Inorganic Chemistry Communications (v.3, #3)

The first near regular trigonal bipyramid [Cu(phen)2Cl]+ type compound has been synthesized, which possesses a dimer structure constituted through C–H⋯Cl hydrogen bondings and π–π interactions between phen rings.
Keywords: Crystal structures; Copper(II) complexes; Hydrogen bonding; π–π Stacking;

The reaction between Nb2S4aq 4+ and K3nta (nta is nitrilotriacetate, N(CH2COO)3 3−), followed by slow oxidation in air, leads to complete desulfurisation of the starting Nb(IV) complex, oxidation of Nb(IV) to Nb(V) and crystallisation of the title complex with hitherto unknown [Nb2(O)2(μ-OH)2]4+ core. The crystal structure of the product has been determined.
Keywords: Niobium complexes; Nitrilotriacetates; Polynuclear complexes; Crystal structures;

Hydrothermal synthesis of [Ba3Cl2][Sn3O4(OH)8], a compound with alternating ionic and covalent layers by Mingmei Wu* ; Xiulin Li; Guoping Shen; Alvin Siu; Samuel M.-F Lo; Herman H.-Y Sung; Ian D Williams* (99-101).
[Ba3Cl2][Sn3O4(OH)8] (1), is formed through hydrothermal synthesis in the BaCl2/SnCl4 system. 1 is orthorhombic, Pnma, a=7.836(2), b=18.350(4), c=10.258(2) Å, V=1475 Å3 and composed of alternating layers of covalent stannate and ionic barium chloride components. The ‘covalent’ layers consist of hydroxy stannate trimers [Sn3O4(OH)8], connected through μ3-O to other units forming puckered 2-D sheets. These sheets are then intercalated by the barium and chloride ions, which have a complex set of ionic contacts.
Keywords: Hydrothermal synthesis; Tin oxides; Layer compounds; Intercalation;

The new heterobimetallic complex [(CO)4Mo(μ-Cl)3Mo(SnCl3)(CO)3] (1) has been prepared by photochemical reaction of Mo(CO)6 with SnCl4. The structure of complex 1 was established by X-ray crystallography. The basic structural units of 1 are two seven-coordinate molybdenum atoms, which are linked by three chlorine atoms occupying a bridging position between the molybdenum atoms. The mononuclear seven-coordinate complex [MoCl(SnCl3)(CO)3(NCMe)2] (2) is formed by reaction of [(CO)4Mo(μ-Cl)3Mo(SnCl3)(CO)3] with acetonitrile. Treatment of compound 2 with propionitrile affords [MoCl(SnCl3)(CO)3(NCEt)2] (3). A single-crystal X-ray diffraction study of the complex [MoCl(SnCl3)(CO)3(NCEt)2] (3) showed that the environment of the molybdenum atom is a distorted capped octahedron with the SnCl3 anionic ligand occupying the unique capping position above an octahedral face defined by the bridging chlorine and two carbonyl groups.
Keywords: Molybdenum(II) complexes; Tin(II) complexes; Crystal structures; Seven-coordinate complexes;

Synthesis and X-ray crystal structure of monomeric lanthanocene aryloxide complexes with a tridentate Schiff base ligand by Muhammad Yousaf; Qiancai Liu; Jiling Huang; Yanlong Qian* ; Albert Sun-Chi Chan* (105-106).
Reaction of tris(cyclopentadienyl)lanthanide with the tridentate Schiff base N-1-(ortho-methoxyphenyl)salicylideneamine in THF at room temperature affords the isolation of monomeric lanthanocene Schiff base complexes, (η 5-C5H5)2Ln (OC14H13NO) (Ln=Sm (1), Er (2), Dy (3), Y (4)), which have been characterized by elemental analysis and mass spectra. The X-ray determination of 1 indicates that the complex is monomeric in which the metal center is coordinatively saturated by two cyclopentadienyl rings and two oxygens and one nitrogen from the Schiff base ligand. The average Sm–C bond distance is 2.723(7) Å, while those of the metal center to the Schiff base oxygens and nitrogen atoms are 2.232(4), 2.572(4) and 2.534(4) Å, respectively.
Keywords: Lanthanocene; Schiff base; Synthesis; Crystal structures;

