Inorganic Chemistry Communications (v.4, #11)

Announcing “Mini-Reviews” by Umberto Belluco; Daniel G. Nocera; Albert S.C. Chan (v).

A Zn coordination polymer [Zn(bbdc)(H2O)] n with 3D network structure was prepared by the hydrothermal reaction. Each Zinc(II) center was coordinated by three oxygen atoms from bbdc ligand and one oxygen atom from water molecule to display a slightly distorted tetrahedral geometry.A Zn coordination polymer [Zn(bbdc)(H2O)] n (bbdc=4,4-bibenzene-dicarboxylate) with 3D network structure was prepared by the hydrothermal reaction of Zn(CH3CO2)·2H2O,H2bbdc and H2O in a molar ratio of 1:1:1556 at 170°C and characterized by single-crystal X-ray diffraction analysis. Each Zinc(II) center was coordinated by three oxygen atoms from bbdc ligand and one oxygen atom from water molecule to display a slightly distorted tetrahedral geometry.
Keywords: Hydrothermal synthesis; Zinc(II) complex; Coordination polymer; Crystal structure;

One-pot synthesis of manganese(I) and rhenium(I) alkylcarbonato complexes, fac-(CO)3(dppp)MOC(O)OR. Possible trapping of intermediate diphosphine dimers, [(CO)3(dppp)M]2 by Karen Johnson; Tyan Frazier; Thomas M. Becker; Kristine Miller; Douglas M. Ho; Jeanette Krause-Bauer; Santosh K. Mandal (602-605).
The reactions of Mn2(CO)10 and Re2(CO)10 with dppp, where, dppp is 1,3-bis(diphenylphosphino)propane, in primary alcohols, yielded the corresponding hydrides, fac-(CO)3(dppp)MH under argon atmosphere. However, similar reactions of the metal carbonyls with diphosphines in alcohols in the presence of air or carbon dioxide afforded one equivalent of the corresponding hydrides, fac-(CO)3(dppp)MH and one equivalent of the alkylcarbonato complexes, fac-(CO)3(dppp)MOC(O)OCH2R. The rhenium propylcarbonato complex, fac-(CO)3(dppp)ReOC(O)OCH2CH2CH3 is very stable and has been characterized by X-ray crystal structure determination. The manganese-analog, fac-(CO)3(dppp)MnOC(O)OCH2CH2CH3 is moisture-sensitive and converted slowly to the known carbonato-bridged complex, (CO)3(dppp)MnOC(O)OMn(dppp)(CO)3.
Keywords: Manganese; Rhenium; Propylcarbonato complexes; Crystal structure;

An OO chelating diselenito is found in the X-ray structure of [Pt(PPh3)2(Se2O5)]. The possible preference of the cis-Pt(PPh3)2 moiety towards O, rather than softer donor ligand atoms, is briefly discussed on the basis of other examples.
Keywords: Chelating diselenito; Methylsulfanylacetato; Methylsulfanylbenzoato; Platinum phosphine complexes;

Unexpected chlorination of a pyrazole ligand. Structural characterisation of a new binuclear Cu(II) complex by Josefina Pons; Arafa Chadghan; Angel Alvarez-Larena; Joan Francesc Piniella; Josep Ros (610-612).
Crystallisation of Cu(HL1)2Cl2·EtOH (HL1=3-phenyl-5-(6-methyl-2-pyridyl)pyrazole) in DMF affords [Cu2(ClL1)2Cl2(DMF)2], where the C-chlorination of the pyrazolyl ring and the formation of a dinuclear compound is observed. The deprotonated pyrazolyl ligands have three co-ordination positions (two pyrazole nitrogens and one pyridine nitrogen) and simultaneously act as chelate and bridging ligands.
Keywords: Copper complexes; Dinuclear complexes; Pyrazole complexes; Crystal structures;

