Inorganic Chemistry Communications (v.3, #12)

Dinitrogen bonding modes to molecular nickel(II) halides: a matrix isolation IR and DFT study by Adam J Bridgeman; Owen M Wilkin; Nigel A Young (681-684).
A combination of matrix isolation IR and DFT studies has shown that when monomeric nickel dihalides ( NiX 2,  X=Cl,  Br ) are condensed in solid nitrogen matrices the initial species formed are NiX2⋯(N2) n with a physisorbed type of interaction between the nitrogen and the nickel centre. These can be converted by photolysis into pseudo-tetrahedral NiX2(η 1-N2)2 moieties with end-on bonded dinitrogen ligands in a chemisorbed type of interaction, but only if the matrix is deposited at less than 10 K. On warming to ca. 20 K the chemisorbed species revert to the physisorbed state. For CoBr2 only very very weak new bands were observed after photolysis in a nitrogen matrix, and no new bands were observed after photolysis for NiF2, FeBr2 or ZnBr2 in nitrogen matrices.
Keywords: Nickel bromide; Nickel chloride; Matrix isolation; Dinitrogen complexes; DFT calculations;

The metal-chain complexes (X)[Os(CO)3(CNBut)]3Mn(CO)5 (X=Cl, Br, I) by Faming Jiang; Hilary A. Jenkins; Glenn P.A. Yap; Roland K. Pomeroy (685-689).
In what is a new metal-chain forming reaction, (X)[Os(CO)3(CNBut)]3Mn(CO)5 (X=Cl, Br, I) complexes have been prepared by the successive addition of Os(CO)4(CNBut) to Mn(CO)5(X) in hexane. The crystal structure of the iodo derivative reveals it to contain an approximately linear Os3 Mn chain of metal atoms.
Keywords: Tetranuclear Os/Mn complex; OsMn bond; Crystal structure; 13C NMR spectrum;

A tetranuclear cadmium(II) complex of 2(2-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1 H-imidazol-1-oxy 3-N-oxide (NIToPy) with CdCl2,[Cd4Cl8(NIToPy)4], has been structurally and magnetically characterized. The structure is based on a novel chloro-bridged tetranuclear cadmium quasi-cubane cluster, in which each cadmium atom is chelated by one NIToPy radical, and coordinated with four bridging chlorine atoms. The temperature dependence of the magnetic susceptibility measurements shows a weak ferromagnetic coupling between the radicals. An excellent simulation of the experimental data with the prism type four spins Hamiltonian H=−2J 1(S 1 S 2+S 2 S 3+S 3 S 4+S 1 S 4)−2J 2 S 2 S 4 obtained the parameters: J1=1.12  cm −1, J2=−0.20  cm −1 , and g=2.04.
Keywords: Cadmium compound; Nitronyl nitroxide; Crystal structure; Magnetic properties;

A three-dimensional coordination network of [AgL(MeCN)] (L=4,5-dichloro-2-cyano-3,6-dione-1,4-cyclohexen-1-ol anion) has been synthesized and crystallographically characterized. The silver(I) atom in the title compound is coordinated by two chelating oxygen atoms from one L ligand and two nitrogen atoms from an MeCN ligand and a cyano group of another L ligand at the equatorial positions, and by one oxygen atom from the third L ligand at the apical direction, completing a distorted square pyramidal geometry. Each L ligand acts in μ 4-mode to link three silver(I) atoms into a three-dimensional network, which shows room-temperature emission upon photoexcitation at 350 nm.
Keywords: Silver(I); Coordination polymer; Structure; Photoluminescence;

Hydrothermal synthesis and crystal structure of the first layered iron molybdate KH3FeII 2MoVI 2O10 by Li-Juan Zhang; Yun-Shan Zhou; Jing-Lin Zuo; Zhi Yu; Hong-Kun Fun; Ibrahim Abdul; Xiao-Zeng You (697-699).
The layered iron molybdate compound, KH3FeII 2MoVI 2O10, has been hydrothermally synthesized and structurally characterized for the first time. The compound crystallizes in monoclinic space group C2/m with a=9.6448(7), b=6.5946(4), c=7.8563(5)  A ̊ , β=115.950(1)°, V=449.31(5)  A ̊ 3 , Z=2, and R1=0.0313, wR2=0.0817. The structure consists of FeO6 octahedra and MoO4 tetrahedra. Each FeO6 octahedron shares edges with its adjacent FeO6 octahedra and leads to a chain consisting of edge-sharing FeO6 octahedron. The parallel chains are linked through MoO4 tetrahedra. Each MoO4 tetrahedron shares corners with two adjacent Fe octahedra through the vertical oxygen atoms of each FeO6, and two adjacent Fe octahedra through an oxygen atom bridging the two adjacent Fe octahedra of its neighboring chain, respectively. A ∞-like 2D layers and pseudo-six-side tunnels are formed and the potassium cations are located in the pseudo-channels.
Keywords: Hydrothermal synthesis; Crystal structure; Iron molybdate; Layer;

