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.     

Reactions and properties of some trimethyleneplatinum(IV) complexes: X. Reaction with iodide and thiocyanate ions

The reaction between the platinacyclobutanes [$\text{PtX}{}_2\text{(CH}{}_2\text{CRR′C}$H₂)L₂] (X  Cl, Br; L  C₅H₅N, 4-CH₃C₅H₄N; R, R′  H, CH₃; R  H, R′  CH₃, C₆H₅) and iodide and thiocyanate ions in methyl cyanide solution has been studied. The C₃ moiety is eliminated as the cyclopropane and the process is first order with respect to the platinacyclobutanes and zero to half order with respect to the salt (MY). With the iodides the rate increases in the order Li < Na < K, Et₄N, and methyl substitution in the cyclobutane ring reduces the rate of reaction with Et₄NI. Added pyridine retards the reaction when L  C₅H₅N (X  Cl; R, R′  H) and added dimethylsulphoxide accelerates it.The mechanism suggested involves dissociation of an L ligand and attack of Y^? ions and of M⁺Y^? ion pairs on the five-coordinate intermediate formed.     

A novel synthesis of carbene complexes of manganese and molybdenum containing the trichlorogermyl group

A number of carbene complexes of formulas Cl₃GeMn(CO)₄C(OR′)R and C₅H₅Mo(CO)₂(GeCl₃)C(OR′)CH₃ (R = CH₃, C₆H₅; R′ = CH₃, C₂H₅) have been prepared by the reaction of [N(C₂H₅)₄]GeCl₃ with CH₃Mn(CO)₅, C₆H₅Mn(CO)₅, or C₅H₅Mo(CO)₃CH₃ followed by alkylation of the resulting trichlorogermylacylcarbonylmetallate ion. The compound C₅H₅Mo(CO)₂(GeCl₃)$\text{COCH}{}_2\text{CH}{}_2\text{C}$H₂ has been prepared directly by the reaction of [N(C₂H₅)₄]GeCl₃ with C₅H₅Mo(CO)₃(CH₂)₃Br.     

Isomerisation in the chemistry of platinacyclobutane complexes

The platinacyclobutane complexes PtCl₂L₂(C₃H₅Me)], L  pyridine, CD₃CN, or tetrahydrofuran, exist as mixtures of isomers containing P$\text{tCH}{}_2\text{CHMeC}$H₂ or P$\text{tCHMeCH}{}_2\text{CH}{}_2$ groups in rapid equilibrium. Decomposition occurs in some cases to give [PtCl₂L(CH₃CH₂CHCH₂)]. Stereospecific skeletal isomerisation also occurs in metallocyclobutanes containing the groups P$\text{tCHRCHRC}$H₂  P$\text{tCHRCH}{}_2\text{C}$HR, when R  aryl further decomposition gives ν-allylplatinum complexes.     

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.     

Darstellung und eigenschaften von und reaktionen mit metallhaltigen heterocyclen: XXV. Synthese und eigenschaften neuer platina- und rhodacycloalkane durch substitution und oxidative addition einer CCl-bindung

The platinacyclopentane derivative [Cl(CH₂)₃R₂P](Cl)$\text{PtPR}{}_2\text{CH}{}_2\text{CH}{}_2\text{CH}{}_2$ is formed by action of Cl(CH₂)₃PR₂ on Pt(COD)₂ in n-hexane via the not isolable Pt[PR₂(CH₂)₃Cl]₂ (R  C₆H₁₁) by oxidative addition of a CCl bond to platinum. [μ-CIRh(CO)₂]₂ reacts in benzene with Cl(CH₂)₃PR₂ under partially CO substitution to give the stable intermediate Cl(OC)Rh[PR₂(CH₂)₃Cl]₂. In boiling toluene oxidative addition of a CCl bond to rhodium occurs under formation of the phospharhodacyclopentane [CI(CH₂)₃R₂P] Cl₂(OC)-$\text{RhPR}{}_2\text{CH}{}_2\text{CH}{}_2\text{CH}{}_2$ (R  C₆H₅). The ³¹P{¹H}-NMR spectra of the rhodium compound is characterized by an ABX system, that of the platinum by superposition of an ABX pattern with an AB spectrum.     

