Synthesis and Structure of a Molecular Zinc Phosphate [(C12H8N2Zn)2(HPO4)(H2PO4)2]

A hydrothermal reaction of a mixture of ZnCO₃, phosphoric acid, 1, 10‐phenanthroline in H₂O gave rise to large plates of a new zinc phosphate, [(C₁₂H₈N₂Zn)₂(HPO₄)(H₂PO₄)₂], I . The structure consists of ZnO₃N₂ distorted trigonal‐bipyramidal and PO₄ tetrahedral units linked through their vertices to give rise to a zero‐dimensional molecular solid (monomer). The structure of the monomer appears to be similar to the secondary building unit (SBU) 4 = 1, commonly found in many fibrous zeolites. To our knowledge, this is the first time this building unit has been isolated. The structure, with a unique composition, is stabilized by hydrogen bond interactions between the terminal —OH groups forms a one‐dimensional molecular wire and also by strong π…π interactions between the 1, 10‐phenanthroline units. Photoluminescence studies show that there is a ligand‐to‐metal charge transfer (LMCT). Crystal data: orthorhombic, space group = Fdd2 (no. 43), a = 40.4669(1), b = 7.4733(2), c = 17.4425(5)Å, V = 5274.9(2)ų, Z = 8.     

Hydrothermal synthesis and structures of two zero-dimensional zinc phosphate polymorphs

Two polymorphs of zero-dimensional zinc phosphate with the formula, ⁰_∞[Zn(2,2′-bipy)(H₂PO₄)₂], have been synthesized employing hydrothermal technique and their structure determined by single crystal X-ray diffraction. Both the structures consists of ZnO₃N₂ distorted trigonal-bipyramidal and PO₂(OH)₂ tetrahedral units linked through their vertices giving rise to a zero-dimensional molecular zinc phosphate. The structures are stabilized by extensive hydrogen bond interactions between zero-dimensional monomers. The structures display subtle differences in their packing created by hydrogen bond interactions. Crystal data: polymorph I, triclinic, space group (No. 2), , , , α=67.32(3)°, β=81.67(3)°, γ=69.29(3)°, , Z=2; polymorph II, triclinic, space group (No. 2), , , , α=97.37(2)°, β=100.54(2)°, γ=100.98(2)°, , Z=2.     

Synthesis and investigation of mono- and binuclear cyano-bridged complexes of rhodium,ruthenium, and palladium

Binuclear Rh^III and Ru^II complexes of the [M¹-CN-M²]⁺BF ₄ ^– (M¹ and/or M² are (⁵-Cp)(³-C₃H₅)Rh and (⁶-C₆H₆)(³-C₃H₅)Ru) type, heteronuclear organometallic compound (⁵-Cp)(³-C₃H₅)RhCNPd(³-C₃H₅)Cl, and mononuclear Rh^III and Ru^II complexes [(³-C₃H₅)LM(MeCN)]⁺ _BF4 ^– (M = Rh, L = ⁵-Cp; M = Ru, L = ⁶-C₆H₆) were synthesized. An electrochemical study of these compounds in solutions demonstrates that the bond between the bridged CN ligand and the metal atoms is rather strong, and there is no dissociation into mononuclear fragments in solutions. The kinetics of the reaction of [(⁵-Cp)(³-C₃H₅)Rh(MeCN)]⁺ _BF4 ^– with halide ions was studied by electrochemical methods. The ligand exchange proceeds by a bimolecular dissociative-exchange mechanism.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 968–973, May, 1995.     

New synthetic route to polyphosphine ligands bearing 1,2,4,5-tetrakis(phosphino)benzene framework: structural characterizations of 1,4-(PPh2)2-2,5-(PR2)2-C6F2 (R = Ph, Pr, Et)

Reactions of 1,4-dibromo-2,5-difluorobenzene with two equivalents of lithium diisopropylamide at low temperature (T < −90 °C) followed by a quench with a slight excess of ClPPh₂ afford 1,4-dibromo-2,5-bis(diphenylphosphino)-3,6-difluorobenzene (1) in good yields. Reacting 1 with two equivalents of BuLi followed by a quench with a slight excess of ClPR₂ yield novel 1,2,4,5-tetrakis(phosphino)-3,6-difluorobenzenes 1,4-(PPh₂)₂-2,5-(PR₂)₂-C₆F₂ (R = Ph (2a); R = ⁱPr (2b); R = Et (2c)) in moderate yields. Compounds 1 and 2a-c were characterized by multinuclear NMR spectroscopy and elemental analyses. In addition, molecular structures of 2a-c have been determined by single crystal X-ray crystallography. Phosphorus atoms of PPh₂/PR₂ substituents in 2a-c are displaced from the plane of the central phenyl ring due to steric interactions with neighboring groups.     

