Substitution reactions of trans-[PdXPh(SbPh3)2J (X=Cl or Br) with nitrogen,phosphines and arsenic donor ligands. Crystal structures of trans-[PdClPh(PPh3)2], [PdClPh(bipy)], [PdClPh(dppm)]2, and [PdBrPh(dppm)]2

Exchange reactions of trans-[PdXPh(SbPh₃)₂] (1) (X=Cl or Br) with ligands L in refluxing dichloromethane give the palladium phenyl complexes [PdXPhL₂] (X=Cl, L=PPh₃, AsPh₃, L₂=2,2′-bipyridine (bipy), 4,4′-dimethyl-2,2′-bipyridine (dmbipy), 1,10-phenanthroline (phen); X=Br, L=PPh₃, L₂=bipy). Treatment of the complexes with bis(diphenylphosphino)methane (dppm) in refluxing dichloromethane gives [PdXPh(dppm]₂. These complexes have been characterised by microanalysis, IR and ¹H NMR spectroscopic data together with single crystal X-ray determinations of the phenyl palladium complexes, trans-[PdClPh(PPh₃)₂], [PdClPh(bipy)], [PdClPh(dppm)]₂, and [PdBrPh(dppm)]₂.     

Tertiary phosphine complexes of cyclopentadienylmolybdenum carbonyl halides. Stereoselective syntheses and isomer separations

Pure cis and trans isomers of CpMo(CO)₂(L)X (Cp = η⁵-C₅H₅, L = PPh₃ or PBu₃, X = Br, or I) have been separated by chromatography and characterized by infrared and proton NMR spectroscopy. The reactions of trans-CpMo(CO)₂(L)CH₃ with HgX₂ (X = Cl, Br, I, SCN) afford cis-CpMo(CO)₂(L)X in high yield. Both linkage isomers are obtained in the reaction with Hg(SCN)₂, L = PPh₃. The mercuric halides react with CpMo(CO)₂(L)COCH₃ to form the metalmetal bonded derivatives trans-CpMo(CO)₂(L)HgX. Reactions of CpMo(CO)₂(L)CH₃ or CpMo(CO)₂(L)COCH₃ with bromine or iodine yield the halide complexes CpMo(CO)₂(L)X (X = Br and I, respectively), the product mixtures containing high proportions of the trans isomers.     

The syntheses and coordination properties of M(CO)3X(DAB) (M = Mn,Re; X = Cl,Br, I; DAB = 1,4-diazabutadiene)

M(CO)₅X (M = Mn, Re; X = Cl, Br, I) reacts with DAB (1,4-diazabutadiene = R₁N=C(R₂)C(R₂)′=NR′₁) to give M(CO)₃X(DAB). The ¹H, ¹³C NMR and IR spectra indicate that the facial isomer is formed exclusively. A comparison of the ¹³C NMR spectra of M(CO)₃X(DAB) (M = Mn, Re; X = Cl, Br, I; DAB = glyoxalbis-t-butylimine, glyoxyalbisisopropylimine) and the related M(CO)₄DAB complexes (M = Cr, Mo, W) with Fe(CO)₃DAB complexes shows that the charge density on the ligands is comparable in both types of d⁶ metal complexes but is slightly different in the Fe-d⁸ complexes. The effect of the DAB substituents on the carbonyl stretching frequencies is in agreement with the A′(cis) > A″ (cis) > A′(trans) band ordering.Mn(CO)₃Cl(t-BuNCHCHNt-Bu) reacts with AgBF₄ under a CO atmosphere yielding [Mn(CO)₄(t-BuNCHCHN-t-Bu)]BF₄. The cationic complex is isoelectronic with M(CO)₄(t-BuNCHCHNt-Bu) (M = Cr, Mo, W).     