Alternativ-Liganden VII1: Chelatkomplexe des typs (Me = CH3; X = CH3, Cl)

Chelate complexes of the type (CO)₄M$\text{nPMe}{}_2\text{CH}{}_2\text{Ch}{}_2\text{S}$iX₂ (X = Me, Cl) have been prepared from Na[Mn(CO)₅] and HMn (CO)₅, respectively, by two-step reactions with the ligands Me₂PCH₂CH₂SiX₂R′ using alkali salt, amine or HCl elimination. (CO)₄M$\text{nPMe}{}_2\text{Ch}{}_2\text{CH}{}_2\text{S}$iCl₂ is also obtained by cleavage of Mn₂(CO)₁₀ with Me₂PCH₂CH₂SiCl₃. IN the case of HMn (CO)₅ the intermediates (CO)₄Mn (H) L [L = Me₂PSiMe₃, Me₂PCH₂CH₂SiMe₂ (NMe₂), Me₂PCH₂CH₂SiCl₂ (NMe₂] can be isolated. The new compounds were identified by analytical and spectroscopic (IR, PMR, MS) methods.     

Transition metalcarbon bonds: XL. Palladium(II) complexes of [(dimethylamino)methyl]-ferrocene

C₅H₅FeC₅H₄CH₂NMe₂ reacts with sodium chloropalladate(II) in the presence of sodium acetate to give the internally metallated binuclear species [$\text{Pd}{}_2\text{X}{}_2\text{{C}{}_5\text{H}{}_5\text{FeC}{}_5\text{H}{}_3\text{CH}{}_2\text{N}$Me₂}₂] (X = Cl). The corresponding iodide was prepared as were mononuclear species [$\text{Pd(acac) {C}{}_5\text{H}{}_5\text{FeC}{}_5\text{H}{}_3\text{CH}{}_2\text{N}$Me₂}] and [$\text{Pd-{C}{}_5\text{H}{}_5\text{FeC}{}_5\text{H}{}_3\text{CH}{}_2\text{N}$Me₂}L] L = PMe₂Ph, AsMe₂Ph, P(OMe)₃ or PPh₃. ¹H NMR data are given.     

Intramolecular metalation of PBut2Ph and PBut3 in palladium acetate complexes

Reaction of [PdCl₂(PBu^t₂Ph)]₂ with silver acetate gives the internally metalated complex [P$\text{dCH}{}_2\text{CMe}{}_2\text{P}$Bu^tPh]₂(μ-Cl)₂. This reacts with TlC₅H₅ and LiC₅Me₅ with chloride-bridge cleavage to yield C₅R₅P$\text{dCH}{}_2$PBu^tPh (R = H, Me). The complex [P$\text{dCH}{}_2\text{CMe}{}_2\text{P}$Bu^t₂]₂(μ-Cl)₂,prepared from [PdCl₂(PBu^t₃)]₂ and CH₃COOAg, is analogously converted into C₅R₅$\text{PdCH}{}_2\text{CMe}{}_2\text{P}$Bu^t₂. The chloride complex C₅H₅Pd(PBu^t₅Ph)CI does not eliminate HCl to form C₅H₅P$\text{dCH}{}_2\text{CMe}{}_2\text{P}$Bu^tPh.     

Reactions of hydridosilacyclobutanes with low-valent complexes of iron or platinum

Unstable transition metal compounds formed from hydridosilacyclobutanes are described: 1-methyl-1-silacyclobutane reacts with nonacarbonyldiiron to give the complexes [Fe(CO)₄(H){$\text{Si(Me)CH}{}_2\text{CH}{}_2\text{C}$H₂}] and [$\text{Fe{CH}{}_2\text{CH}{}_2\text{CH}{}_2\text{Si}$(H)Me}(CO)₄], and with bis(triphenylphosphine)(ethylene)platinum(0) to give [Pt(H)(PPh₃)₂{$\text{Si(Me)CH}{}_2\text{CH}{}_2\text{C}$H₂}].     