The X-ray structure analysis of [Et2In(μ,λ-O2C)–C6H4–2–NH2] n (1) reveals an extended one-dimensional chain comprised of an array of five-coordinate indium centers. The chain unit repeated along two-fold screw axis is defined by the diethylindium moiety chelated asymmetrically by the carboxylate group with one of the two carboxylate oxygens acting as bridge to the next indium center in the chain. The NH2 group does not participate in the coordination of the metal center but is involved in an intermolecular hydrogen bond.
Keywords: Crystal structures; Indium carboxylates; Donor–acceptor bond; Hydrogen bond;

Reaction between cis-[Pt(NH3)2(H2O)2]2+ and (2-methylsulfanyl)phenyl phosphonic acid (H2mspp) did not yield the expected cis-diammine [(2-methylsulfanylphenyl)phosphonato]platinum(II) but the dimeric compound [{Pt(mspp)(NH3)}2]·6H2O in which the dianionic mspp2− ligand acts both as chelator and bridging ligand. Thus, the high trans-effect of the sulfanyl group apparently leads to elimination of one NH3 ligand. An X-ray crystal structure analysis of the dimeric complex is reported.
Keywords: Platinum complexes; 2-Methylsulfanylphenyl phosphonic acid; X-ray diffractometry;

Polylinked adamantanoid structure of Cd(SePh)2 by K.S. Anjali; Jagadese J. Vittal (708-710).
The solid state structure of Cd(SePh)2 is built up of adamantanoid cages linked through four vertices to form a three-dimensional nonmolecular polyadamantanoid or superdiamondoid network, 3 [(μ-SePh)6Cd4(μ-SePh)4/2].
Keywords: Adamantane-like compounds; Cadmium(II); Selenolate; Polyadamantanoids;

Rhodium catalysed hydroformylation using diphenylphosphine functionalised carbosilane dendrimers by Debby de Groot; Peter G. Emmerink; Caroline Coucke; Joost N.H. Reek; Paul C.J. Kamer; Piet W.N.M. van Leeuwen (711-713).
Diphenylphosphine functionalised carbosilane dendrimers Si((CH2) n Si(CH3)2(CH2PPh2))4 (n=2,3; generation 1–3) and Si((CH2) n Si(CH3)(CH2PPh2)2)4 (n=2,3; generation 1–2) have been synthesised and used as ligands in the rhodium catalysed hydroformylation of 1-octene. The activity of the system depends on the size and flexibility of the dendrimeric ligand.
Keywords: Carbosilane dendrimers; Hydroformylation; Phosphines; Rhodium; Catalysis;

Dendrimer-bound tertiary phosphines for alkene hydroformylation by Loı̈c Ropartz; Russell E. Morris; Gary P. Schwarz; Douglas F. Foster; David J. Cole-Hamilton (714-717).
Dendrimer-based phosphines with 8, 24 and 72 PR2 arms (R=Me, Et, hexyl, Cy or Ph) based on polyhedral oligomeric silsesquioxane (POSS) cores have been synthesized and shown to catalyse hydroformylation reactions, in some cases with higher linear:branched product ratio (1:b) than their monomeric analogues.
Keywords: Dendrimer; Phosphine; Rhodium; Hydroformylation; Alcohols;

A linear trinuclear mixed oxidation state cobalt(III/II/III) complex with pyrazolate bridging ligands by Timothy S. Billson; Jonathan D. Crane; O. Danny Fox; Sarah L. Heath (718-720).
A linear, trinuclear cobalt complex with pyrazolate bridges has been prepared and structurally characterised. The outer cobalt centre is low spin, octahedral cobalt(III) and is coordinated by a tetra-anionic tetradentate ligand. Two of these outer cobalt(III) complexes act as bidentate chelating ligands to the central cobalt(II) ion, which adopts a distorted, flattened, tetrahedral geometry.
Keywords: Cobalt; Trinuclear complex; Mixed oxidation states; Pyrazolate ligands;

Structure and electrochemistry of a tetrakis(ferrocenecarboxylato)diruthenium(II,III) diadduct: evidence for ferrocenyl–ferrocenyl communication by Michael W. Cooke; Christopher A. Murphy; T.Stanley Cameron; Jannie C. Swarts; Manuel A.S. Aquino (721-725).
1-Propanol and ethanol adducts of tetrakis(ferrocenecarboxylato)diruthenium(II,III) hexafluorophosphate have been synthesized and the 1-propanol diadduct has been characterized by X-ray crystallography. The cyclopentadienyl rings of all four ferrocenyl groups showed on average a 13° deviation from the eclipsed conformation. Cyclic voltammetry measurements in 1,2-dichloroethane show an irreversible RuIIIRuII/RuIIRuII reduction and four partially superimposed one-electron ferrocenyl-centred electron transfer processes. The existence of ferrocenyl-based mixed-valent intermediate states posessing FeIII and FeII sites are implied by the splitting of the ferrocenyl wave into two observable cathodic and anodic peaks. The first cathodic wave shows typical desorption behaviour. Osteryoung Square Wave Voltammetry (OSWV) supports the above findings.
Keywords: Diruthenium carboxylates; Ferrocene carboxylate; Cyclic voltammetry; Crystal structure;

Index (727-729).

Index (731-750).