0000000001302632
AUTHOR
Pauli Saarenketo
Reactivity of Distibanes toward Trialkylalanes and -gallanes: Syntheses and X-ray Structures of Bisadducts and Heterocycles
Reactions between distibanes of the type Sb2R4 and trialkylalanes and -gallanes R‘3M in 1:2 stoichiometry yield eight bisadducts of the type [Sb2R4][MR‘3]2 (R = Me, R‘ = t-Bu, M = Al 1, Ga 2; R = Et, M = Al, R‘ = Me 3, Et 4, t-Bu 5; M = Ga, R‘ = Me 6, Et 7, t-Bu 8), which were characterized by multinuclear NMR studies and elemental analysis. In addition, 1, 2, 5, and 8 are the first structurally characterized neutral main group Lewis acid−distibane bisadducts. 1−8 are unstable in solution toward the formation of heterocycles of the type [R2SbMR‘2]x. [Me2SbGa(t-Bu)2]3 (9) and [Et2SbGa(t-Bu)2]2 (10) have been isolated and their solid state structures determined by single-crystal X-ray diffrac…
Redox-induced coordination isomerization of a phosphoniobenzophospholide.
1-Triphenylphosphoniobenzo[c]phospholide 1 reacts with [M(CO)(5)Br] (M = Mn, Re) and [Mn(CO)(3)(naphthalene)][BF(4)] to give complexes cis-[M(CO)(4)(1)Br] (5 a,b) and [Mn(CO)(3)(1)][BF(4)] (6 a[BF(4)]), respectively, featuring eta(1)(P)- and eta(5)(pi)-coordination of the phosphole ring. The corresponding reactions with [M(2)(CO)(10)] proceed with conservation of the metal-metal bond and yield, depending on the reaction temperature, dinuclear complexes [M(2)(CO)(8)(1)] (M=Mn, 7 a) or [M(2)(CO)(6)(1)(2)] (M=Mn, Re, 8 a,b) with mu(2)-bridging eta(1)(P):eta(2)(Pdbond;C) coordination of the phosphole moiety. All complexes formed were characterized by spectroscopic data; 5 b, 6 a[BF(4)], and 8 a…
Synthesis, structural diversity, inter-conversion and reactivity of Cu(II) complexes of hydroxy-rich molecules
Tetranuclear Cu(II) complexes having linear, cubane and pseudodouble-cubane cores were synthesized using hydroxy-rich molecules possessing amine and imine groups. The products were structurally characterized and were studied for their ability to oxidize catechol as well as for their inter-conversion between mono- and tetra-nuclear complexes.
An ab Initio MO Study of Silver Triflate Complexation in [2.2.1]Cyclophane π-Prismands
Ab initio Hartree-Fock and DFT MO calculations have been used to study the conformations of six [2.2.1]cyclophane π-prismands and the formation of their π-complexes with silver triflate (AgSO 3 CF 3 ). The lowest energy cyclophane conformations and their silver triflate π-complexes have been calculated with HF/3-21G* and B3LYP/3-21G* levels of theory. The nature of bonding in silver triflate π-complexes has been studied with natural bond orbital analysis (NBO). Energies of the calculated cyclophanes and complexes, together with the formation energies of those complexes, have also been discussed. The results have been compared to available X-ray crystal structures and also to results of the …
Complexation behaviour of hexadentate ligands possessing N2O4and N2O2S2cores: differential reactivity towards Co(ii), Ni(ii) and Zn(ii) salts and structures of the products
Reactions of divalent metal salts of Co, Ni and Zn with 1,2-di(salicylaldimino-o-phenylthio) ethane (H2L1) and 1,2-di(naphthaldimino-o-phenylthio) ethane (H2L2), having N2O2S2 cores, and 1,2-di(O-salicylaldimino-o-hydroxyphenyl) ethane (H2L3), having a N2O4 core, have been explored. Out of the three ligands and the nine products obtained from the corresponding reactions, two ligands and seven products were crystallographically characterized. However, all the ligands and the products were characterized by analytical and spectral methods. Reaction of H2L1 and H2L2 with Co(II) salts results in oxidative cleavage of the C-S bond to produce a Co(III) product bound to two dissimilar tridentate li…
Crystal structure of 4,6-O-ethylidene-N-(2-hydroxybenzylidene)-β-D-glucopyranosylamine
4,6-O-Ethylidene-N-(2-hydroxybenzylidene)-β-D-glucopyranosylamine was synthesized and characterized using analytical, spectral and single-crystal X-ray diffraction methods. The anomeric nature of the saccharide moiety was proposed based on 1H NMR studies and was confirmed by the crystal structure. The lattice structure of this compound was compared with that of its analogues.
