}$-(O)F result. When the latter two compounds are reacted further with LiNC(CF₃)₂, N(CH₃)CH₂CH₂N(CH₃)PF₂NC(CF₃)₂ and $\text{N(CH}{}_3\text{CH}{}_2\text{CH}{}_2\text{N(CH}{}_3\text{)P}$(O)NC(CF₃)₂) form.     

Electrochemical fluorination of chlorine-containing amines

The electrochemical fluorination of chlorine-containing alkylamines has been studied. It was found that, in general, the carbon-chlorine bond in the alkylamines is retained during electrochemical fluorination is anhydrous hydrogen fluoride, yielding chlorine-containing polyfluoroalkylamines. Perfluoroalkylamines and fluorocarbons were also produced.By the use of this method, several new chloropolyfluoroamines such as (CF₃)₂NCF₂CClF₂, (C₂F₅)₂NCF₂CClF₂, (CF₃)(C₂F₅)NCF₂CClF₂, (CClF₂CF₂)₂NCF₃, (CClF₂CF₂)₂NC₂F₅, (C₂F₅)(CClF₂CF₂)NF, (CClF₂CF₂)₂NF, (CF₃)₂NCF₂CF₂CClF₂, $\text{CF}{}_2\text{(CF}{}_2\text{)}{}_3\text{N}$CF₂CClF₂, and $\text{CF}{}_2\text{CF}{}_2\text{OC}{}_2\text{F}{}_4\text{N}$CF₂CClF₂ have been isolated and characterized.     

Reactivite d'alcynes fluores vis-a-vis de methylthiolates [(η5-C5H5)M(SMe)(CO)3] et d'hydrures [(η5-C5H5)MH(CO)3] de molybdene et de tungstene

The electron deficient acetylene, hexafluorobut-2-yne, reacts with molybdenum and tungsten methanethiolate derivatives (prepared in situ) to give vinyl and three-, five-, or six-membered heterocyclic derivatives: [Cp(OC)- $\text{MoC(O)C(CF}{}_3\text{)C(CF}{}_3\text{)C(O)S}$Me], [Cp(OC)₂$\text{MC(CF}{}_3\text{)C(CF}{}_3\text{)C(CF}{}_3\text{)C(O)S}$Me], [CpW(CO)₃C(CF₃C(CF₃)SMe], [CpW{η³-$\text{C(CF}{}_3\text{)C(CF}{}_3\text{)C(SMe)OC}$(O)}-(CO)₂]. These reactions contrast with those of trifluoropropyne where no organometallic species are obtained. On heating or irradiation with CF₃CCCF₃ [CpMH(CO)₃] gives known bridged species and in the presence of dimethyl disulphide the vinyl derivative [CpM(CO)₃C(CF₃)C(CF₃)H]and an isomer of undetermined structure.     

Cyclometallation reactions XII. On the effect of various leaving groups on internal metallation reactions with alkylmanganese complexes

The interaction of azobenzene and MnR(CO)₅ (R  Me, Et, CH₂Ph, CH₂-C₆Me₅, COCF₃, COCH₂C₆F₅, COCH₂OPh, Ph or C₆F₅) affords M$\text{n(C}{}_6\text{H}{}_4\text{NN}$Ph)-(CO)₄, together with a binuclear complex Mn₂(CO)₆(C₁₂H₁₀N₂) in some cases. The metallation reaction is shown to proceed most readily with Mn-(CH₂Ph)(CO)₅; with this reagent, the metallated complexes M$\text{n(C}{}_6\text{H}{}_4\text{CH}{}_2\text{P}$Me₂)-(CO)₃[PMe₂(CH₂Ph)] (two isomers) and M$\text{n(C}{}_6\text{H}{}_4\text{CH}{}_2\text{A}$sMe₂(CO)₄ have been obtained on treatment with EMe₂(CH₂Ph) (E  P and As, respectively).     

