Inorganic Chemistry Communications (v.7, #11)

Contents list (iii-viii).

The X-ray crystal structure of 2-tert-butylindolizine-3-selenoaldehyde by Pravat Bhattacharyya; Alexandra M.Z. Slawin; J. Derek Woollins (1171-1173).
2-tert-butylindolizine-3-selenoaldehyde is the first crystallographically uncomplexed characterised selenoaldehyde.The title compound is the first crystallographically characterised uncomplexed selenoaldehyde. The indolizine ring and selenocarbonyl group are coplanar with each other, the carbon–selenium bond length [1.808(5) Å] is essentially identical to those observed in selenoketones. The indolizine rings are stacked in the lattice with their planes parallel within the layers.
Keywords: Selenoaldehyde; X-ray crystallography; Selenium; Indolizine; Selenation;

The hetero-nuclear diselenolate complex 4 can be obtained from the reaction of 16-electron pseudo-aromatic cobalt complex 3 with W(CO)3(py)3 in the presence of BF3OEt2. The molecular structures of 3, 4 have been characterized by X-ray crystallographic analyses.The 16-electron half-sandwich cobalt complex Cp tt Co[Se2C2(B10H10)] (Cp tt  = η5-1,3- t Bu2C5H3) (3) has been synthesized by the reaction of [(THF)3LiSe2C2B10H10Li(THF)]2 (2) with Cp tt Co(CO)I2 (1). The hetero-binuclear complex Cp tt CoW(CO)2[Se2C2(B10H10)]2 (4) was obtained from the reaction of 3 with W(CO)3(py)3 in the presence of BF3  · Et2O. The molecular structures of 3 and 4 have been determined by X-ray crystallographic study.
Keywords: Cobalt; Tungsten; Half-sandwich complexes; Carborane;

Novel platinum complexes having chirality and free tertiary amine groups for multiple interactions with DNA by Mi Sook Seo; Youn Soo Sohn; Beom-Seok Yang; Wonwoo Nam; Kwan Mook Kim (1178-1180).
Chiral ethylenediamine ligands with free tertiary amine groups and their platinum complexes are synthesized. The platinum complexes have both chirality and additional DNA interacting groups. The hydrogen bonding interactions in the crystal structure lead to the dimerization of two platinum complexes having pocket-like cavity with chiral shapes.Chiral ethylenediamine ligands with free tertiary amine groups and their platinum complexes are synthesized. The platinum complexes have both chirality and additional DNA interacting groups. The hydrogen bonding interactions between chlorides and two tertiary amine groups in the crystal structure lead to the dimerization of two platinum complexes having pocket-like cavity with chiral shapes.
Keywords: Chiral amine; Platinum; Anticancer; Multiple DNA interaction;

A novel cadmium coordination polymer, [Cd1.5(bbta)1.5(NCS)3] n consists of the S-bonded octahedral Cd(SCN)6 and N-bonded octahedral Cd(NCS)3(bbta)3 and possesses unprecedented one-dimensional hetero-triple-stranded chain with alternate two [Cd(NCS)3] and one [Cd(bbta)3], which exhibits blue luminescent emission at room temperature in the solid state.A novel cadmium coordination polymer, [Cd1.5(bbta)1.5(NCS)3] n (1) (bbta = 1,2-bis(benzotriazol-1-yl)ethane), possessing the S-bonded octahedral Cd(SCN)6 and N-bonded octahedral Cd(NCS)3(bbta)3 and unprecedented one-dimensional hetero-triple-stranded chain with alternate two [Cd(NCS)3] and one [Cd(bbta)3], has been prepared, which exhibits blue luminescent emission at room temperature in the solid state.
Keywords: Coordination polymer; Luminescence; Cadmium; Bis(benzotriazole) ligand; Thiocyanate; Triple-stranded chain;

A new novel one-dimensional (1D) polymer involving both tetra- and hexacoordinate mercury(II) complex, [Hg3(4,4′-bipy)2(CH3COO)2(SCN)4] n , has been synthesized and characterized. The single-crystal X-ray data of the compound show the complex to be an infinite 1D helical chain, two of the Hg atoms are four-coordinate and one is six-coordinate.■■■.A new novel one-dimensional (1D) polymer involving both tetra- and hexacoordinate mercury(II) complex, [Hg3(4,4′-bipy)2(CH3COO)2(SCN)4] n , has been synthesized and characterized. The single-crystal X-ray data of the compound show the complex to be an infinite 1D helical chain, two of the Hg atoms are four-coordinate and one is six-coordinate.
Keywords: Helical chain polymer; Tetracoordinate mercury(II) complex; Hexacoordinate mercury(II) complex;

