Synthesis and multinuclear magnetic resonance spectroscopy of the novel ionic Pt(II) mixed-ligands complexes cis- and trans-[Pt(amine)2(pyrimidine)2](NO3)2

Novel ionic mixed-ligands complexes of the types cis- and trans-[Pt(amine)₂(pm)₂](NO₃)₂ (where pm = pyrimidine) were synthesized and studied in the solid state by IR spectroscopy and in aqueous solution by multinuclear (¹⁹⁵Pt, ¹H and ¹³C) magnetic resonance spectroscopy. The results of the solution NMR characterization have shown that the isolated compounds are pure. In ¹⁹⁵Pt NMR, the cis RNH₂ complexes were observed at slightly lower fields (ave. −2441 ppm) than the equivalent trans analogues (ave. −2448 ppm). For Me₂NH, the difference between the two isomers is larger (29 ppm). The complexes are observed at lower fields (difference of 100 ppm) than the corresponding [Pt(amine)₄]²⁺ complexes, which might indicate the presence of π-backdonation in the Pt-pm bond. In ¹H NMR, the coupling constants ³J(¹⁹⁵Pt-¹H_amine) are larger in the cis compounds (38-48 Hz) than in the trans analogues (30-36 Hz). The ³J(¹⁹⁵Pt-¹H_pm) values are also larger for the cis isomers. In ¹³C NMR spectroscopy, the coupling constants ³J(¹⁹⁵Pt-¹³C_amine) are 36 Hz (ave.) for the cis complexes and 26 Hz (ave.) for the trans isomers, while the ²J(¹⁹⁵Pt-¹³C_amine) are 18 Hz (cis) and 14 Hz (trans), respectively. The ³J(¹⁹⁵Pt-¹³C_5(pm)) values are 36 Hz (cis) and 28 Hz (trans). A few ²J(¹⁹⁵Pt-¹³C_pm) couplings were observed (7-10 Hz).     

Synthesis and characterization of complexes of the type [Pt(amine)4]I2 and trans-[Pt(CH3NH2)2(H3CNC(CH3)2)2]I2 by crystallography and multinuclear magnetic resonance spectroscopy

Complexes of the type [Pt(amine)₄]I₂ were synthesized and characterized mainly by multinuclear (¹⁹⁵Pt, ¹H and ¹³C) magnetic resonance spectroscopy. The compounds were prepared with different primary amines, but not with bulky amines, due to steric hindrance. In ¹⁹⁵Pt NMR, the signals were observed between −2715 and −2769 ppm in D₂O. The coupling constant ³J(¹⁹⁵Pt-¹H) for the MeNH₂ complex is 42 Hz. In ¹³C NMR, the average values of the coupling constants ²J(¹⁹⁵Pt-¹³C) and ³J(¹⁹⁵Pt-¹³C) are 18 and 30 Hz, respectively. The crystal structure of [Pt(EtNH₂)₄]I₂ was determined by X-ray diffraction methods. The Pt atom is located on an inversion center. The structure is stabilized by H-bonding between the amines and the iodide ions. The compound with n-BuNH₂ was found by crystallographic methods to be [Pt(n-BuNH₂)₄]₂I₃(n-BuNHCOO). The crystal contains two independent [Pt(CH₃NH₂)₄]²⁺ cations, three iodide ions and a carbamate ion formed from the reaction of butylamine with CO₂ from the air. When the compound [Pt(CH₃NH₂)₄]I₂ was dissolved in acetone, crystals identified as trans-[Pt(CH₃NH₂)₂(H₃CNC(CH₃)₂)₂]I₂ were isolated and characterized by crystallographic methods. Two trans bonded MeNH₂ ligands had reacted with acetone to produce the two N-bonded Schiff base Pt(II) compound.     