The reaction of 2-[((2-(4-imidazoyl)ethyl)amino)carbonyl]-6-[((2-amino-2-methylpropyl)amino)methyl]pyridine (L) with ZnII(NO3)2·6H2O has afforded a novel one-dimensional polymeric ZnII complex, (ZnII(L)(NO3)2) n (2). Complex 2 crystallizes in the space group P21/n with a=8.955(3), b=13.216(3), c=18.941(3) Å, β=103.39(2)°, V=2180.6(10) Å3, and Z=4. The geometry of each ZnII is approximately a trigonal bipyramid: three nitrogens and one oxygen of the amide group are coordinated to the zinc while the fifth site is occupied by the imidazole nitrogen of a neighboring unit.
Keywords: Zinc complexes; Bleomycin; Crystal structures; NMR;

Study of Cu2+ mediated oxidation of thiosemicarbazide, thiocarbohydrazide and thiourea by Shyamal K. Chattopadhyay; Thomas C.W. Mak (111-113).
Thiosemicarbazide, thiocarbohydrazide and thiourea undergo Cu2+ mediated oxidation in DMF in the presence of 2,2′-bipyridine (bpy) to produce cis-[Cu(bpy)(H2O)2SO4].
Keywords: Thiosemicarbazide; Thiourea; Cu2+ mediated oxidation;

A new one-dimensional organic/inorganic hybrid, (1,10-phen)2Mo3O9 (1), has been prepared by a hydrothermal method using (nBu4N)2Mo6O19 and 1,10-phenanthroline and structurally characterized. The compound crystallizes in the monoclinic space group C2 with a=14.9794(3), b=9.7102(2), c=10.3280(2) Å, β=118.0949(6)°, V=1325.23(5) Å3, Z=2, and R1=0.0335, wR2=0.0877. The structure consists of a chain of corner-sharing {MoO4N2} octahedra and {MoO4} tetrahedra that alternate such that each {MoO4N2} octahedron corner-shares with another such octahedron and an {MoO4} tetrahedron; consequently, each {MoO4} tetrahedron corner-shares with two {MoO4N2} octahedra. The chains in the crystal are parallel to each other along both b and c axes and form pseudo-two-dimensional channels through the hydrogen bonds along both a and b axes.
Keywords: Hydrothermal synthesis; Isopolymolybdate; Inorganic/organic hybrid; Crystal structures;

[Ni4(S2C7H10)4], the first tetranuclear cyclic nickel(II) complex with bifunctional thiolate ligands, is described. It has been obtained by oxidation of the mononuclear precursor complex [Ni(S2C7H10)2]2−.
Keywords: Crystal structures; Nickel complexes; Thiolate complexes;

Synthesis, spectral properties and crystal structures of copper(II) isonicotinates, first example of uncoordinated isonicotinates by Peter Segl’a; Martina Palicová; Marian Koman; Dušan Mikloš; Milan Melnı́k (120-125).
The syntheses and crystal structures of solid complexes [Cu(en)2(H2O)2](isonic)2 and [Cu(isonic)(dien)(H2O)1.5]·0.5SO4·2.5H2O (en=ethylenediamine; dien=diethylenetriamine; isonic=isonicotinate) are reported. The crystal structure of [Cu(en)2(H2O)2](isonic)2 comprises [Cu(en)2(H2O)2]2+ cations and isonicotinate anions. To our knowledge, this is the first example which contains uncoordinated isonicotinate anions. The crystal structure of [Cu(isonic)(dien)(H2O)1.5]·0.5SO4·2.5H2O contains two cations [Cu(isonic)(dien)(H2O)]+ and [Cu(isonic)(dien)(H2O)2]+, sulfate anions and water molecules. The SO4 2− anion takes part in an extensive system of hydrogen bonds including both uncoordinated and partially also coordinated water molecules. Based on the molecular structure the electronic, IR and ESR spectra are discussed.
Keywords: Ethylenediamine; Diethylenetriamine; Crystal structures; Copper(II) complexes; Isonicotinate complexes;