Cyclometallation reactions of N-(benzylidene)benzylamines with palladium compounds

The cyclometallation of p-RC₆H₄CHNCH₂C₆H₂, (R = H, Cl, NO₂) by PdX₂ (X = Cl, AcO) has been studied.In every case the cyclometallation occurs with formation of a five-membered ring containing the methine group. The structure of these compounds [$\text{PdX(}\text{p}\text{-RC}{}_6\text{H}{}_3\text{CHN}$CH₂C₆H₅)]₂, derived from ¹H NMR spectra, are different from those reported previously. Reaction of these compounds with PEt₃ gives the compounds [PdX(p-RC₆H₃CHNCH₂C₆H₅)(PEt₃)₂] but with an excess of PPh₃ only the complexes [$\text{PdX(}\text{p}\text{-RC}{}_6\text{H}{}_3\text{CHN}$CH₂C₆H₅)(PPh₃)] are formed.     

The preparation and characterization of a platinum ether complex

The reaction of [Pt((F₃C)CCH(CF₃))(P(C₂H₅)₃)₂CH₃OH]PF₆ with allene in methanol affords a novel metallocyclic ethereal complex [$\text{Pt((F}{}_3\text{C)CHC(CF}{}_3\text{)C(CH}{}_3\text{)CH}{}_2\text{O}$CH₃)(P(C₂H₅)₃)₂]PF₆, which has been characterized by ¹H, ²H, ¹⁹F and ³¹P NMR spectroscopy. Its structure has also been determined by a single crystal X-ray analysis. The crystal are monoclinic, space group P2₁/n, with cell dimensions a 20.012(5), b 17.222(5), c 8.902(3) Å and β 91.54(5)°. The structure was refined by full matrix least-squares methods on F, using 3097 unique observations collected by automated four circle diffractometer. Refinement converged at R  0.066. The Pt atom has a distorted square-planar coordination geometry, with cis P atoms, and PtP distances of 2.219(4) Å (trans to O) and 2.324(4) Å (trans to C). These results show the ethereal group is a weak ligand to platinum(II) but because of the chelating effect, its displacement by other ligands is thermodynamically not favorable. The mechanism of formation of the ethereal complex is also discussed.     

Formation of an iridium σ-cyclopropane complex by the intramolecular activation of a cyclopropylphosphine: Rearrangement to a chelating σ-vinyl complex

When (t-Bu)₂PCH₂CHCH₂CH₂ is combined with [IrCl(C₈H₁₄)₂]₂ in toluene, the σ-bound cyclopropane complexes

(P(t-Bu)₂CH₂$\text{CHCH}{}_2\text{C}$H₂) (1a, 1b) are formed. Complexes 1a,1b react readily with H₂ to form IrClH₂P(t-Bu)₂CH₂$\text{CHCH}{}_2\text{C}$H₂)₂ (2). In polar solvents 1a,1b isomerize to the σ-vinyl chelated complex $\text{IrClH(P(t-Bu)}{}_2\text{CH}{}_2\text{C(CH}{}_3\text{)C}$H)(P(t-Bu)₂CH₂$\text{CHCH}{}_2\text{C}$H₂) (3). The structure of this 5-coordinate, 16-electron Ir^III complex was deduced from spectroscopic data, reaction chemistry, and from the crystal structure of its CO adduct (4). Compound 4 crystallizes in the monoclinic space group C_2h⁵-P2₁/n (a 15.610(14), b 15.763(16), c 11.973(13) Å, and β 104.74(5)°) with 4 molecules per unit cell. The final agreement indices for 2326 reflections having F_o² > 3σ(F_o²) are R(F) = 0.089 and R_w(F) = 0.095 (271 variables) while R(F²) is 0.148 for the 3423 unique data. Bond lengths in the 5-atom chelate ring $\text{IrPCCC}$ are IrP 2.341(4), PC 1.857(26), CC 1.520(30), CC 1.341(25), and CIr 1.994(21) Å. The IrCl distance is 2.479(5) Å.     