Synthesis and study of Pt(II)-aromatic amines complexes of the types cis- and trans-Pt(amine)2(NO3)2 and cis-Pt(amine)2(R(COO)2)

Complexes of the types cis- and trans-Pt(amine)₂(NO₃)₂ with amines containing a phenyl group were synthesized and studied mainly by IR and multinuclear magnetic resonance spectroscopies. The cis complexes could be synthesized pure only with the amines of the type Ph-R-NH₂ (R = alkyl), while pure trans compounds were synthesized with all the studied amines. In ¹⁹⁵Pt NMR spectroscopy, the dinitrato complexes of the amines Ph-R-NH₂ were observed around −1700 ppm for the cis isomers and at about −1580 for the trans complexes. For the other amines, where a phenyl ring is directly attached to the amino group, the signals were observed at lower fields, −1528 ppm for cis-Pt(PhNH₂)(NO₃)₂ and around −1450 ppm for all the trans isomers. There is a linear relationship between the δ(Pt) of the Pt(amine)₂(NO₃)₂ complexes and the pK_a of the protonated amines. The coupling constants ²J(¹⁹⁵Pt-¹HN) are larger in the cis compounds (ave. 76 Hz) than in the trans isomers (ave. 63 Hz). The complexes cis-Pt(amine)₂(R(COO)₂) with bidentate dicarboxylato ligands were also synthesized and characterized mainly by IR spectroscopy. The compounds apparently decompose in DMF and are too insoluble in other solvents for solution studies.     

Synthesis and multinuclear magnetic resonance spectroscopy of the novel ionic Pt(II) mixed-ligands complexes cis- and trans-[Pt(pyrazine)2(Ypy)2](NO3)2 where Ypy = pyridine derivative

Novel ionic mixed-ligands complexes of the types cis- and trans-[Pt(pz)₂(Ypy)₂](NO₃)₂ (where Ypy is a pyridine derivative and pz = pyrazine) were synthesized and studied mainly in the solid state by IR spectroscopy and in aqueous solution by multinuclear (¹⁹⁵Pt, ¹H and ¹³C) magnetic resonance spectroscopy. The trans isomers with ligands containing a methyl group in ortho position on the pyridine ring could not be synthesized. The results of the solution NMR characterization have shown that the isolated compounds are pure. In ¹⁹⁵Pt NMR, the cis complexes containing a methyl group in ortho positions were observed at lower field (average −2337 ppm) than the other cis compounds (average −2427 ppm), which is explained by the solvent effect. The trans isomers were observed at very slightly lower fields (average −2422 ppm) than the equivalent cis complexes (average −2427 ppm). In ¹H NMR, the coupling constants ³J(¹⁹⁵Pt-¹H_Ypy) and ³J(¹⁹⁵Pt-¹H_pz) are larger in the cis compounds (∼40 Hz) than in the trans complexes (∼31 Hz). A few ⁴J(¹⁹⁵Pt-¹H_pz) were observed (∼16 Hz). In ¹³C NMR spectroscopy, the coupling constants ³J(¹⁹⁵Pt-¹³C_pz) and ³J(¹⁹⁵Pt-¹³C_Ypy) are also larger in the cis configuration (∼30 and ∼38 Hz, respectively) than in the trans isomers (∼20 Hz). One ⁴J(¹⁹⁵Pt-¹³C_pz) could be calculated (17 Hz). The presence of the syn and anti rotamers were observed in all the cis complexes containing a pyridine derivative with a -CH₃ group in ortho position. They were observed in ¹⁹⁵Pt, ¹H and ¹³C NMR spectroscopy. The proportion of the two rotamers is about 55% and 45%.     