Synthesis and characterization of 4,6-O-butylidene-N-(2-hydroxybenzylidene)-beta-D-glucopyranosylamine: crystal structures of 4,6-O-butylidene-alpha-D-glucopyranose, 4,6-O-butylidene-beta-D-glucopyranosylamine and 4,6-O-butylidene-N-(2-hydroxybenzylidene)-beta-D-glucopyranosylamine
4,6-O-Butylidene-N-(2-hydroxybenzylidene)-β-D-glucopyranosylamine was synthesized and characterized using analytical, spectral and single-crystal X-ray diffraction methods. 1H and 13C NMR studies showed the presence of the β-anomer, which has also been confirmed by the crystal structure. The molecular structure of this compound showed the presence of the tridentate ONO ligation-core. Both precursors, 4,6-O-butylidene-α-D-glucopyranose and 4,6-O-butylidene-β-D-glucopyranosylamine were characterized using single crystal X-ray diffraction. The α-anomeric nature of the former and β-anomeric nature of the latter were proposed based on 1H NMR studies and were confirmed by determining the crystal …
Synthesis of Hydroquinoid C- and O-Biphenyl Disaccharides by Chromium-Templated Benzannulation Reactions
Organometallic monosaccharides 6−10 containing a chromium styrylcarbene skeleton have been synthesized in quantitative yield from O-glycoside methylcarbene complexes 1−5 bearing diisopropylidene-protected glucose, mannose, galactose, or fructose in a trans-selective aldol condensation with benzaldehyde. These compounds undergo a chromium-templated benzannulation upon reaction with ethynyl glucoside to give diastereoisomeric mixtures of Cr(CO)3 complexes. The differences in their thermodynamic stability was exploited in a diastereoselective synthesis of hydroquinoid biphenyl disaccharides 12−16 in 67−88% yields. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Red and blue luminescent metallo-supramolecular coordination polymers assembled through π–π interactions †
The use of π-stacking interactions to control the aggregation of photo-active metal centres is explored through the design of bis(2,2′;6′,2′′-terpyridyl) metal complexes functionalised with biphenyl ‘tails’. Aryl–aryl interactions control the aggregation of the metal complexes into polymetallic arrays in the solid state. Cobalt(II), ruthenium(II), nickel(II), copper(II), zinc(II) and cadmium(II) bis-ligand complexes and a mixed ligand ruthenium(II) complex have been structurally characterised. The solid-state structures are dependent on which units dominate the π-stacking. For cobalt, ruthenium, nickel and copper, biphenylene–biphenylene interactions lead to linear rod-like arrays, while fo…
Synthesis and X-ray structure of amide-based macrocycles, catenanes and pretzelane
The syntheses and crystal structure studies of amide-based catenanes derived from m-phenylene diacrylic acid and 5-acetoxy isophthalic acid (17% and 3% yield of 4a and 4b resp.) and octalactam macrocycles (21% yield of 3) are described. Hydrogen bonding patterns play a key role in the formation of the different conformations of octalactam 3. The crystal structures of 3 reveal a number of hydrogen-bonding interactions between the macrocycle and two different solvent molecules, which are presumably responsible for the different conformations. Furthermore, we report the X-ray structure of a catenane, which was converted into a “pretzelane” by bridging two phenolic hydroxy groups with a p-xylyl…
Glycosylamines of 4,6-O-butylidene-α-d-glucopyranose: synthesis and characterization of glycosylamines, and the crystal structure of 4,6-O-butylidene-N-(o-chlorophenyl)-β-d-glucopyranosylamine