Synthetic models for active sites of reduced blue copper proteins: minimal geometric change between two oxidation states for fast self-exchange rate constants by Kiyoshi Fujisawa; Koyu Fujita; Tatsuya Takahashi; Nobumasa Kitajima; Yoshihiko Moro-oka; Yuki Matsunaga; Yoshitaro Miyashita; Ken-ichi Okamoto (1188-1190).
We have prepared two thiolato copper redox pairs ligated by HB ( 3 , 5 - i Prpz ) 3 - as models for blue copper proteins. The electron self-exchange rate constants of both Cu(II/I) redox pairs (1/2 and 3/4) and the activation parameters of Cu(II/I) redox pairs (1/2) were determined by the dynamic 1H NMR line-broadening techniques in (CD3)2CO.We have prepared two thiolato copper redox pairs ligated by HB ( 3 , 5 - i Prpz ) 3 - as models for blue copper proteins. The k ex value of the coordination number invariant Cu(II/I) couples is 51 times faster than that of the coordination number variant Cu(II/I) couples at −20 °C. We also discuss the electron-transfer process.
Keywords: Copper(I); Hydrotris(pyrazolyl)borate; Blue copper protein; Crystal structure; Model complex;

Synthesis and crystal structures of metal complexes with 4,5-imidazole-dicarboxylate chelates: self-assembled structures via NH⋯O=C intermolecular hydrogen bonds by Emi Shimizu; Mitsuru Kondo; Yumiko Fuwa; Ram. P. Sarker; Makoto Miyazawa; Masaru Ueno; Tetsuyoshi Naito; Kenji Maeda; Fumio Uchida (1191-1194).
New metal complexes with two imidazole-carboxylate sets were synthesized and structurally characterized. These complexes show unique hydrogen bonded self-assembled structures connected by NH⋯O=C and OH⋯O=C intermolecular hydrogen bonds.New metal complexes with two imidazole-carboxylate sets, [Zn(hmia)2(H2O)2] (hmia = 1-hydroxymethyl-4-imidazoleacetate) (1) and [M(Himdc)2(H2O)2] (imdc = 4,5-imidazoledicarboxylate) (M = Zn (2), Co (3), Cu (4)), were synthesized and structurally characterized. For all metal complexes, coordination of the two N–O sets of chelating ligands and two water molecules produces a distorted (13) and an elongated (4) octahedral coordination center, in which these monomeric units are connected by various intermolecular hydrogen bonds.
Keywords: Crystal structure; Imidazole complex; Hydrogen bonded assembly; Coordination network;

The monooxo molybdenum(VI) complexes, MoO(cat)L, where L2−  = dianion of N-4-diethylaminosalicylidene-N′-4-nitrobenzoyl hydrazine and cat2−  = catecholate, 4-methylcatecholate, 3,5-di-tert-butylcatecholate, or 4-nitrocatecholate have been prepared. Based on spectroscopic data and structure of similar complexes, a distorted octahedral structure for the MoO(cat)L complexes with four oxygen donor atoms from ligands L2− and cat2− defining the equatorial plane and the multiply bonded oxo ligand and the azomethine nitrogen donor defining the two trans vertices of the octahedron has been suggested.Preparation and spectroscopic characterization are reported for monooxo molybdenum(VI) complexes, MoO(cat)L, where L2−  = dianion of N-4-diethylaminosalicylidene-N′-4-nitrobenzoyl hydrazine and cat2−  = catecholate (Cat2−), 4-methylcatecholate (Mecat2−), 3,5-di-tert-butylcatecholate (DTBcat2−), or 4-nitrocatecholate (NO2cat2−). The compounds were prepared by replacement of an oxo group on MoO2L with a catechol. The MoO(cat)L complexes exhibit a Mo=O stretching vibration (ν Mo=O) at 935–938 cm−1 and a series of five absorptions in the UV–Vis region including a long wave-length band at 655–658 nm which is attributed to cat → Mo charge transfer. The 1H and 13C NMR data are reported and found to be consistent with the formation of monomeric MoO(cat)L compounds.
Keywords: Mo(VI) complexes; Catecholate complexes; Spectroscopic properties; Six-coordinate complexes;