Functionalised dithiocarbamate complexes: Synthesis and molecular structures of bis(2-methoxyethyl)dithiocarbamate complexes [M{S2CN(CH2CH2OMe)2}2] (M = Ni, Cu, Zn) and [Cu{S2CN(CH2CH2OMe)2}2][ClO4]

The bis(2-methoxyethyl)dithiocarbamate complexes [M{S₂CN(CH₂CH₂OMe)₂}₂] (M = Ni, Cu, Zn, Pd) are readily prepared and the three lighter complexes have been crystallographically characterised. Disproportionation of [Cu{S₂CN(CH₂CH₂OMe)₂}₂] upon addition of Cu(ClO₄)₂ · 6H₂O affords the copper(III) complex [Cu{S₂CN(CH₂CH₂OMe)₂}₂][ClO₄] which has also been crystallographically characterised. Unlike other copper(III) dithiocarbamate salts, there are no intermolecular cation-cation or cation-anion interactions.     

Synthesis and characterization of three group 10 complexes containing nido-carborane diphosphine: [MCl(PPh3){7,8-(PPh2)2-7,8-C2B9H10}] (M = Ni, Pd, Pt)

Three group 10 complexes containing nido-carborane diphosphine, [NiCl(PPh₃){7,8-(PPh₂)₂-7,8-C₂B₉H₁₀}] (1), [PdCl(PPh₃){7,8-(PPh₂)₂-7,8-C₂B₉H₁₀}] · 1.25CH₂Cl₂ (2) and [PtCl(PPh₃){7,8-(PPh₂)₂-7,8-C₂B₉H₁₀}] · 2.5CH₂Cl₂ (3) have been synthesized by the reactions of [M(PPh₃)₂Cl₂] (M = Ni, Pd, Pt) with closo carborane diphosphine 1,2-(PPh₂)₂-1,2-C₂B₁₀H₁₀ in ethanol. For complex 3, it could also be obtained under solvothermal condition. All three complexes were characterized by elemental analysis, FT-IR, ¹H and ¹³C NMR spectroscopy and X-ray structure determination. Single crystal structures show that their structures are similar to each other. In each complex, the nido [7,8-(PPh₂)₂-7,8-C₂B₉H₁₀]⁻, which resulted from the degradation of the initial closo ligand 1,2-(PPh₂)₂-1,2-C₂B₁₀H₁₀ during the reaction process, was coordinated bidentately through the P atoms to M(II) ion, and this resulted in a stable five-membered chelating ring between the bis-diphosphine ligand and the metal. The coordination mode of the metal can be described as a slightly distorted square-planar, in which the remaining two positions were occupied by one Cl⁻ and one PPh₃ group.     

Synthesis and structural characterization of dinuclear iridium hydrido complex with 3,6-bis(2-pyridyl)tetrazine, [Ir2(H)4(PPh3)4(bptz)](PF6)2 · 4CH2Cl2

Reaction of the precursor Ir complex [Ir(H)₂(PPh₃)₂(Me₂CO)₂]PF₆ with 3,6-bis(2-pyridyl)tetrazine (bptz) in CH₂Cl₂ gave a novel dinuclear Ir hydrido complex [Ir₂(H)₄(PPh₃)₄(bptz)](PF₆)₂ · 4CH₂Cl₂. Crystallographic study described an interesting coordination environment having a π-π interaction and ¹H NMR study showed unique upfield shifts of pyridyl rings that are likely induced by the ring current effect of neighboring PPh₃ ligands.     

X-ray crystal Structure of [1,2-bis(diphenylphosphino)ethane]bis(3,5-dimethylpyrazole-N)platinum(II) tetrafluoroborate dichloromethane solvate, [(Ph2PCH2CH2PPh2)Pt(3,4-Me2pzH)2][BF4]2·CH2Cl2

The crystal structure of the compound [(Ph₂PCH₂CH₂PPh₂)Pt(3,5-Me₂pzH)₂][BF₄]₂·CH₂Cl₂ has shown that the ligands around the Pt atom are approximately in a square planar coordination, whereas the pyrazole rings point roughly in the same direction, away from the coordination plane. This unusual conformation is probably due to the hydrogen bonds with fluorine atoms of the BF₄^? anion. Bond distances and angles are compared with those in other pyrazole complexes.     