A total of nine glycosylamines of 4,6-O-butylidene-α-D-glucopyranose were synthesized using primary amines having various groups in their ortho- or para-positions. Among these, six are monoglycosylamines, including one primary glycosylamine, and three are bis-glycosylamines. All these compounds were characterized by 1H, 1H–1H COSY, 1H–13C COSY and 13C NMR spectroscopy and FTIR spectra. The FAB mass spectra provided the molecular weights of the products by exhibiting the corresponding molecular ion peaks. The crystal structure of 4,6-O-butylidene-N-(o-chlorophenyl)-β-D-glucopyranosylamine revealed the C-1 glycosylation, the β-anomeric nature, and the 4C1 chair conformation of the saccharide …
C–S bond cleavage by cobalt: synthesis, characterization and crystal structure determination of 1,2-di-(o-salicylaldiminophenylthio)ethane and its Co(III) product with C–S bond cleaved fragments
1,2-Di-(o-salicylaldiminophenylthio)ethane reacts with Co(II) salts to form a complex with oxidative cleavage of the C–S bond, to result in the formation of a Co(III) complex of the cleaved ligands.
Stereocontrolledα-Alkylation of Fully ProtectedL-Serine
Diastereoselective alkylation of the (2S,4S) and (2R,4S) diastereomers of 3-tert-butyl 4-methyl 2-tert-butyl-1,3-oxazolidine-3,4-dicarboxylate (1a/b) is reported. Formation of both diastereomers of these oxazolidines was achieved by changing the order of protection steps, and their relative and absolute configurations were determined by NOESY spectroscopy. The use of the bulky ring substituent tBu together with Boc as the N-protecting group led to the exclusive formation of only one alkylated diastereomer. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Mono-, di- and tri-nuclear Ni(II) complexes of N-, O-donor ligands: structural diversity and reactivity
A series of mono-, di- and tri-nuclear Ni(II) complexes of N, O-donating molecules possessing ---H2C---NH--- and ---HC=N--- moieties have been synthesized and characterized and the structures have been determined by single crystal X-ray diffraction. All these exhibited interesting molecular packing in their crystal lattices. Di-nuclear complexes were found to be cleaved in pyridine to result in mononuclear ones with additional coordinations being provided by pyridine. Di-nuclear complexes were found to form urea adducts as demonstrated based on absorption and vibrational studies.
First Crystallographic Investigation of Complexes of cis-VO2+, cis-MoO22+, and trans-UO22+ Species with Schiff-Base Molecules Derived from 4,6-O-Ethylidene-β-D-glucopyranosylamine
The interaction of Schiff-base ligands derived from 4,6-O-ethylidene-β-D-glucopyranosylamine with cis-VO 2 + , cis-MoO 2 2+ , and trans-UO 2 2+ species have been studied by isolating and characterizing the corresponding products. The structures of one complex of each type of species have been established by single-crystal X-ray diffraction analysis. In all the complexes, the saccharide moiety adopts a chair conformation and has a β-anomeric form. A gradual increase in coordination number (5, 6, and 7) and a gradual variation in the geometry (distorted trigonal-bipyramidal, distorted octahedral, and pentagonal-bipyramidal) are observed on going from the complexes of cis-VO 2 + (mononuclear) …
Mn(IV) and Co(III)-complexes of –OH-rich ligands possessing O2N, O3N and O4N cores: syntheses, characterization and crystal structures
Mn(IV) and Co(III) complexes of tridentate –OH–rich ligands possessing O2N, O3N and O4N donor sets were synthesized, characterized and their structures were established by single crystal X-ray diffraction, where the binding core is O4N2. In the structurally characterized complexes, the coordination geometry about the metal ion was found to be distorted octahedral.