A desamidination process forming a novel guanidine derivative during the complexation between copper(II) and guanidinoacetic acid by Jussara L. de Miranda; Judith Felcman; Otavio Versiane; Marcelo H. Herbst (1198-1201).
A novel trianionic disubstituted guanidine, (1 N-carboxymethylguanidino)hydroxyacetic acid-C5H6N3O5), oag3−, has been formed through a desamidination process occurred during copper(II) complexation with guanidinoacetic acid, C3H7N3O2 (Gaa), which produced [Cu2(oag)(Gaa)(H2O)]NO3  · 2H2O (1).A novel trianionic disubstituted guanidine, (1 N-carboxymethylguanidino)hydroxyacetic acid-C5H6N3O5), oag3−, has been formed through a desamidination process occurred during copper(II) complexation with guanidinoacetic acid, C3H7N3O2 (Gaa), which produced [Cu2(oag)(Gaa)(H2O)]NO3  · 2H2O (1). A proposal mechanism of formation of 1 is presented based on the low temperature electron paramagnetic resonance and previous potentiometric studies, which have indicated the presence of CuH2Gaa as the precursor species.
Keywords: Guanidinoacetic acid; Copper(II); Transamidination;

The synthesis of molybdenum complex with novel P(OH)3 ligand is achieved by the one-pot reaction of Mo(CO)6 with HP(O)(OEt)2 and water. The structure of product was determined by X-ray analysis.The synthesis of molybdenum complex with novel P(OH)3 ligand is achieved by the one-pot reaction of Mo(CO)6 with HP(O)(OEt)2 and water. The structure of product was determined by X-ray analysis.
Keywords: Phosphorous acid ligand; Molybdenum hexacarbonyl; (CO)5MoP(OH)3 compound; H-phosphonate; X-ray structure;

A horse-like picture drawn by hydrothermal reactions, and formed through the linkage of [ Cu 8 I Br 12 ] 4 - chains by the tetranuclear copper-hydroxo clusters [Cu4(OH)4(phen)4]4+ as the bridges.The hydrothermal reaction of CuBr2, CuBr and 1,10-phen gives birth to a 2-D coordination polymer [ Cu 4 II ( OH ) 4 (1,10-phen)4][ Cu 8 I Br 12 ] (1), consisting of the unique [ Cu 8 I Br 12 ] 4 - chains linked by the stepped-cubane copper(II)-hydroxo clusters [ Cu 4 II ( OH ) 4 ( phen ) 4 ] 4 + as the bridges. Compound 1 possesses high thermal stable. The non-linear optical property of 1 was studied, and the compound exhibits the reverse saturable absorption (α 2  = 0.80 × 10−11 m W−1) and self-defocusing performance (n 2  = −1.55 × 10−18 m2  W−1).
Keywords: Copper halide; Stepped cubane; Non-linear optics; Hydrothermal synthesis;

Redox reactions via outer sphere charge transfer complexation: the interaction of ferrocenes with σ- and π-type acceptors by H.M.A. Salman; M.R. Mahmoud; M.H.M. Abou-El-Wafa; U.M. Rabie; R.H. Crabtree (1209-1212).
Interactions of ferrocenes with iodine as a typical σ-acceptor or with DDQ and CHL as π-acceptors always led to the oxidation of these ferrocenes to the corresponding ferricinium salts. This type of oxidation is proposed to occur via initial formation of outer sphere charge transfer complexes.Decamethylferrocene Cp 2 ∗ Fe , ferrocene (Cp2Fe), 1,1′-dimethylferrocene. ((MeCp)2Fe), and 1,2-diferrocenylethane (Fc2C2H4) were studied as donors for charge transfer complexation with iodine (I2) as a typical σ-type CT acceptor and with 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), and p-chloranil (CHL) as typical π-type CT acceptors. Oxidation of the ferrocenes to the corresponding ferricinium salts is proposed to occur via initial formation of outer sphere charge transfer complexes. UV–Vis spectra for the mixtures of any of the ferrocene donors with I2 or DDQ in CH2Cl2 showed the characteristic bands of the triiodide ion, I 3 - and the DDQ •- anion radical. With CHL, the same behavior occurred only for Cp 2 ∗ Fe to give Cp 2 ∗ Fe + and CHL •- radicals. Elemental analyses of the isolated solid complexes indicated the formation of [ferrocene]I3 for ferrocenes and I2, except for (Fc2C2H4) which gave [(Fc2C2H4)]I5. Ferrocene–DDQ complexes were 1:1 except for (MeCp)2Fe and (Fc2C2H4) which gave 1:2 complexes. By using n-hexane as a non-polar solvent instead of CH2Cl2, the CT band of the Cp 2 ∗ Fe adduct has been observed and the formation constant for this CT complexation was found to be 3900 (±500) dm3  mol−1.
Keywords: Ferrocenes; Redox reactions; CT complexes; IR; UV–Vis spectroscopy;