Synthesis and kinetic studies of new bipyridyl platinum(II) phenoxide complexes by phase transfer catalysis: Crystal structure of [(bipy)Pt(OC6H4-4-OMe)2]

The synthesis of new platinum bipy (bipy = 2,2′-bipyridyl) complexes containing phenoxide ligands is reported, together with kinetic studies of their oxidative addition reactions with MeI to produce phenoxo platinum(IV) complexes. Complexes of the form [(bipy)Pt(OC₆H₄-4-X)₂] (X = OCH₃, CH₃, H, Br, Cl) are prepared by the reaction of the chloro complex [(bipy)PtCl₂] with substituted phenols and KOH in a two phase system of water and chloroform in the presence of benzyl triphenylphosphonium chloride. Platinum(IV) complexes are formed by oxidative addition of MeI to the platinum(II) complexes obtained. The complexes are characterized by elemental analysis, UV-Vis, IR, mass spectrometry and ¹H and ¹³C NMR spectroscopy.The reaction of methyl iodide with [(bipy)Pt(OC₆H₄-4-OMe)₂] to give [(bipy)PtMe(I)(OC₆H₄-4-OMe)₂] follows the rate law rate = k₂[(bipy)Pt(OC₆H₄-4-OMe)₂][MeI]. The values of k₂ increase with increasing polarity of the solvent, suggesting a polar transition state for the reaction.     

Equilibrium and structural studies on Co(II), Ni(II), Cu(II) and Zn(II) complexes with N-(2-benzimidazolyl)methyliminodiacetic acid: crystal structures of Ni(II) and Cu(II) complexes

Combined pH-metric, UV-Vis, ¹H NMR and EPR spectral investigations on the complex formation of M(II) ions (M=Co, Ni, Cu and Zn) with N-(2-benzimidazolyl)methyliminodiacetic acid (H₂bzimida, hereafter H₂L) in aqueous solution at a fixed ionic strength, I=10⁻¹ mol dm⁻³, at 25 ± 1 °C indicate the formation of M(L), M(H₋₁L)⁻ and M₂(H₋₁L)⁺ complexes. Proton-ligand and metal-ligand constants and the complex formation equilibria have been elucidated. Solid complexes, [M(L)(H₂O)₂] · nH₂O (n=1 for M = Co and Zn, n=2 for M = Ni) and {Cu (μ-L) · 4H₂O}_n, have been isolated and characterized by elemental analysis, spectral, conductance and magnetic measurements and thermal studies. Structures of [Ni(L)(H₂O)₂] · 2H₂O and {Cu(μ-L) · 4H₂O}_n have been determined by single crystal X-ray diffraction. The nickel(II) complex exists in a distorted octahedral environment in which the metal ion is coordinated by the two carboxylate O atoms, the amino-N atom of the iminodiacetate moiety and the pyridine type N-atom of the benzimidazole moiety. Two aqua O atoms function as fifth and sixth donor atoms. The copper(II) complex is made up of interpenetrating polymeric chains of antiferromagnetically coupled Cu(II) ions linked by carboxylato bridges in syn-anti (apical-equatorial) bonding mode and stabilized via interchain hydrogen bonds and π-π stacking interactions.     

Homoleptic platinum(II) and palladium(II) complexes of 1,5,9-trithiacyclododecane: the crystal structures of [Pt(12S3)2](PF6)2 · 2CH3NO2 and [Pd(12S3)2](BF4)2 · 0.5H2O

