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Konstantin A Udachin

Publications and source records attributed to Konstantin A Udachin.

At least 19 recordsLinked to original sources

Non-covalent polymerisation in the solid state: halogen-halogen vs. methyl-methyl interactions in the complexes of 2,4-di(2-pyridyl)-1,3,5-triazine ligands.

Fe(II), Co(II), Ni(II) and Cu(II) complexes based on the triazine ligand 2,4-di(2'-pyridyl)-6-(p-bromo-phenyl)-1,3,5-triazine have been synthesised and characterised. The electrochemical, magnetic and spectroscopic properties of the complexes have also been investigated, and the electron deficient triazine ligand has been shown to affect each of these properties. Further investigation of solid state structures of the ligand and its Fe(II), Co(II) and Cu(II) complexes has established that stabilising Br-Br interactions exist which link neighbouring molecules to form one-dimensional tapes. A slight modification of the ligand, i.e., using 2,4-di(2'-pyridyl)-6-(p-methylphenyl)-1,3,5-triazine, in which the phenyl substituent has changed from a bromine to a methyl group, eliminates the one-dimensional tape and gives rise to significant pi-stacking interactions in the solid state.

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Pseudopolymorphism of aliphatic amine/4-tert-butylcalix[4]arene inclusion compounds: supramolecular stabilization as a route to polar clusters and layers.

4-tert-Butylcalix[4]arene (4tBC4A) is a versatile host capable of forming a variety of 1:1 and 2:1 inclusion compounds typically stabilized through van der Waals interactions. Preliminary studies in our group have demonstrated that inclusion of n-butylamine in 4tBC4A results in a series of pseudopolymorphic inclusion compounds, including a new 3:1 inclusion motif. Using a combination of SCXRD, TGA, solid state NMR, and PXRD, we now elaborate upon the relationship between these pseudopolymorphs. We also demonstrate that larger amines demonstrate a similar degree of pseudopolymorphism, allowing for the production of customized materials using self-assembly guided by competing weak forces. Finally, we comment on the structural implications of the relative dominance such forces in the formation of calixarene-based supramolecular frameworks.

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Phototransformation of stilbene in van der Waals nanocapsules.

We have utilized para-hexanoylcalix[4]arene nanocapsules as hosts to carry out phototransformations of cis- and trans-stilbene. Single-crystal X-ray diffraction studies were performed to define precisely the location of encapsulated stilbenes inside the capsule and to analyze possible pathways of phototransformation. cis-Stilbene stacks as a pi-pi dimer located at the center of the capsule, whereas trans-stilbene does not form such a dimer. Irradiation of the crystalline inclusion complexes of each isomer of stilbene in the solid state leads to the appearance of the second isomer, and after prolonged photolysis, photodimerization also occurs. syn-Tetraphenylcyclobutane is formed as the major product of dimerization and its yield depends on the time and intensity of irradiation. In most cases, the single crystals of the complexes remain intact during irradiation; hence, the nanocapsules have the potential to serve as robust nanoreactors in the solid state. The confinement in the nanocapsules is sufficient to keep the reacting molecules together, although this is less restrictive than for trans-stilbene crystals, in which the molecules cannot achieve a favorable orientation for dimerization.

Calixarenes↗

Reactivity patterns of thermally stable, terminal, electrophilic phosphinidene complexes towards diazoalkanes: oxidation at the phosphorus centre and formation of P-bound eta1-phosphaazine, eta1-phosphaalkene and eta3-diazaphosphaallene complexes.

The thermally stable, terminal phosphinidene complexes [CpM(CO)2(eta1-PNiPr2)]AlCl4(Cp= Cp, Cp*; M = Fe) and [Cp*M(CO)3(eta1-PNiPr2)]AlCl4 (M = Cr, Mo, W) react with Ph2C=N=N to form terminal P-coordinated eta1-phosphaazine and eta3-diazaphosphaallene ligands, respectively, whereas [CpFe(CO)2(eta1-PNiPr2)]AlCl4 reacts with Me3SiCHN2 affording a terminal phosphorus bound eta1-phosphaalkene complex.

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Reactivity of electrophilic micro-phosphinidene complexes with heterocumulenes: formation of the first sigma-pi-aminophosphaimine complexes [Mn2(CO)8{micro-eta1,eta2-P(NiPr2)=NR}] and diazoalkane insertions into metal-phosphorus bonds.

The bridging phosphinidene complexes [Mn2(CO)8(micro-PNiPr2)] and [Co2(CO)4(micro-dppm)(micro-PNR2)](NR2=NiPr2, TMP) react with heterocumulenes RN3, CH2N2 and Ph2C=N=N to form complexes with micro-eta1,eta2-aminophosphaimine, micro-eta1,eta2-aminophosphaalkene and micro-eta1,eta2-aminophosphadiphenylmethylazaimine ligands, respectively.

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Transformation of mu4-phosphinidenes at an Ru5 center: isolation and structural characterization of hydroxyphosphinidene cluster acids, fluorophosphinidenes, and a novel mu5-phosphide.