The synthesis of triethylene glycol methyl ether end-grafted first and second generation carbosilane dendrimers is described. Their reaction behaviour towards K+ and Na+ is reported.The synthesis of first and second generation carbosilane dendrimers with end-grafted triethylene glycol methyl ether units is reported. The reaction chemistry of Me2Si(CH2CH2CH2SiMe2CH2(CH2CH2O)4Me)2 (4), Si(CH2CH2CH2SiMe2CH2(CH2CH2O)4Me)4 (5) and Si(CH2CH2CH2SiMe(CH2CH2CH2SiMe2CH2(CH2CH2O)4Me)2)4 (7) towards alkali metal ions is described. ESI-TOF studies reveal that in 4 one, in 5 two and in 7 up to four metal ions can be trapped, which enables 4, 5 and 7 as possible ionophores for chemical sensors.
Keywords: Carbosilane dendrimers; Chemical sensors; Hydrosilylation; Metallodendrimers; Triethylene glycol ether;

The sandwich-type units [Cd4(H2O)2(2,2′- bpy)2]Cd[Mo6O12(OH)3(PO4)2(HPO4)2]2 are connected by octahedrally coordinated cadmium into a chain {[Cd4]Cd[Mo6P4]2} n . The coordination cations [Mo2O4(2,2′-bpy)2]2+ link to the neighboring chains, forming a 3D open framework structure.The title organic–inorganic hybrid cadmium molybdenum(V) phosphate has been hydrothermally synthesized. The sandwich-type units [Cd4(H2O)2(2,2′-bpy)2]Cd[Mo6O12(OH)3(PO4)2(HPO4)2]2 ([Cd4]Cd[Mo6P4]2) are connected by octahedrally coordinated cadmium into a chain {[Cd4]Cd[Mo6P4]2} n . The coordination cations [Mo2O4(2,2′-bpy)2]2+ link to the neighboring chains, forming a 3D open framework structure. The title complex represents the first sandwich-type cadmium hetereopolymolybdate with 3D network.
Keywords: Heteropolyanion; Cadmium; 3D network; Crystal structure; Hydrothermal synthesis;

Magnetic coupling switch by means of host–guest chemistry in a polyether side-arm by Takashi Nakabayashi; Takayuki Ishida; Takashi Nogami (1221-1224).
Complexation from the polyether ligand (LH2), Ni(CH3CO2)2, and Ba(CF3SO3)2 gave BaNiL·2CF3SO3, which showed ferromagnetic coupling ascribable to the dimer structure determined by means of X-ray crystallographic analysis. After removal of Ba2+ by treatment with guanidinium sulfate, NiL was isolated as an empty host, which did not show ferromagnetic coupling.Complexation from the polyether ligand (LH2), Ni(CH3CO2)2, and Ba(CF3SO3)2 gave BaNiL·2CF3SO3, which showed ferromagnetic coupling ascribable to the dimer structure determined by means of X-ray crystallographic analysis. After removal of Ba2+ by treatment with guanidinium sulfate, NiL was isolated as an empty host, which did not show ferromagnetic coupling.
Keywords: Ferromagnetic interaction; Supramolecular chemistry; Crown-ether;

The synthesis, characterization, and the result of the X-ray crystal structure determination of trans - [ Rh ( NO ) ( NO 2 ) 2 ( Bu 2 t PH ) 2 ] is presented.A convenient synthesis of trans - [ Rh ( NO ) ( NO 2 ) 2 ( Bu 2 t PH ) 2 ] (1) from rhodium(III) chloride trihydrate, sodium nitrite, and Bu 2 t PH in ethanolic solution is described. The crystal and molecular structure of 1 was determined by a single-crystal X-ray diffraction study.
Keywords: Rhodium; Nitrite; Nitric oxide; Secondary phosphines; Crystal structure;