Purification of gaseous CO from Fe(CO)5 traces formed in steel storage cylinders by Jan Fiedler; Michèle Salmain; Gérard Jaouen; Lubomı́r Pospı́šil (613-616).
High purity gaseous CO stored in a steel tank contains a volatile iron carbonyl compound that easily contaminates electrochemical samples saturated with CO. The impurity yields a voltammetric reduction peak at −2.0 V in non-aqueous solvents (acetonitrile, acetone and tetrahydrofurane) and IR absorption at 2024 and 2001  cm −1 characteristic of metal carbonyls. This impurity is Fe(CO)5 and can be removed efficiently by bubbling CO through aqueous NaOH solution. This purification procedure is adequate for the electrochemical studies of metal carbonyls under CO atmosphere. Failure to remove this volatile impurity may lead to misinterpretation of electrocatalytic and ligand substitution reactions.
Keywords: Gaseous CO; Impurity; Iron carbonyls; Voltammetry; Materials; Purification;

Unusual reactions of ruthenium–polycyanocarbon complexes: formation of an η 2-CNR ligand and cleavage of C(sp2)–CN bonds by Michael I. Bruce; Brian W. Skelton; Allan H. White; Natasha N. Zaitseva (617-620).
Unusual formation of an η 2-bonded polycyanocarbon ligand from tetracyanoethene, C2(CN)4 (tcne) and the allylic ligand in Ru{η3 -CHPhCHCCPh(CCPh)}(PPh 3)Cp (1), and migration of CN from the polycyanocarbon in Ru{C[C(CN)2]CPhC(CN)2}(dppm)Cp (3), have been established by crystal structure determinations on Ru{C(CHCHPh)CPhC[CPhC(CN)2]C(CN)(η2 -CN)}(PPh 3)Cp (2) and Ru(CN){C(CN)C[CPhC(CN)2]PPh 2 CH 2 PPh 2}Cp (4), which are the respective products.
Keywords: Ruthenium; Cyanocarbon; Crystal structure; CN group migration;

The hydrothermal reaction of CoCl2·6H2O, NaVO3, 1,3-di-4-pyridylpropane (bpypr) and water in the mole ratio 1.0:1.1:2.0:1500 at 120 °C for 48 h yields [Co 3(bpypr)4(H 2 O)4 V 6 O 18]·2H 2 O  ( 1 ·2H 2 O) as red crystals in 45% yield. The structure of 1 is constructed from three distinct substructures: two-dimensional {Co(bpypr)2} n 2n+ networks, one-dimensional {Co(H2O)2(bpypr)} n 2n+ chains and vanadate spirals. Each vanadate chain links two adjacent networks, while vanadate and cobalt chains interlink to form a three-dimensional framework. Crystal data for C26H34N6O12Co1.5V3: monoclinic P21/n, a=13.0977(7) Å, b=16.5226(a) Å, c=15.3842(8) Å, β=102.246(1)°, V=3253.5(3) Å3, Z=4, D calc.=1.706 g cm −3 . Synopsis: The hydrothermal reaction of CoCl2·6H2O, NaVO3, 1,3-di-4-pyridylpropane (bpypr) and water yields the three-dimensional organic–inorganic hybrid material [Co3(bpypr)4(H2O)4V6O18]·2H2O, shown below.
Keywords: Bimetallic oxide; Hybrid material; Hydrothermal synthesis; Cobalt vanadate;

The reduction of (n-Bu4N)[AuIII(dmit)2] electrochemically and with BH4 leads to unstable monomeric [Au II (dmit)2]2−  (5d 9,S=1/2) which was characterized by X-band EPR spectra of solutions and [AuII/NiII(dmit)2]2− powder samples. For the analysis of the latter the large 197 Au nuclear quadrupole interaction must be included.
Keywords: Gold(II) complexes; 1,3-dithiolo-2-thione-4,5-dithiolate; EPR-spectroscopy;

The first substituted boranonucleic acids: a novel synthetic route by Kamesh Vyakaranam; Geeta Rana; Bernard F. Spielvogel; Narayan S. Hosmane (629-631).
Diethylchlorophosphite-cyanoborane ( 1 ) was prepared in 65% yield by the reaction of sodium cyanoborohydride and bromine followed by refluxing with diethylchlorophosphite. Compound 1 was reacted further with several commercially available nucleosides to give substituted boranonucleic acids in 46–91% yields.
Keywords: Boranophosphate; Borane; Cyanoboranes; Nucleic acids; Derivatized boranes;