Coordination complexes containing multidentate ligands : V. The reactions between trans-carbonylchlorobis(triphenylphosphine)iridium and trans-carbonylchloro(triphenylarsine)iridium and some tridentate group VB ligands

Bis[3-(dimethylarsino)propyl]phenylarsine, (tas), reacts with trans-Ir(CO)(EPh₃)₂ X (E = P, As; X = F, Cl, Br, I) to yield the (Ir(CO)(tas)] X complexes. In contrast, the similar ligand bis[3-(dimethylarsino)propyl]phenylphosphine, (dap), reacts with trans-Ir(CO)(EPh₃)₂X (E = P, As; X = Cl, Br, I) to yield a mixture of [Ir(CO)(dap)X] and [Ir(CO)(dap)]X, and with trans Ir(CO)(EPh₃)₂F (E = P, As) to yield solely [Ir(CO)(dap)F]. The cations [Ir(CO)(L)]⁺ (L = tas, dap) readily yield tetraphenylborate derivatives, [Ir(CO)(L)]BPh₄. The oxygenation of [Ir(CO)(tas)]⁺ in solution proceeds almost to completion after 15 h, whereas [Ir(CO)(dap)]⁺ does not appear to undergo oxygenation.     

Hydrolyse und Halogenidaustausch von Pentahalogenomonocarbonylosmaten(III)

Hydrolysis and Halide Exchange of Pentahalogenomonocarbonyl Osmates(III) The aquo complexes [OsX₄(CO)(H₂O)]^?, [OsX₃(CO)(H₂O)] and [OsX₂(CO)(H₂O)₃]⁺, X ? Cl, Br, I, produced by the stepwise hydrolysis of [OsX₅(CO)]^2?, are isolated as pure solutions by ionophoresis and characterized by their absorption spectra. Due to stability of the monaquo complexes and the different trans-effect of the halides it is possible to prepare the mixed complexes [OsX_4–nY_n(CO)(H₂O)]^?, X ≠ Y = Cl, Br, I, n = 1–3, and for n = 2 the pure stereoisomers are formed. A systematic shift is found in charge-transfer bands to the shorter wavelengths when the halides are replaced by H₂O, I by Br or Cl and Br by Cl.     

Transition-Metal Complexes with Bidentate Ligands Spanning trans-Positions. IX. Preparation and 1H-NMR. Studies of complexes [MX2(1)] and [M′Cl(CO)(1)] (M = Pd,Pt; M′ = Rh,Ir; X = Cl,Br, I; 1 = 2, 11-Bis-(diphenylarsinomethyl)benzo[c]phenanthrene) and crystal and molecular structure of [PtCl2(1)]

The preparation of the bidentate ligand 2, 11-bis(diphenylarsinomethyl)benzo-[c]-phenanthrene ( 1 ) is described. This ligand reacts with appropriate substrates to give mononuclear square planar complexes of type [MX₂( 1 )] (M = Pd, Pt; X = Cl, Br, I) and [M′Cl(CO)( 1 )] (M′ = Rh, Ir) in which ligand 1 spans trans-positions. This is confirmed by the crystal structure of [PtCl₂( 1 )]. ¹H-NMR. spectra of the complexes are discussed and compared with those of model compounds trans-[MCl₂( 12 )₂] (M = Pd, Pt) and [M'Cl(CO)( 12 )₂] (M′ = Rh, Ir; 12 = AsBzPh₂).     

Preparation and spectroscopic studies of some cyclic urea adducts of triphenyl-tin and -lead halides

1,3-Dimethyl-2-imidazolidinone (dimethylethylene urea, DMEU) and 1,3-di- methyl-3,4,5,6-tetrahydro-2(IH)-pyrimidinone (dimethylpropylene urea, DMPU) adducts of the type Ph₃SnX·L (X = Cl, Br and I), Ph₃PbX·L (X = Br, I), 3Ph₃PbCl·2DMEU and 2Ph₃PbCl · DMPU have been prepared and characterized. Assignments are made for ν(CO) and ν(CN) frequencies in the IR, and for skeletal frequencies observed in both the IR and Raman spectra in the range 400 to 100 cm^?1 Infrared measurements show that the adducts are bound through the carbonyl oxygen, and are highly dissociated in dichloromethane solution. ¹H and ¹¹⁹Sn or ²⁰⁷Pb NMR measurements reveal that ligand exchange, fast on the NMR time scale, occurs in solution. Coordination of the ligand causes a large upfield shift in the ¹¹⁹Sn or ²⁰⁷Pb resonances, but Ph₃MI · L have shifts similar to those for the parent iodides, indicating almost complete dissociation. Thermodynamic parameters are reported for the dissociation of Ph₃SnX · DMPU (X = Cl, Br) in CH₂Cl₂ solution.     