Temperature dependence of X- and Q-band EPR spectra of the dinuclear manganese(II) complex [(NO2Bpmp)Mn2(mu-OAc)2]+: determination of the exchange constant and of the spin parameters for the S=1, 2, and 3 spin states

A new dinuclear manganese(II) complex was synthesised with the biscompartimental ligand 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-nitrophenol (NO(2)BpmpH) and characterised by X-ray crystallography. Magnetic susceptibility measurements revealed that the two high-spin Mn(II) ions are antiferromagnetically coupled with a singlet-to-triplet separation of 7.2 cm(-1). The powder EPR spectra were recorded for both X- and Q-bands between 1.8 K and 35 K. A detailed analysis of these spectra led to the determination of three out of five individual spin-state zero-field splitting parameters. From the proposed simulations, the exchange coupling constant J and the intermetallic distance have been computed.     

Structural studies of new chiral nickel (II) complexes of cyclams: The influence of a systematically varied number of amide groups

The synthesis and structures of nickel (II) complexes of chiral cyclams originating from l-proline are presented. Upon addition of nickel acteate, oxocyclams having amide groups underwent deprotonation forming distorted square-planar complexes. In the case of the all-amine analogue a six-coordinate octahedral complex is formed.     

A correlation study of bisphosphine ligand bite angles with enantioselectivity in Pd-catalyzed asymmetric transformations

Among the bisphosphine ligands, we have previously developed C_n-TunePhos (n = 1-6) as a family of ligands with tunable bite angles. The increase in spacer -CH₂- groups in this family of ligands causes changes in ligand dihedral angle, which in turn causes P-Pd-P bite angle variation. Pd-catalyzed asymmetric alkylations and cycloadditions have been tested with C_n-TunePhos ligands. This study aims at a possible correlation between ligand bite angles with enantioselectivity of the Pd-catalyzed asymmetric products.     

A bifunctional platinum(II) complex capable of intercalation and hydrogen-bonding interactions with DNA: binding studies and cytotoxicity

The interactions of [Pt(CNN)(4-dpt)]PF(6), (1; 4-dpt=2,4-diamino-6-(4-pyridyl)-1,3,5-triazine, HCNN=6-phenyl-2,2'-bipyridine) with double-stranded DNA, poly(dA-dT)(2), and poly(dG-dC)(2) were examined by spectroscopic, electrophoretic, and hydrodynamic methods. The spectroscopic data were analyzed with McGhee, van't Hoff, and Gibbs-Helmholtz equations. In a comparative study, [Pt(CNN)(py)]PF(6) (2; py=pyridine) was prepared and the nature of its binding towards DNA was investigated [preliminary results: ChemBioChem 2003, 4, 62-68]. For reactions with calf thymus DNA at 20 degrees C, the intrinsic binding constants for 1 and 2 are (4.6+/-0.2)x10(5) and (2.3+/-0.3)x10(4) mol(-1) dm(3), respectively. Results of DNA-binding reactions revealed that 1 and 2 preferentially bind to the AT sequence of duplex DNA. Intercalation is the preferred binding mode for 2, whereas both intercalation and minor-groove binding are observed for 1. Complex 1 is cytotoxic against a number of carcinoma cell lines, including KB-3-1, CNE-3, and HepG2, and remains potent against multidrug- or cisplatin-resistant KB-V-1 and CNE1 cell lines, for which the resistance ratios are 1.6 and 1.5, respectively. Importantly, 1 is almost an order of magnitude less toxic to the normal cell line CCD-19Lu (IC(50)=176+/-1.7 microM) and it selectively induced apoptosis leading to cancer cell death with less than 5 % detectable necrosis.     

Oxomolybdenum(VI) and (IV) complexes of pyrazole derived ONO donor ligands – synthesis,crystal structure studies and spectroelectrochemical correlation

Four cis-dioxomolybdenum complexes of general formula [MoO₂(Lⁿ)EtOH] (n = 1–4) and one oxomolybdenum(IV) complex [MoO(L⁴)EtOH], with potentially tridentate Schiff bases derived from 5-methyl pyrazole-3-carbohydrazide and salicylaldehyde/substituted salicylaldehyde/o-hydroxy acetophenone have been prepared. The Mo(IV) complex is derived from the Mo(VI) dioxo complex by oxotransfer reaction with PPh₃. The complexes are characterized by elemental analysis, electronic spectra, IR, ¹H NMR, and by cyclic voltammetry. All the Mo(VI) species are crystallographically characterized. The complexes have a distorted octahedral structure in which the ligand behaves as a binegative donor one, leaving the pyrazole –N uncoordinated towards the metal center. It is also revealed from the crystal structure that the Mo(VI) center enjoys an NO₅ donor environment.