N-halogeno-compounds. Part 9 [1]. Azoxy- and azo-arenes derived from 4-(dichloroamino)tetrafluoropyridine; crystal structure of trans-2,3,5,6-tetrafluoro-4-(2,4,6-trimethylphenyl-onn-azoxy)pyridine

The nitrosoarenes ArNO (Ar = C₆H₅, 2-MeC₆H₄, 2,4,6- Me₃C₆H₂ and C₆F₅) have been condensed with 4-(dichloroamino)- tetrafluoropyridine to provide the azoxy-compounds py_FN$\text{N}\text{+}$($\text{N}\text{-}$)Ar (py_F = 2,3,5,6-tetrafluoro-4-pyridyl); de-oxygenation of the first three with triphenylphosphine or triethyl phosphite gave the corresponding azo-compounds, and the reverse reaction was achieved in the case of py_FNNC₆H₂Me₃-2,4,6 using peroxytrifluoroacetic acid. Thermolysis of 4-azidotetrafluoropyridine in the presence of pentafluoronitrosobenzene provided the perfluorinated azoxy-compound py_FN$\text{N}\text{+}$($\text{O}\text{-}$)C₆F₅. X-Ray methods have been used to determine the molecular geometry of py_FN$\text{N}\text{+}$($\text{O}\text{-}$)C₆H₂Me₃-2,4,6.     

Darstellung ylidischer metallacyclopropankomplexe durch ringverkleinerung metallacyclischer vinylketonkomplexe. Molekülstruktur von C5H5W(CO)2[(PMe3)HC-CH(COMe)]

The addition of trimethylphosphane to five-membered metallacyclic vinylketone complexes of the type Ar$\text{M(CO)}{}_2\text{(HCCHCO}$R) (I) (Ar = η⁵-aromatic ring system: C₅H₅, C₅H₄Me, C₅Me₅; R = Me, Et, n-Bu; M = Mo, W) in pentane solution results in the formation of the ylidic metallacyclopropane complexes Ar$\text{M(CO)}{}_2\text{[(PMe}{}_3\text{)-HCC}$H(COR)] (II). In these 1:1 adducts the three-membered ring is stabilized by an electron-donating phosphonium and an electron-attracting acyl substituent. The negative charge in the ylidic complexes II is localized on the central metal providing it with Lewis base properties. An extraordinary high electron density can be observed on the metal of the derivative C₅H₅$\text{W(CO)(PMe}{}_3\text{)[(PMe}{}_3\text{)HCC}$H-(COMe)] (III) which is formed by a 1:2 addition of C₅H₅W(CO)(C₂H₂)-(COMe) and PMe₃. The metallacyclopropane complexes II and III are characterized by IR, ¹H NMR, ¹³C NMR, ³¹P NMR and mass spectroscopy. For C₅H₅$\text{W(CO)}{}_2\text{[(PMe}{}_3\text{)HCC}$H(COMe)], the results of an X-ray structure determination are presented.     

Konfiguration und konformation von methyl- und aminylradikalen mit CF3S-substituenten

From the hyperfine ESR-splitting patterns of, $\text{a(}{}^{13}\text{C}{}_{\mathrm{\gamma }}\text{), a(}{}^{14}\text{N}\text{)}\text{and}\text{a(}{}^{19}\text{F}\text{)}$ it is concluded that the radicals (CF₃S)₃C·, (CF₃S)₂HC·, (CF₃S)H₂C·, (CF₃S)₂N· and (CF₃S)₃Si· are planar π-radicals existing in a nearly fully staggered conformation. The force which promotes the staggered conformation arises from conjugative delocalization between the 2 p_z-unpaired electron and the p-type lone pair on the sulfur atoms of the CF₃S-groups, causing a stabilization of the radicals. The electronegative CF₃-group decreases the extent of conjugative electron delocalization.Whereas fluorine atoms adopt equivalent positions in the radicals the staggered conformation implies inequivalence of the protons in CF₃SCH₂.     