Darstellung und spektroskopische charakterisierung von mer-trihalogeno-carbonyl-oxalato-osmaten(III)

Upon treatment of trans-[OsX₄(CO)₂]^? or [OsX₅(CO)]^2? with oxalate in aqueous solution new complexes of the type mer-[OsX₃(CO)ox]^2? (X  Cl, Br, I) are formed. The IR and Ra spectra are assigned according to point group C_s. In the UV/VIS spectra, recorded at 10 K, charge transfer transitions from ligand levels, splitted by spin-orbit coupling, (π + σ)t_1u(X) and πt_2u(X) to t_2g(Os³⁺) are observed. Two weak bands with vibrational fine structure in the NIR region are assigned to intraconfigurational transitions within the ground term of osmium(III). The assignment is confirmed by bands of the same frequency observed in the electronic Raman spectrum.     

Alkinylverbindungen von übergangsmetallen : XXXIX. Planare palladium(II) komplexe des typs trans-[p-C6H4(CCPd(X)(PEt3)2)2](n+2)+ (n = summe der ionenladungen von X)

Preparation and properties of the diamagnetic planar complexes trans-[p-C₆H₄(CCPd(X)(PEt₃)₂)₂] (X = Cl, Br, I, NCS) and trans-[p-C₆H₄(CCPd(X)(PEt₃)₂)₂](ClO₄)₂ (X = PEt₃, pyridine) are described. The structures of the compounds have been determined by ³¹P and ¹H NMR spectroscopy. The IR spectra are discussed.     

A carbon-13 NMR study of some metal carbonyl compounds containing one-electron ligands

Carbon-13 NMR spectral data for complexes having the general formula CpM(CO)_nX (Cp = η⁵-C₅H₅; M = Mo or W, n = 3; M = Fe, n = 2; X = halogen, methyl or acetyl) and their phosphine and isocyanide substitution products are reported. For CpM(CO)₃X complexes two carbonyl resonances (1 : 2 ratio) are observed in all cases, consistent with the retention of the “piano-stool” geometries observed in the solid state. Substituted complexes CpM(CO)₂(L)X (M = Mo or W; L = PR₃ or cyclohexyl isocyanide) are unequivocally assigned cis or trans geometries on the basis of the number of observed carbonyl resonances and values of ²J(PC) for the phosphine substituted derivatives. Spectral data for [M(CO)₅X]^? (M = Cr, Mo or W; X = Cl, Br or I) and η⁷-C₇H₇Mo(CO)₂X and the halide derivatives above generally show an increase in the shielding for carbonyls adjacent to the halide ligand in the order Cl < Br < I. Carbonyl resonances are more shielded in isostructural complexes in the order Cr < Mo < W (triad effect).     

Ligating properties of thionitrosoamines: III. Carbonyl complexes of rhodium(I) and rhodium(III) containing N-thionitrosodimethylamine

Me₂NNS reacts with [Rh(CO)₂Cl]₂ to produce the complex cis-Rh(SNNMe₂)(CO)₂Cl (1). The latter undergoes reversible CO substitution by Me₂NNS to give the complex trans-Rh(SNNMe₂)₂(CO)Cl (2a). Complexes 1 and 2a, in solution lose CO and Me₂NSS, respectively, to give the complex trans-(μ-Cl)₂[Rh(SNNMe₂)(CO)]₂ (3). Complex 1 can also be prepared by bubbling CO through a CH₂Cl₂ solution of Rh(SNNMe₂)(diene)Cl (diene = 1,5-cyclooctadiene (4a), norbornadiene (4b)) obtained by a bridge-splitting reaction of Me₂NNS with [Rh(diene)Cl]₂. 1 and 2a react with EPh₃ (E = P, As, Sb) to give the complexes trans-Rh(EPh₃)₂(CO)Cl. The complexes trans-Rh(E′Ph₃)₂(CO)X (X = Cl, E′ = As, Sb; X = Br, NCS, E′ = As) undergo reversible E′Ph₃ displacement upon treatment with Me₂NNS to give the complexes trans-Rh(SNNMe₂)₂(CO)X (X = Cl (2a), Br (2b), NCS (2c)). Oxidative additions of Br₂, I₂, or HgCl₂ to 2a produce stable adducts, while the reaction of 2a with CH₃I gives an inseparable mixture of the adduct Rh(SNNMe₂)₂(CO)(CH₃)ClI and the acetyl derivative Rh(SNNMe₂)₂(CH₃CO)ClI. A mixture of the acetyl derivative (μ-Cl)₂[Rh(SNNMe₂)(CH₃CO)I]₂ and the adduct (μ-Cl)₂[Rh(SNNMe₂)(CO)(CH₃)I]₂ is obtained by treating 1 with CH₃I. The IR spectra of all the compounds are consistent with S-coordination of Me₂NNS. Because of the restricted rotation around the NN bond, the ¹H NMR spectra of the new compounds exhibit two quadruplets in the range 3.5–4.3δ when ⁴J(HH) = 0.7–0.5 Hz. When ⁴J(HH) < 0.5 Hz, the perturbing effect of the quadrupolar relaxation of the ¹⁴N nucleus obscures the spin-spin coupling and two broad signals are observed in the range 3.6–4δ.     