The synthesis, spectroscopy, electrochemistry, and crystal structures of two new mononuclear homoleptic Pt(II) and Pd(II) complexes with the crown trithioether 1,5,9-trithiacyclododecane (12S3) are reported. In contrast to behavior with analogous smaller ring trithiacrowns, both metal complexes exhibit exodentate axial sulfur donors, a consequence of the preferred conformation of the 12S3 ligand. The lack of two axial metal-sulfur interactions correlates with the observed electronic spectroscopy and oxidative electrochemistry displayed by the complexes and contrasts with properties exhibited by complexes containing smaller polythioether macrocycles. The two complexes have electronic spectra dominated by charge transfer, not d-d bands and show no M²⁺/M³⁺ couples. Both complexes show a fluxional 12S3 ligand in solution due to a 1,5-metallotropic shift, an uncommon observation of this particular type of intramolecular ligand exchange. The ¹⁹⁵Pt NMR chemical shift of −4201 ppm for [Pt(12S3)₂]²⁺ is consistent with an alternating positioning of the four sulfur lone pairs on the coordinated thioethers. Although 12S3 is poorly pre-organized for facial complexation, its flexibility to position a sulfur in an exodentate fashion enables it to form stable complexes with d⁸ metal ions such as Pt(II) and Pd(II).     

Cobalt(II) and nickel(II) coordination polymers constructed from P,P′-diphenylmethylenediphosphinic acid (H2pcp) and 4,4′-bipyridine (bipy): Structural isomerism in [Co(pcp)(bipy)0.5(H2O)2]

The P,P′diphenylmethylenediphosphinic acid (H₂pcp) reacts with Co(ClO₄)₂ · 6H₂O and 4,4′-bipyridine to give a mixture of two polymeric isomers of formula [Co(pcp)(bipy)_0.5(H₂O)₂], {red (1) and pink (2)} and the new violet hybrid [Co(Hpcp)₂] (3). The pure red and violet species have been obtained by the reaction of H₂pcp with Co(CH₃COO)₂ · 4H₂O and bipy or with Co(ClO₄)₂ · 6H₂O, respectively. The analogous reaction of Ni(CH₃COO)₂ · 4H₂O or Ni(ClO₄)₂ · 6H₂O with H₂pcp and bipy affords only the [Ni(pcp)(bipy)_0.5(H₂O)₂] species (4). The two cobalt isomers present different structural arrangements. Whereas the red isomer (1) shows an undulated 2D layered structure, the pink one (2) forms an infinite monodimensional strand. Both the architectures extend to higher dimensions through hydrogen bonding interactions. The nickel derivative is isomorphous with the red cobalt isomer. The violet [Co(Hpcp)₂] (3), which is isomorphous with the complexes of the reported series [M(Hpcp)₂], M = Ca(II), Mg(II), presents a monodimensional polymeric structure. Compounds 1 and 4 show a very similar thermal behaviour, the two water molecules being lost in the temperature range 25-150 and 160-320 °C, respectively. Temperature dependent X-ray powder diffractometry (TDXD) has been performed on compound 1 in order to follow the structural transformations that occur during the heating process.     

Synthesis and characterization of some oxovanadium(V) complexes with internally functionalized oximes: Crystal and molecular structures of heptacoordinated [VO{ONC(CH3)(C4H3O-2)}3] and [VO{ONC(CH3)(C4H3S-2)}3] · 0.5C6H6

New oxovanadium(V) complexes with internally functionalized oximes of the type VO{OPrⁱ}_3−n{ONC(CH₃)(Ar)}_n] (where Ar = C₄H₃O-2, C₄H₃S-2 and C₅H₄N-2 and n = 1-3) have been prepared in quantitative yields by the reaction of VO(OPrⁱ)₃ with the corresponding oximes in various stoichiometric ratios in refluxing anhydrous benzene. The products have been characterized by elemental analyses and spectroscopic (FT IR, ¹H, ¹³C{¹H} and ⁵¹V NMR) studies. FAB mass spectral analysis of [VO{OPrⁱ}{ONC(CH₃)C₄H₃S}₂] indicates the monomeric nature of the complex. ⁵¹V NMR values for these complexes suggest the formation of tetra-coordinate species in solution. However, the single crystal X-ray diffraction studies of [VO{ONC(CH₃)(C₄H₃O-2)}₃] and [VO{ONC(CH₃)(C₄H₃S-2)}₃] · 0.5C₆H₆ exhibit the presence of vanadium(V) atoms in a unique hepta-coordination state with distorted pentagonal bipyramidal geometry in the solid state. The oxo- atom occupies the axial position while the oximato ligands are bonded in a dihapto (η²-N,O) manner with the formation of three membered rings.     