Acid hydrolysis of [Ru(5)(CO)(15)(mu(4)-PN(i)Pr(2))] (2) or protonation of the anionic PO cluster [Ru(5)(CO)(15)(mu(4)-PO)](-) (3) affords the hydroxyphosphinidene complex [Ru(5)(CO)(15)(mu(4)-POH)].1.[H(2)N(i)()Pr(2)][CF(3)SO(3)], which cocrystallizes with a hydrogen-bonded ammonium triflate salt. Reaction of [Ru(5)(CO)(15)(mu(4)-PN(i)Pr(2))] (2) with bis(diphenylphosphino)methane (dppm) leads to [Ru(5)(CO)(13)(mu-dppm)(mu(4)-PN(i)Pr(2))] (4). Acid hydrolysis of 4 leads to the dppm-substituted hydroxyphosphinidene [Ru(5)(CO)(13)(mu-dppm)(mu(4)-POH)] (5), which is analogous to 1, but unlike 1, can be readily isolated as the free hydroxyphosphinidene acid. Compound 5 can also be formed by reaction of 3 with dppm and acid. The cationic hydride cluster [Ru(5)(CO)(13)(mu-dppm)(mu(3)-H)(mu(4)-POH)][CF(3)SO(3)] (6) can be isolated from the same reaction if chromatography is not used. Compound 4 also reacts with HBF(4) to form the fluorophosphinidene cluster [Ru(5)(CO)(13)(mu-dppm)(mu(4)-PF)] (7), while reaction with HCl leads to the mu-chloro, mu(5)-phosphide cluster [Ru(5)(CO)(13)(mu-dppm)(mu-Cl)(mu(5)-P)] (8).

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Metal-templated diyne cyclodimerization and cyclotrimerization.

Reaction of [Pt(CH3)2(COD)] (COD = 1,5-cyclooctadiene) with Ph2PCCCCPPh2 led to a mixture of [{Pt(CH3)2}2(mu-Ph2PC4PPh2)2] (1) and [{Pt(CH3)2}3(mu-Ph2PC4PPh2)3] (2). Reaction of [PtCl2(COD)] with Ph2PCCCCPPh2 led to a mixture of the thermally unstable compounds [{PtCl2}2(mu-Ph2PC4PPh2)2] (3) and [{PtCl2}3(mu-Ph2PC4PPh2)3] (4) which transform into [{PtMe2}2{mu-C8(PPh2)4}] (5) and [{PtMe2}3{mu3-C12(PPh2)6}] (6) containing 8-membered diene-diyne and 12-membered triene-triyne rings, respectively. Compound 2 can be converted to [{PtMe2}3{C12(PPh2)6}] (7) by heating with CuCl at 80 degrees C, while 1 can be heated without significant cycloaddition.

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Locating dynamic species with X-ray crystallography and NMR spectroscopy: acetone in p-tert-Butylcalix[4]arene.

The exact location and orientation of dynamic species in structural studies continues to be a serious challenge, yet it is of paramount importance in modeling guest--host interactions so as to improve our understanding of the multiple weak interactions that govern many chemical and biological processes. The acetone guest in the tBC (p-tert-butylcalixarene) host presents such a challenge, as initial guest positions obtained from single crystal X-ray diffraction (XRD) are incompatible with the 2H NMR spectrum. A detailed consideration of the diffraction data showed that more complicated structural models could be constructed that were consistent with the NMR data and still yielded satisfactory diffraction residuals. These models agree that one acetone methyl group is inserted into the deep cavity, and that it exchanges with the second methyl group outside. The outside methyl group in turn can switch positions with the carbonyl group, but the distribution of the methyl and carbonyl groups over the two sites is not equal. One factor that poses additional difficulty in deciding between models is whether the actual space group is tetragonal (P4/n), or twinned monoclinic (P2/n). All of the structural models considered here disagree substantially with the one proposed in an earlier publication.

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Fluorinated aminoalkoxide and ketoiminate indium complexes as MOCVD precursors for In2O3 thin film deposition.

The syntheses of two distinctive types of indium complex derived from trimethylindium (InMe(3)) are reported. The first kind has a generalized structural formula [InMe(2)(amak)](2), where (amak)H is an abbreviation for a series of chelating amino alcohol ligands HOC(CF(3))(2)CH(2)NHR, R = (CH(2))(2)OMe (1), Me (2), and Bu(t) (3), as well as HOC(CF(3))(2)CH(2)NMe(2) (4); while the second type of complex is illustrated by [InMe(2)(keim)] (5), for which (keim)H is a tridentate ketoimine ligand of structural formula O=C(CF(3))CH(2)C(CF(3))=NCH(2)CH(2)NMe(2). The solid-state structures of 2 and 5 were determined using single crystal X-ray diffraction studies. For the aminoalkoxide complexes 2-4, the existence of dimeric In(2)O(2) core structures in the solid state has been established with the amino fragment located trans to the alkoxide ligands, in a molecular arrangement which is in contrast to the distorted, trigonal bipyramidal geometry observed for the ketoiminate complex 5. Moreover, VT NMR studies of 2 revealed a rapid dimer-to-monomer equilibration and simultaneous rupture of the N-->In dative interaction, affording two interconvertible isomers related by having the N-Me substituents in either trans or cis dispositions. For complexes 2 and 5, deposition of In(2)O(3) thin films was successfully conducted at temperatures 400-500 degrees C, using O(2) as the carrier gas to induce indium oxide deposition and to suppress carbon impurity present in the thin film. Scanning electron micrographs (SEMs) revealed the surface morphologies. The atomic composition of these films was examined by both X-ray photoelectron spectroscopy (XPS) and Rutherford backscattering (RBS) methods, while X-ray diffraction studies (XRD) confirmed the formation of a preferred orientation along the (222) planes.

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Thermally programmable gas storage and release in single crystals of an organic van der Waals host.

A single crystal of a low density form of guest-free p-tert-butylcalix[4]arene can take up and release small guest molecules by controlling the temperature and pressure without changing the structure. Using NMR spectroscopy with flowing hyperpolarized xenon, we have shown that at room temperature access of xenon to the pore system is difficult, whereas it is relatively easy at 100 degrees C. There are good prospects for simple van der Waals materials such as the title material to be used as programmable zeolite mimics.

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