A new chiral copper(II) complex of N,N,N′-tris(2-pyridylmethyl)-S-(aminomethyl)piperidine =  S-pipda has been synthesised and structurally characterized; the compound has a square-based pyramidal structure, interacting with an oxygen atom of perchlorate ion with a Cu⋯O distance of 3.539(10) Å.The synthesis of a new chiral pentadentate polypyridylmethyl ligand derived from S-(2-aminomethyl)piperidine, N,N,N′-tris(2-pyridylmethyl)-S-2-(aminomethyl)piperdine, S-P3pipda (1), is described. The physicochemical properties of its copper(II) complex were examined by UV–Vis and CD spectroscopies, X-ray crystallography, and electrochemistry.
Keywords: Copper(II) complex; 1R,2R-diaminocyclohexane; Optical active; Crystal structure;

This work reports the porphyrin ring current effect as a tool for the investigation of coordinated pyridine and DMF ligands and X-ray crystals of the two five-coordinate and mononuclear cadmium (II) porphyrin complexes Cd[(p-Cl)4tpp](py) (5) and Cd[(p-Cl)4tpp](DMF) (6) with square-based pyramidal geometries.The crystal structures of [meso-tetra-(p-chlorophenyl)porphyrinato](pyridine)cadmium(II) pyridine solvate Cd[(p-Cl)4tpp](py) · py [or 5  · py], and [meso-tetra-(p-chlorophenyl)porphyrinato](dimethylformamide)cadmium(II) toluene solvate Cd[(p-Cl)4tpp](DMF) · toluene [or 6  · toluene] were determined. The ring current effect provides a complementary method for the investigation of coordinated pyridine and DMF ligand in complexes 5 and 6, respectively.
Keywords: Crystal structures; Cadmium meso-tetra-(p-chlorophenyl)porphyrin complexes; Ring current effect; Five-coordinate square-based pyramidal geometries;

Spectroscopic and electrochemical characterization of solutions and films of a new redox couple: Co(II)/Co(III) N-confused porphyrin by I. Zilbermann; E. Maimon; R. Ydgar; A.I. Shames; E. Korin; L. Soifer; A. Bettelheim (1238-1241).
The films of Co(II) N-confused tetraphenylporphyrin are stable in aqueous base, insensitive to air and show a relatively high oxidation potential attributed to the Co(II)/Co(III)NCTPP couple: 0.025 V vs. Ag/AgCl/KCl (satd.) in 1 M NaOH.Co(II) ion was introduced in N-confused tetraphenylporphyrin (NCTPP) as evidenced by ESR and UV–Vis spectroscopy as well as electrochemical methods. The Co(II)NCTPP complex shows a typical ESR spectrum of a high spin 3d7 Co(II) ion, Soret bands at 460 and 445 nm in CH2Cl2 and CH3CN, respectively, and oxidation potential of +0.55 V vs. Ag/AgCl/KCl (satd.). Adsorbed films of Co(II)NCTPP on glassy carbon electrodes are stable and show reversible redox waves in aqueous basic solutions attributed to the Co(II)/Co(III)NCTPP couple with E 1/2  = +0.025 V at pH 14. It is also shown that NCTPP can be electropolymerized and the films readily metallate with Co(II) ions.
Keywords: N-confused porphyrins; Co(II) complex; Spectroscopy; Redox; Electropolymerization;

A chair-piperazine bridged N,N-dimethylformamide coordinated dicopper(II/II) complex [ Cu 2 II ( μ - L ) ( DMF ) 2 ] ( ClO 4 ) 2 (DMF =  N,N-dimethylformamide) (2) was crystallized from the 3-phenyl substituted imidazolidine and ethoxy bridged [ Cu 2 II ( μ - L ′ ) ( μ - OEt ) ] ( ClO 4 ) (1) complex synthesized from the reaction of Cu(ClO4)2  · 6H2O, EtONa and ligand H2L′ [2-(2′-phenyl)-1,3-bis{3′-aza-4′-(2″-hydroxyphenyl)-prop-4-en-1′-yl}-1,3 imidazolidine].First N,N-dimethylformamide coordinated chair-piperazine bridged dicopper(II/II) complex [ Cu 2 II ( μ - L ) ( DMF ) 2 ] ( ClO 4 ) 2 was obtained following a solution transformation of the heterocyclic imidazolidine spacer of the new μ-bis(tridentate) ligand (H2L′).
Keywords: Bis(tridentate); Imidazolidine ring; Schiff base; Dicopper complex; Crystal structure; Magnetic properties;