Hydrothermal synthesis and structure of a bi-capped Keggin polyoxoanion, [AsIII 2AsVMo8VIV 4O40]5− by Guoyou Luan; Yangguang Li; Enbo Wang; Zhengbo Han; Changwen Hu; Ninghai Hu; Hengqing Jia (632-634).
The title compound, [NH3CH2CH2CH2NH2][NH3CH2CH2CH2NH3]2[AsIII 2AsVMo8VIV 4O40]·5H2O, was hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. Crystal data: monoclinic, C2/c, a=45.375(9)  A ̊ , b=11.774(2)  A ̊ , c=23.438(5)  A ̊ , β=96.62(3)°. X-ray crystallographic study showed that the crystal structure was constructed by bi-capped α-Keggin fragments [AsIII 2AsVMo8VIV 4O40]5− polyoxoanion.
Keywords: Polyoxometalate; Hydrothermal synthesis; Crystal structure; Bi-capped Keggin;

Structure and magnetic properties of [Cr(en)2(ox)][Cr(en)(ox)2]·2H2O,Δ-[Cr(en)3]Δ-[Cr(ox)3] and Δ-[Co(en)3]Δ-[Cr(ox)3] by Xaio Hua; Krister Larsson; Teresa J. Neal; Graeme R.A. Wyllie; Maoyu Shang; A. Graham Lappin (635-639).
Interactions between metal ion complexes in the compounds Δ-[Cr(en)3]Δ-[Cr(ox)3] and Δ-[Co(en)3]Δ-[Cr(ox)3] have been investigated by X-ray crystallography and magnetic susceptibility measurements. Crystals of both compounds are hexagonal and are isostructural with the known Δ-[Co(en)3]Δ-[Rh(ox)3] [Inorg. Chem. 30 (1991) 4954] with chains of alternating anions and cations parallel to the crystallographic c-axis. The susceptibility behavior suggests that magnetic interactions are stronger in Δ-[Cr(en)3]Δ-[Cr(ox)3] where both anion and cation are paramagnetic than in Δ-[Co(en)3]Δ-[Cr(ox)3] where only the anion is paramagnetic. Single crystal studies with the former compound reveal that magnetic interactions along the c-axis chains, where the Cr–Cr distances are shortest, are weaker than those involving off-axis interactions. Magnetic measurements were also made on [Cr(en)2(ox)][Cr(en)(ox)2]·2H2O. The structure of this compound has been previously reported.

A novel one-dimensional oxalato-bridged copper(II) complex with 2,2-bipyridine by Oscar Castillo; Antonio Luque; Sonia Iglesias; Carmen Guzmán-Miralles; Pascual Román (640-642).
The crystal structure of the compound {[Cu(ox)(bpy)]·2.5H2O} n 1 (ox=oxalate dianion, bpy=2,2-bipyridine) consists of columnar stacks of neutral [Cu(ox)(bpy)] units linked by semicoordination Cu–O bonds. The magnetic properties show the occurrence of alternating ferro–antiferromagnetic interactions (J AF =−2.1  cm −1 and J F =+0.2  cm −1 ).
Keywords: Oxalato bridge; Polynuclear complex; Copper complex; Bipyridine; Crystal structure;

Novel hexamercaptotin: synthesis and characterization of [N(CH3)4]2Sn(SH)6 and [N(C2H5)4]2Sn(SH)6 complexes by Jing-Cao Dai; Li-Ming Wu; Chuan-Peng Cui; Zhi-Yong Fu; Sheng-Min Hu; Wen-Xing Du; Wen-Jian Zhang; Xin-Tao Wu (643-647).
Mercaptotin complexes are difficult to synthesize since they are usually transient intermediates. Here, we report the synthesis and crystal structure of two examples of stable hexamercaptotin complexes [N(CH3)4]2Sn(SH)6 (1) and [N(C2H5)4]2Sn(SH)6 (2), and discuss their stability by use of quantum chemistry method. Both the complexes 1 and 2 were obtained by hydrothermal synthesis and were crystallized in monoclinic space group, C2/m, Z=8, a=25.724(8), b=18.183(6), c=9.097(3) for 1, and C2/c, Z=4, a=14.0733(14), b=14.4018(14), c=13.2538(13) for 2. Single crystal X-ray diffraction analysis revealed that the Sn(IV) centers of 1 and 2 are octahedrally coordinated to six [SH] ligands and all of the six hydrosulfuryl groups are located in terminal positions. The computational results of quantum chemistry method show that highly symmetric coordination of [SH] ligands can be effective in stabilizing stannanethiols entities.
Keywords: Crystal structure; Mercaptotin complex; Sn–SH bond energy; Stability;