Darstellung und charkterisierung von pentahalogenomonocarbonylosmaten(III)

By decarbonylation of trans-[OsBr₄(CO)₂]^- and exchange of the pure halogen monocarbonyls [OsX₅(CO)]^2? (X Cl, Br, I) can be prepared and isolated as stable salts with various cations. The complexes are characterized by UV-VIS and vibrational spectra and the observed bands are assigned. The stability and behaviour in solution are comparable with similar hexahalo- or pentahalo-nitrosyl compounds.     

Reactivity of [M(CO)3(NN)(thioureas)] (M = Mo,W; NN = 2,2′bipyridine, 1,10-phenanthroline) complexes towards systems with mercury-halides bonds. Trimetallic compounds with XMHgM′X (M′ = Mo,W; X = Cl,Br, I) bondings

New heterotrimetallic complexes were isolated by reaction of M(CO)₃(NN)L (M = Mo, W; NN = bipy, phen; L = thioureas) either with HgX₂ (X = Cl, Br, I) giving complexes of the formula [M(CO)₃(NN)(X)]₂Hg or with M′(CO)₃(NN′)(Cl)(HgCl) (M′ = Mo, W; NN′ = bipy, phen) producing compounds of the type (Cl)(NN)(CO)₃MHgM′(CO)₃(NN′)(Cl). These new photosensitive substances were characterized through IR spectroscopy and conductivity measurements. Structures involving XMHgM′X bonding are proposed and the reactions are discussed in terms of an insertion of the fragment M(CO)₃(NN) into the HgX bonds.     

Carbonylrhodium(I) complexes with heterocyclic nitrogen compounds

Crystalline complexes of rhodium(I) of the type [Rh(CO)₂(NN)] [RhX₂-(CO)₂] (NN  2,2'-bipyridyl, 1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 4,7-dipheynl-1,10-phenanthroline; X = Cl, Br) have been prepared. An ionic chain-like structure involving metal-metal interactions has been established by measurement of the reflectance spectra, absorption electronic spectra and electrical conductivities. The IR spectra have been examined over the 50–4000 cm^-1 range.     

The infrared spectra of ethylenediamine complexes—II. Tris-, bis- and mono(ethylenediamine) complexes of metal(II) halides

The i.r. spectra of the complexes M(en)₃X₂ (M = Mn, Fe, Co, Ni, Cu, Zn), trans-Cu(en)₂X₂, Ni(en)₂X₂ and M(en)X₂ (M = Ni, Cu, Zn; X = Cl, Br, I) have been studied. Assignments are proposed for the tris(ethylenediamine) complexes on the basis of ¹⁵N-, N₂D₄- and C₂D₄-labelling of en and the effects of metal ion substitution in relation to our earlier study of [M(en)₃]SO₄ complexes. Assignments for the bis(ethylenediamine) complexes are based on our observations of halogen-sensitivity and earlier studies on metal isotope labelling and ligand deuteration of the halide complexes and a normal coordinate analysis of the [Cu(en)₂]²⁺ species. The spectra of the halide complexes have been extended below 200 cm⁻¹ for the first time. Finally, the spectra of the mono(ethylenediamine) complexes are discussed in relation to their known or probable structures.     