The photodecomposition of platinacycloalkanes in solution: II. 1,4-butanediylplatinum(II) and (IV) compounds

The products of the photolysis of a number of platinacyclopentanes in solution at 25°C under a variety of conditions have been determined. With [I₂P$\text{tCH}{}_2\text{CH}{}_2\text{CH}{}_2\text{C}$H₂(L₂)] (L = PMe₂Ph, PPh₃) in CH₂Cl₂, CH₂Br₂ and (CH₃)₂SO the hydrocarbon products are exclusively ethylene and but-1-ene. Formation of the latter through a 1,3-hydrogen shift is preceded by phosphine ligand dissociation. The photolysis of [ICH₃P$\text{tCH}{}_2\text{CH}{}_2\text{C}$H₂(L₂)] gave methane, ethylene, but-1-ene and n-pentane together with a little n-butane, the methane being formed from internal hydrogen abstraction by the CH₃ group in the excited reactant molecule. Photodecomposition of the platinum(II) compounds [P$\text{tCH}{}_2\text{CH}{}_2\text{CH}{}_2\text{C}$H₂(L₂)] (L = (PMe₂Ph)₂, (PPh₃)₂, Ph₂PCH₂CH₂PPh₂) gave ethylene, but-1-ene, pent-1-ene (with the halogenated solvents) and with some systems appreciable yields of n-butane, the latter being the results of internal abstraction of two hydrogen atoms by the C₄H₈ moiety. The formation of pentene is probably preceeded by the addition of CH₂Cl₂ or CH₂Br₂ to the excited reactant molecule. Addition of diphenylphosphine promotes the production of n-butane.     

Reactions and properties of some trimethyleneplatinum(IV) complexes: V. The kinetics and mechanism of formation from arylcyclopropanes

The kinetics of the reaction of arylcyclopropanes (4-XC₆H₄C₃H₅, X = H, Me, EtO) with either [Pt₂Cl₂(μ-Cl)₂(C₂H₄)₂] or [{$\text{PtCl}{}_2\text{(CH}{}_2\text{CH}{}_2\text{C}$H₂)} in tetrahydrofuran to give in each case [{$\text{PtCl}{}_2\text{(CHArCH}{}_2\text{C}$H₂)}₄] and ethylene or cyclopropane, respectively, have been studied. The reactions are essentially first order in both arylcyclopropane and platinum complexes. The order of reactivity follows the series X = EtO > > Me > H, and [Pt₂Cl₂(μ-Cl)₂(C₂H₄)₂]> [{$\text{PtCl}{}_2\text{(CH}{}_2\text{CH}{}_2\text{C}$H₂)}4] and the rate is accelerated in polar solvents. Mechanisms in which the arylcyclopropane first coordinates to platinum and then undergoes ring opening reactions are proposed.     

The preparation and catalytic hydroformylation activity of some halocarbonylrhodium(I) complexes containing phosphinoalkylorganosilicon ligands

The synthesis and properties of a series of trans-halocarbonylrhodium(I) complexes containing the phosphinoalkylorganosilicon ligands Me₃SiCH₂PPh₂, Me₃Si(CH₂)₃PPh₂, and PPh₂CH₂(Me)$\text{Si(OSiMe}{}_2\text{)}{}_3\text{O}$ have been investigated. The complexes could be prepared by an exchange reaction involving RhCl(CO)(PPh₃)₂ and the organosilicon ligands or in better yields by the reaction of Rh₂Cl₂(CO)₄ with the ligands. Iodorhodium derivatives were obtained as the exclusive products in the latter reaction if a small amount of LiI was present. The catalytic activity of RhCl(CO)(PPh₂CH₂SiMe₃)₂ was similar to that of RhCl(CO)(PPh₃)₂ in the hydroformylation of hex-1-ene at 100°C and 1000 psi pressure of H₂/CO. The catalytic properties of the iodo derivatives RhI(CO)L₂ [L = Me₃SiCH₂PPh₂, Me₃Si(CH₂)₃PPh₂, and PPh₂CH₂(Me)$\text{Si(OSiMe}{}_2\text{)}{}_3\text{O}$] varied considerably, with RhI(CO)(PPh₂CH₂SiMe₃)₂ producing an unexpectedly low linear/branched aldehyde product ratio.     

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.     