The platinum complexes with histamine: Pt(II)(Hist)Cl2, Pt(II)(Iodo-Hist)Cl2 and Pt(IV)(Hist)2Cl2

The Pt(II) and Pt(IV) complexes with histamine were calculated by using more than 20 DFT functionals and various basis sets. Based on the comparison between the X-ray and theoretical geometrical parameters of the Pt(II)(Hist)Cl₂ complex the MPW1PW91, OPW91 and SVWN5 functionals combined with the 6-311G^∗∗ basis set for non-metallic and SDD (ECP) basis set for platinum were found to yield the most satisfactory agreement. The structure of the Pt(II) complex with iodohistamine important for pharmacy, so far isolated only in minute amounts, was predicted by using the MPW1PW91 functional. Comparison of the theoretical NMR chemical shifts of the Pt(II)(Hist)Cl₂ complex with those found experimentally have shown that the theoretical ¹H and ¹³C NMR chemical shifts are in plausible agreement with the experimental ones, whereas the theoretical ¹⁹⁵Pt chemical shifts fit the experimental values only when the relativistic approach is applied within the ZORA formalism. We confirmed suitability of the three selected functionals for reproduction of the experimental structure of Pt complexes at fourth oxidation state by using the cis- and ions as models. Finally, with the selected theoretical methods, the structures and stabilities of four Pt(IV)(Hist)₂Cl₂ complex isomers were predicted.     

Ru2(CO)4(OOCR)2L2 sawhorse-type complexes containing axial 5-(4-pyridyl)-10,15,20-triphenylporphyrin ligands

The thermal reaction of Ru₃(CO)₁₂ with various carboxylic acids (benzoic, 4-hydroxyphenylacetic, ferrocenic, stearic, oleic, 4-(octadecyloxy)benzoic) in refluxing tetrahydrofuran, followed by addition of 5-(4-pyridyl)-10,15,20-triphenylporphyrin (L), gives the dinuclear complexes Ru₂(CO)₄(OOCR)₂L₂ (1: R = -C₆H₅, 2: R = -CH₂-p-C₆H₄OH, 3: R = -C₅H₄FeC₅H₅, 4: R = -(CH₂)₁₆CH₃, 5: R = -(CH₂)₇CHCH(CH₂)₇CH₃, 6: R = -p-C₆H₄O(CH₂)₁₇CH₃). Complexes 1-6 were characterised by IR, NMR, and ESI-MS as well as by elemental analysis. The UV-Vis spectra show the Soret band centred at 417 nm and the Q bands at 515, 550, 590 and 645 nm, respectively.     

Novel reactivity aspects of cis-bis(1-alkenyl)platinum(II) compounds of the type Pt(CH2(CH2)nCHCH2)2L2 (where L2 = dppp, dppe, dppm and n = 1, 2)

We describe the synthesis, structure and reactivity of novel bis(1-alkenyl)platinum(II) complexes, Pt[CH₂(CH₂)_nCHCH₂]₂L₂ (where L₂ = dppp, dppe, dppm and n = 1, 2). The stability of the title complexes with the different ligands is discussed. The steric, chelating and electronic properties of the ligands have a significant impact on the structure as well as on the reactivity of the complexes. Novel reactions with elemental sulfur and carbon dioxide are described and discussed.     