Preparation and characterization of tris(iso‐propyl)stibine complexes of palladium and platinum

Tris(iso‐propyl)stibine complexes of palladium and platinum of the type [MX₂(SbⁱPr₃)₂] [M, X = Pd, Cl (1a), Pd, Br (1b), Pd, I (1c), Pt, Cl (2)] have been prepared and characterized by elemental analysis, IR and ¹H NMR spectral data. The structure of 1a, established by X‐ray structural analysis, revealed that the palladium atom is in a square planar environment with mutually trans SbⁱPr₃ ligands. Copyright © 2001 John Wiley & Sons, Ltd.     

Phosphine carbonyl-technetium(I) and -technetium(III) complexes

Treatment of trans-[TcX₄L₂] (X Cl, Br and L PPH₃, PMe₂Ph) with carbon monoxide (1 atm) in boiling ethyleneglycol methyl ether, gives trans-[TcX-(CO)₃L₂]. Under these conditions the mer-[TcX₃(PMe₂Ph)₃] (X Cl, Br) gives a mixture of the trans-[TcX(CO)₃(PMe₂Ph)₂] and cis-[TcX(CO)₂(PMe₂Ph)₃] complexes, but when added free dimethylphenylphosphine is present only the second product is obtained. Carbon monoxide reacts with mer-[TcCl₃(PMe₂Ph)₃] in refluxing ethanol to give [TcCl₃(CO)(PMe₂Ph)₃] a C_{3 v} seven-coordinate technetium(III) complex.The stereochemistry of the complexes was determined from their IR and¹H NMR spectra.     

Carbonyl and hydridocarbonyl complexes of ruthenium (II) and osmium (II) with tertiary arsines

Ruthenium halides (Cl and Br) react with monotertiary arsines-Ph₂RAs (R=Me, Et, Pr ⁿ ) in methoxyethanol, in the presence of aq. formaldehyde to give monocarbonyl complexes of ruthenium(II) of the type RuX₂(CO) (Ph₂RAs)₃. Carbonylation of an ethanolic solution containing ruthenium trichloride and the arsine at room temperature yieldtrans dicarbonyl compounds of the formula RuCl₂(CO)₂ (Ph₂RAs)₂. The osmium monocarbonyls OsX₂(CO) (Ph₂RAs)₃ (X=Cl, Br; R=Me, Et) react with NaBH₄ in methanol to yield complexes of the composition OsHX(CO) (Ph₂RAs)₃. The ruthenium analogues RuHCl(CO) (Ph₂RAs)₃ have also been made. Structures have been assigned to all these compounds on the basis of IR and NMR spectral results.     

NMR exchange studies on the complexes trans-[PtX2(C2H4)(Him)] (X = Cl,Br; Him = imidazole)

The ¹H-NMR spectra of the complexes trans-[PtX₂(C₂H₄)(Him)] (X = Cl or Br, Him = imidazole) are discussed. Variable temperature spectra are used to monitor the exchange processes which occur in acetone-d₆ solution. It is found, contrary to previous work, that intermolecular exchange occurs for both the chloro- and bromo- complexes. In addition, it is also found that changing the solvent has a marked effect on the rate of exchange. Using an iterative simulation program and assuming intermolecular exchange, the rate constants for the exchange process are determined by band shape analysis, and the enthalpy and entropy of activation are calculated.     

The isolation of intermediates in hydrogen halide additions to some iridium complexes

The complexes [Ir(cod)L_n]PF₆(I, L = PPh₃, PMePh₂; n = 2. L = PMe₂Ph; n = 3) react with HX to give [IrHX(cod)L₂]PF₆ (II, L = PMePh₂ or PMe₂Ph) or [IrHX₂(cod)(PPh₃)] (III). The intermediates [IrX(cod)L₂] have, in two cases (L = PMePh₂, X = I, Br), been directly isolated from the reaction mixtures at 0°C, and are also formed from I with KX (L = PPh₃, X = Cl; L = PMePh₂, X = Cl, Br, I); these intermediates protonate to give II (L = PMePh₂), or an equimolar mixture of III and I (L = PPh₃, X = Cl). Surprisingly, I₂ reacts with I in MeOH to give III (L = PPh₃). The stereochemistries of II and III were determined by < ¹H NMR and especially by new methods using ¹³C NMR spectroscopy. The complexes I exhibit a Lewis acid reactivity pattern.