Die thermische reaktion von C5H5(CO)2FeNa mit benzimidchloriden C6H5(Cl)CNR

η⁵-C₅H₅(CO)₂FeNa reacts with the benzimide chlorides C₆H₅(Cl)CNR (R  CH(CH₃)₂, C₆H₅) in boiling THF to give the η¹-iminoacyl complexes η⁵-C₅H₅ (CO)₂Fe[η¹-C(C₆H₅)NR]. Alternatively, the new Fe complexes [η⁵-C₅H₅(CO)Fe$\text{C(C}{}_6\text{H}{}_5\text{)N(CH}{}_3\text{)C(C}{}_6\text{H}{}_5\text{)N}$CH₃PF₆ (IV) and [η⁵-C₅H₅(CO)₂FeC(C₆H₅)N(CH₃)C(C₆H₅)NCH₃]PF₆ (V) are formed under the same conditions, if R  CH₃. Hudrolysis of the CN single bond of the ligand in V, not stabilized by a chelate effects as in IV, results in the formation of [η⁵-C₅H₅(CO)₂FeC(C₆H₅)NHCH₃]PF₆ (VII). Reaction of η⁵-C₅H₅(CO)₂ with N-benyzylbenzimido chloride yields η⁵-C₅H₅(CO)₂FeCH₂C₆H₅ as the only isolated product.     

Synthesis of homoleptic tris(organo-chelate)iridium(III) complexes by spontaneous ortho-metallation of electronrich olefin-derived N,N′-diarylcarbene ligands and the X-ray structures of fac-[Ir{CN(C6H4Me-p) (CH2)2NC6H3Me-p}3] and mer-Ir{CN(C6H4Me-p)(CH2)2NC6H3Me-p}2 {CN(C6H4Me-p)(CH2)2NC6H4Me-p}Cl (a product of HCl cleavage)

Treatment of [{Ir(COD)(μ-Cl)}₂] with excess of the electron-rich olefin [$\text{CN(Ar)(CH}{}_2\text{)}{}_2\text{N}$Ar]₂ (abbreviated as (L^Ar)₂, Ar = C₆H₄Me-p or C₆H₄OMe-p) affords the ortho-metallated tricycle [$\text{Ir(L}{}^{\mathrm{A}}\text{r}$)₃], which for Ar = C₆H₄Me-p (Ia) with HCL yields [$\text{Ir(L}{}^{\mathrm{A}}\text{r}$)₂(L^Ar)]Cl (IV); X-ray data show that in IV there is an unexpectedly close Ir?C(o-aryl) contact (2;52(1) Å) involving the “free” L^Ar which compares with an IrC(o-aryl) distance of 2.09(3) Å in Ia or 2.07(3) Å in the ortho-metallated L^Ar ligand of complex IV.     

Unusual route to and rearrangement of four-membered ring complexes C5H5Fe (CO) [ (C6H5)2PN(R)CH (C6H5) ]

The amine substituted phosphines (C₆H₅)₂PN(H)CH₂CH₃ and (C₆H₅)₂PN(H)CH₂C₆H₅ react with C₅H₅Fe(CO)₂CH(C₆H₅) (OCH₃) photolytically to give moderate yields of the four-membered chelate ring complexes C₅H₅$\text{Fe (CO) [(C}{}_6\text{H}{}_5\text{)}{}_2\text{PN (CH}{}_2\text{CH}{}_3\text{) C}$H (C₆H₅)] and C₅H₅$\text{Fe (CO) [(C}{}_6\text{H}{}_5\text{)}{}_2\text{PN (CH}{}_2\text{C}{}_6\text{H}{}_5\text{)C}$H(C₆H₅)], respectively. Photolysis of C₅H₅Fe(CO)₂CH(C₆H₅) (OCH₃) in the presence of (S)-(?)-diphenyl(1-phenylethylamino)phosphine leads to the isolation of C₅H₅Fe(CO)[(C₆H₅)2PNC(CH₃) (C₆H₅)]CH₂C₆H₅ which is proposed to arise from a formally 1,3-hydrogen shift rearrangement of an intermediate four-membered chelate ring complex.     