Organopalladium(IV) and platinum(IV) complexes containing the bis(pyrazol-1-yl)borate ligand. Structures of PtMe3{(pz)2BH2}(py) (py=pyridine) and Pt(mq)Me2{(pz)2BH2} (mq=8-methylquinolinyl) and detection of a neutral organopalladium(IV) phosphine complex

Neutral palladium(IV) complexes containing the bis(pyrazol-1-yl)borate ligand, PdMe₃{(pz)₂BH₂}(L) [L=py-d₅ (4), PMe₂Ph (6)], are generated in solution by oxidative addition of iodomethane to [PdMe₂{(pz)₂BH₂}]⁻ at −70 °C followed by addition of L; the Pd(IV) complexes reductively eliminate ethane above 0 °C. Stable Pt(IV) analogues of 4 and 6 have been isolated, and comparison of NMR spectra for Pd(IV) and Pt(IV) species support structural assignments for the unstable Pd(IV) complexes. The complex PtMe₃{(pz)₂BH₂}(py) (1a) has been characterised by X-ray diffraction, together with Pt(mq)Me₂{(pz)₂BH₂} (2) (mq=8-methylquinolinyl); both complexes show a fac-PtC₃ configuration for Pt(IV), and for 2 the PtN distances are ∼0.03 Å shorter than in the isostructural Pd(IV) complex.     

Supramolecular assemblies of new 2-D complexes: Syntheses, crystal structures, spectroscopic and magnetic properties of {[MnAu2(CN)4(NITpPy)2(H2O)2]}n and {[Co(N(CN)2)2(NITpPy)2(H2O)2]}n

Two new complexes, {[MnAu₂(CN)₄(NITpPy)₂(H₂O)₂]}_n (1) and {[Co(N(CN)₂)₂(NITpPy)₂(H₂O)₂]}_n (2), have been synthesized and characterized. The single-crystal X-ray analysis for the complexes 1 and 2 demonstrates that each M(II) (M = Mn or Co) ion assumes a distorted octahedral MN₄O₂ coordination polyhedron. Four nitrogen atoms come from the cyanide groups and the pyridyl rings in a common plane, and two oxygen atoms come from the H₂O molecules in trans-positions. The structures of complexes 1 and 2 illustrate that aurophilicity and/or hydrogen bonding interactions play important roles in increasing dimensionality. Magnetic investigations on complexes 1 and 2 show the presence of weak antiferromagnetic interactions.     

Synthesis, spectroscopic and structural characterization of adducts of stoichiometry CuX:dppe (1:2) (X = I, ClO4, BH4, O3SCF3, SCN, dppe = Ph2P(CH2)2PPh2)

Syntheses and spectroscopic features (IR, NMR and ESI MS) are reported for five 1:2 adducts of CuX with dppe (X = I, ClO₄, NCS, O₃SCF₃ (tfs) BH₄; dppe = Ph₂P(CH₂)₂PPh₂). ESI MS and ³¹P NMR spectroscopy indicate that these species dissociate in solution yielding free diphosphine and 3:2 species. A single crystal X-ray structure determination has been carried out on Cu(dppe)₂NCS defining a four-coordinate complex of the form [(P,P′-dpex)M(P-dpex)X] for M = Cu, the thiocyanate being N-bound; the ionic [Cu(P,P′-dppe)₂]tfs has also been structurally characterized.     

Synthesis and characterization of carbamoyl methyl pyrazole(CMPz) compounds of palladium(II) chloride: The crystal and molecular structure of [PdCl2{C3H3N2CH2CONBu2}2]

Carbamoyl methyl pyrazole compound of palladium(II) chloride of the type [PdCl₂L₂] (where L =  C₅H₇N₂CH₂CON(C₄H₉)₂, C₅H₇N₂CH₂CON(ⁱC₄H₉)₂, C₃H₃N₂CH₂CON(C₄H₉)₂, or C₃H₃N₂CH₂CON(ⁱC₄H₉)₂) has been synthesized and characterized by IR and ¹H NMR spectroscopy. The structure of the compound [PdCl₂{C₃H₃N₂CH₂CONⁱBu₂}₂] has been determined by single crystal X-ray diffraction and shows that the ligands are bonded through the soft pyrazolyl nitrogen atom to the palladium(II) chloride in a trans disposition.