Four-, five- and six-coordinated Zn-II complexes of OH-containing ligands: Syntheses, structure and reactivity
Four-, five- and six-coordinated complexes of Zn-II with OH-rich molecules possessing an ONO binding core were synthesized, characterized and their structures were established by single-crystal X-ray diffraction, The corresponding metal ion geometries were found to be distorted tetrahedral, square pyramidal and octahedral, respectively. The complexes exhibit interesting lattice structures such as layered and corrugated sheets owing to the presence of a number of weak intermolecular interactions. The five-coordinated, water-bound Zn-II complex was studied because of its putative hydrolysis property towards p-nitrophenyl acetate. (C) Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.
N-Glycosylamines of 4,6-O-ethylidene-alpha-D-glucopyranose: synthesis, characterisation and structure of CO2H, Cl and F ortho-substituted phenyl derivatives and metal ion complexes of the CO2H derivative
A saccharide based ligand suitable for metal binding (HLCOOH) has been synthesized using 4,6-O-ethylidene-alpha-D-glucopyranose (4,6-O-EGP) and anthranilic acid. A few analogous glycosylamines with chloro and fluoro ortho substitutions have also been synthesized and characterised. Complexes of HLCOOH with Na+, K+, Mg2+, Ca2+, Ba2+, Cd2+ and Hg2+ have been isolated and characterised fully. The crystal structures of 4,6-O-EGP, the chloro analogue of HLCOOH and the K+ complex of L-COOH are established. The anomeric nature, orientation of the binding core and the co-ordination aspects of K+ have been derived from these structures.
Synthesis, characterisation and crystal structures of Schiff bases from the reaction of 4,6-O-ethylidene-β-D-glucopyranosylamine with substituted salicylaldehydes
Multiple chemical modifications were carried out on D-glucose to result in the corresponding Schiff bases. Such modifications performed on D-glucose not only helped in increasing the solubility of the products in nonaqueous solvents, but also restricted the anomerisation of the saccharide moiety in solution. NMR study of the products revealed the presence of the β-anomeric form of the saccharide moiety in Me2SO solution. All the compounds were characterised by analytical and spectral methods. The literature is devoid of any crystal structures of saccharide–Schiff base combinations of the type reported in this paper. The crystal structures of these molecules exhibited a tridentate, ONO bindi…
CCDC 216935: Experimental Crystal Structure Determination
Related Article: Gudneppanavar Rajsekhar, Chebrolu P. Rao, Pauli Saarenketo, Kalle Nättinen, Kari Rissanen|2004|New J.Chem.|28|75|doi:10.1039/b305313j
CCDC 216932: Experimental Crystal Structure Determination
Related Article: Gudneppanavar Rajsekhar, Chebrolu P. Rao, Pauli Saarenketo, Kalle Nättinen, Kari Rissanen|2004|New J.Chem.|28|75|doi:10.1039/b305313j
CCDC 216934: Experimental Crystal Structure Determination
Related Article: Gudneppanavar Rajsekhar, Chebrolu P. Rao, Pauli Saarenketo, Kalle Nättinen, Kari Rissanen|2004|New J.Chem.|28|75|doi:10.1039/b305313j
CCDC 216933: Experimental Crystal Structure Determination
Related Article: Gudneppanavar Rajsekhar, Chebrolu P. Rao, Pauli Saarenketo, Kalle Nättinen, Kari Rissanen|2004|New J.Chem.|28|75|doi:10.1039/b305313j
CCDC 216931: Experimental Crystal Structure Determination
Related Article: Gudneppanavar Rajsekhar, Chebrolu P. Rao, Pauli Saarenketo, Kalle Nättinen, Kari Rissanen|2004|New J.Chem.|28|75|doi:10.1039/b305313j
CCDC 216930: Experimental Crystal Structure Determination
Related Article: Gudneppanavar Rajsekhar, Chebrolu P. Rao, Pauli Saarenketo, Kalle Nättinen, Kari Rissanen|2004|New J.Chem.|28|75|doi:10.1039/b305313j
CCDC 216929: Experimental Crystal Structure Determination
Related Article: Gudneppanavar Rajsekhar, Chebrolu P. Rao, Pauli Saarenketo, Kalle Nättinen, Kari Rissanen|2004|New J.Chem.|28|75|doi:10.1039/b305313j