Reaction of the complex [Cp*(PPh3)2RuCl] with excess HSiMe2Cl yielded the dihydride silyl derivative [Cp*(PPh3)RuH2(SiClMe2)] (2) which has been crystallographically characterised. Comparison of the structure of 2 with that of the previously reported complex [Cp*(PPri 3)RuH2(SiClHMes)] (1) revealed that the latter complex has non-classical interligand hypervalent interactions between the silyl and one of the hydride ligands.
Keywords: Hypervalent interactions; Ruthenium complexes; Silicon complexes; Hydride complexes;

Mesolamellar molybdenum sulfides with intercalated cetyltrimethylammonium cations by Ying Wang; Jie-Sheng Chen; Ming-Hong Xin; Ru-Ren Xu (129-131).
Two mesolamellar molybdenum sulfides (designated MoS-L-A and MoS-L-B) with intercalated cetyltrimethylammonium surfactant cations have been prepared at room temperature and under mild hydrothermal conditions, respectively. Powder X-ray diffraction and transmission electron microscopy reveal that the materials have interlayer distances of 34 and 28 Å. The oxidation state of Mo in the compounds is +4 whereas the sulfur exists as S2−, S2 and S2 2− species. The inorganic layers of MoS-L-A and MoS-L-B are composed of negatively charged molybdenum sulfide with the negative charges being balanced by the cetyltrimethylammonium cations intercalated between the inorganic layers.
Keywords: Mesolamellar; Molybdenum sulfide; Synthesis; Characterization;

Acyclic imines were hydrogenated with rhodium and iridium complexes modified with chiral phosphite and phosphonite ligands. Iridium neutral precursors provided better activities than the analogous cationic complexes, although enantioselectivity was not induced.
Keywords: Rhodium complexes; Iridium complexes; Chiral phosphite complexes; Chiral phosphonite complexes; Monophosphonite ligand; Hydrogenation; Imines;

The reaction of (t-Bu2C5H3)2HfCl2 (1) with vinyllithium yield ivory coloured crystals identified as (t-Bu2C5H3)2Hf(CHCH2)2 (2). The X-ray structure analysis of 2 shows the presence of the divinyl complex, whereby one of the vinyl groups is partially replaced by chlorine (25%).
Keywords: Hafnium complexes; Vinyl complexes; Crystal structures;

The reaction of 1,3-propanedithiol with [Ru3(CO)10(μ-dppe)] (2) at 66°C afforded the thiolate complexes [(μ-H)Ru3(CO)8{μ-S(CH2)3SH}(μ-dppe)] (6) and [Ru3(CO)52-S(CH2)3S}22-dppe)] (7) in 25 and 23% yields respectively. Compound 6 is formed by simple oxidative addition of one of the S–H bonds of 1,3-propanedithiol while the structurally unique 7 consists of an open triruthenium cluster with four terminal and one asymmetrically bridged carbonyl groups, two doubly bridged propanedithiolate ligands and a chelating dppe ligand.
Keywords: Crystal structures; Ruthenium complexes; Diphosphine complexes; Dithiolate complexes; Cluster complexes;

The complex Ni0(PPh3)2(CO)2 shows a red photoluminescence (λ max=650 nm) at r.t. It is suggested that this emission originates from a Ni0→PPh3 metal-to-ligand charge transfer triplet.
Keywords: Photoluminescence; Charge transfer; Nickel(0) complexes; Carbonyl complexes;

Cleavage of the C–N bond of a peptide group by a copper(II)-peroxide adduct with an η 1-coordination mode by Satoshi Nishino; Mami Kunita; Yoshiyuki Kani; Shigeru Ohba; Hideaki Matsushima; Tadashi Tokii; Yuzo Nishida (145-148).
We have obtained clear evidence that a copper(II)-peroxide adduct with an η 1-coordination mode can cleave the C–N bond of a peptide group and hydroxylate the alkyl group nearby; this may provide helpful information for elucidation of the reaction mechanism of PAM, peptidylglycine α-amidating monooxygenase.
Keywords: Cleavage of protein; Copper(II)-peroxide adduct; η 1-Coordination mode; Model reaction for PAM enzyme;