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 photodecomposition of platinacycloalkanes in solution.: I. 1,3-propanediylplatinum(IV) compounds

The gaseous products of the photolysis at 25°C of the platinacyclobutane compounds [X₂$\text{PtCH}{}_2\text{CH}{}_2\text{C}$H₂(N-N)] where X = Cl, Br and N-N = 1,10-phenanthroline, 2,2′-bipyridine, (CH₂NMe₂)₂, (C₅H₅N)₂ in several solvents, in the absence and presence of various additives, have been determined. With solvents of relatively low dielectric constant (e.g. CH₂Cl₂), over 85 mol % of the hydrocarbon products was propene, the formation of which appears to involve a direct transfer of a hydrogen atom between neighbouring groups in the ring. With solvents of relatively high dielectric constant (MeCN, Me₂SO) in the presence of species, e.g. I^?, SbPh₃, having a high trans effect, cyclopropane is the main volatile product. The effect of added halide ion and of the mixed solvents Me₂SO/PhMe and Me₂SO/PhSH indicates that ionisation of the platinacyclobutane and the formation of platinum substituted propyl ion-radicals precede the formation of cyclopropane (and the small amounts of ethylene produced).The photolysis of [X₂$\text{PtCH}{}_2\text{CH}{}_2\text{C}$H₂(MeCN)₂] in methyl cyanide solution in the presence of Et₃RNX′ (X′ = Cl, R = H; X′ = Br, R = Et) gives appreciable amounts of ethylene in the products (up to 25 mol %). It is suggested that the halide ions add to the platinum to give negatively charged platinacyclobutane species, the photodecomposition of which may give C₂H₄.     

On the possibility of a carbenium ion structure for the complexes [Os3H3(CO)9CCR2]+. Further application of the 187Os nucleus

In the ¹H NMR spectrum of the complex [Os₃H₃(CO)₉C$\text{C(CH}{}_2\text{C}$H₂]⁺ at 30°C, under conditions of rapid exchange, the single hydride resonance has two sets of satellites of equal intensity (separated by 32.0 and 28.8 Hz) caused by ¹⁸⁷Os¹H spin—spin coupling. The spectral data rule out the upright carbenium ion structure for the complex, and are consistent with the fluxional process involving hydrocarbon ligand rotation about the C$\text{C(CH}{}_2\text{)}{}_2\text{C}$H₂ axis in a tilted structure, with concomitant rotation of the Os₃H₃(CO)₉ moiety.     

Synthesis of monohydridohexamethylbenzeneruthenium(II) complexes containing group V donor ligands. Isomerism arising from cyclometallation of a tertiary phosphine at aliphatic and aromatic carbon atoms

The η-hexamethylbenzenehydridoruthenium(II) complexes RuHCl(η-C₆Me₆)L (L = PPh₃ (11), AsPh₃ (12), P(C₆H₄-p-F)₃ (14), P(C₆H₄-p-Me)₃ (15), P(C₆H₄-p-OMe)₃ (16), P-t-BuPh₂ (17), P-i-PrPh₂ (18), P-i-Pr₃ (19), PCy₃ (20) and P-t-BuMe₂ (21)) have been made by heating [RuCl₂(η-C₆Me₆)]₂, the ligand and sodium carbonate in propan-2-ol. The triarylphosphine complexes 11, 14 and 15 react with methyllithium to give aryl ortho-metallated hydridoruthenium(II) complexes such as $\text{RuH(}\text{o}\text{-C}{}_6\text{H}{}_4\text{P}$Ph₂)(η-C₆Me₆) (22) and 19 similarly gives the isopropyl cyclometallated complex $\text{RuH(CH}{}_2\text{CHMeP}$-i-Pr₂(η-C₆Me₆) (29) as a mixture of diastereomers. Reaction of 17 with methyllithium gives initially the t-butyl cyclometallated complex $\text{RuH(CH}{}_2\text{CMe}{}_2\text{P}$Ph₂)(η-C₆Me₆) (25) which isomerizes by a first order process (k$\text{0}\text{?}$.2 h^?1 in C₆D₆ or THF-d₈ at 50°C) to the aryl ortho-metallated complex $\text{RuH(}\text{o}\text{-C}{}_6\text{H}{}_4\text{P}$-t-BuPh)(η-C₆Me₆) (26). The similarly generated isopropyl cyclometallated complex $\text{RuH(CH}{}_2\text{CHMeP}$Ph₂)(η-C₆Me₆) (27) has not been isolated in a pure state owing to rapid isomerization to $\text{RuH(}\text{o}\text{-C}{}_6\text{H}{}_4\text{P}$-i-PrPh)(η-C₆Me₆) (28); both 27 and 28 exist as a pair of diastereomers. The formation of the cyclometallated complexes and the isomerizations are thought to involve intermediate 16-electron ruthenium(O) complexes Ru(η-C₆Me₆)L.