Inorganic Chemistry: Towards the 21st Century. : ACS Symposium Series 211 (Ed. M.H. Chisholm), American Chemical Society,Washington, D.C., 1983, ix + 566 pages, $67.95 ($55.95, USA and Canada)

The preparation of the first mixed metal cyclometallated compounds [ClP$\text{d(}\text{p}\text{-RC}{}_6\text{H}{}_3\text{CHNNCH(}\text{p}\text{-RC}{}_6\text{H}{}_3\text{))P}$tCl]_n (R = H, Cl) are reported; they were made from monocyclopalladated [(AcO)P$\text{d(}\text{p}\text{-RC}{}_6\text{H}{}_3\text{CHNN}$CH(p-RC₆H₄)]₂ and PtCl₄^2?.     

Cyclopentadienyl-ruthenium and -osmium chemistry: XXVIII. Reactions and isomerisation of 1,2-bis(methoxycarbonyl)ethenyl complexes: X-ray structures of Ru{Z)-C(CO2Me)CH(CO2Me)} -(CO)(PPh3)(η-C5H5) · 0.5EtOH,Ru{(E)-C(CO2Me)CH(CO2Me)}(dppe)(η-C5H5) and Ru{C(CO2Me)C(CO2Me)C(CO2Me)CH(CO2Me)} - (PPh3)(η-C5H5)

A reinvestigation of the reaction between C₂(CO₂Me)₂ and RuH(PPh₃)₂(η-C₅H₅) and some related complexes is reported. Initial cis addition is followed by conversion into the trans isomer. In the case of the bis-(PPh₃) complex, isomerisation is followed by chelation of the ester CO group with concomitant displacement of one PPh₃ligand. The resulting chelate complex reacts with CO or CNBu^t to give the (Z)-RuC(CO₂Me)CH(CO₂Me) complexes; the (E)-isomer of the carbonyl complex is obtained by addition of C₂(CO₂Me)₂to RuH(CO)(PPh₃)(η-C₅H₅). The ^1Hand ¹³C NMR spectra are not a reliable guide to assignment of the stereochemistry of the vinyl group. Other products isolated from the initial reaction are the bis-insertion product $\text{Ru{C(CO}{}_2\text{Me)C(CO}{}_2\text{Me)C(CO}{}_2\text{Me)}$CH(CO₂Me)} -(PPh₃)(η-C₅H₅) and the 1/2 PPh₃/C₂(CO₂Me)₂ adduct. The molecular structures of Ru{(Z)-C(CO₂Me)CH(CO₂Me)}(CO)(PPh₃(η-C₅H₅) · 0.5EtOH, Ru{(E)-C(C₂Me)CH(CO₂Me)}(dppe)(η-C₅H₅) and $\text{Ru{C(CO}{}_2\text{Me)C(CO}{}_2\text{Me)C(CO}{}_2\text{-Me)}$CH(CO₂Me)}(PPh₃)(η-C₅H₅) have been determined. The cis isomer is monoclinic, space group P2₁,with a 9.328(8), b 17.385(10), c 10.356(7) Å, β 101.78(3)° and Z = 2; 2107 data with I ≥ 2.5σ(I) were refined to R = 0.076 R_w = 0.085. The trans isomer is triclinic, space group P$\text{1}$, with a 10.404(7) b 11.221(6), c 13.230(9) Å, α 92.67(5), β 110.56(5), γ 106.21(5)° and Z = 2; 2520 data with I ≥ 2.5σ(I) were refined to R = 0.055 R_w = 0.068. The butadienyl complex is monoclinic, space group P2₁/a, with a 19.655(8), b 8.674(4), c 21.060(5) Å, β 116.22(3)° and Z = 4; 2724 data with I ≥ 2.5σ(I) were refined to R = 0.042, R_w = 0.047.