Carbon–oxygen bond formation at organopalladium centres by Allan J. Canty; Melanie C. Done; Brian W. Skelton; Allan H. White (648-650).
The reaction of PdMe2(bpy) (bpy = 2,2-bipyridine) with diaroyl peroxides is a complex process in which initial oxidation of Pd(II) is followed by methyl group exchange between an undetected Pd(IV) intermediate and PdMe2(bpy) to give PdMe(O2CAr)(bpy) and PdMe3(O2CAr)(bpy); the latter Pd(IV) complex decomposes by elimination of Me–Me to give additional PdMe(O2CAr)(bpy) which reacts with (ArCO2)2 to give Me–O2CAr and Pd(O2CAr)2(bpy). The complexes Pd(O2CPh)2(L2) (L2=bpy, N,N,N ,N -tetramethylethylyenediamine) have been characterised by X-ray diffraction.
Keywords: Palladium; Organopalladium(IV); 2,2-bipyridine; N,N,N ,N -tetramethylethlenediamine; Catalysis; Peroxide; Crystal structure;

A new dicopper(II) complex with macrocyclic hexaaza bearing hydroxyethyl pendants by Shu-An Li; Dong-Feng Li; Chun-Ying Duan; Jiang Xia; De-Xi Yang; Wen-Xia Tang (651-655).
A new dicopper(II) complex with 3,6,9,16,19,22-hexaaza-6,19-bis(2-hydroxyethyl)-tricyclo[22,2,2,211,14]triaconta-1,11,13,24,27,29-hexaene(L), was synthesized and characterized. The crystal structure of [Cu2L(N3)2](ClO4)2·2H2O has shown that both Cu2+ ions are in penta-coordination environment with distorted trigonal bipyramid consisting of three N atoms from diethylenetriamine moieties, one N atom from azide and one O atom from hydroxyethyl pendant, and the separation of Cu⋯Cu is 8.11 Å. The two aromatic rings are close to each other, the shortest distance being 3.71 Å for C11⋯C21, and the benzene ring planes from a dihedral angle of 70.9° in molecule. ES-MS spectra showed that the main species, [Cu2(L–H)N3]2+ and [Cu2(L–2H)]2+, were formed by deprotonation of the hydroxyethyl pendants and releasing azides from the Cu(II) complex stepwise.
Keywords: Crystal structure; Dinuclear Cu(II) complex; ES-MS; Hydroxyethyl pendants;

The complex, [MnL(H2O)]2+, has been isolated by the reaction of N,N -bis(picolinylidene)hydrazine with N-(picolinylidene)hydrazine in presence of Mn2+. The pentadentate N5 donor ligand, bis(picolinylidenehydrazyl)(2-pyridyl)methane (L), is formed by the addition of N-(picolinylidene)hydrazine to one of the metal activated azomethine fragment of the tetradentate diazine ligand N,N -bis(picolinylidene)hydrazine. The X-ray structure reveals the trigonal prismatic N5O coordination geometry around the high-spin metal centre in [MnL(H2O)]2+.
Keywords: Manganese(II) complex; Pentadentate ligand; X-ray structure; Trigonal prism.;

Photoinduced denitrosyl dinuclearizing reaction of dinitrosyl-molybdenum [Mo(didentate-N,S)2(NO)2] complexes by Toshiaki Yonemura; Jyunko Nakata; Megumi Kadota; Mayumi Hasegawa; Ken-ichi Okamoto; Tomoharu Ama; Hiroshi Kawaguchi; Takaji Yasui (661-663).
The cis(NO,NO)-trans(S,S)-[MoL2(NO)2] complexes [L = 2-pyrimidinethiolate (pymt) 1 and 2-pyridinethiolate (pyt) 2] were newly prepared by the reaction of the [Mo(NO)2]2+ solution with the thiolate ligands. Under room light, complexes 1 and 2 released one of two nitric oxide (NO) to give μ-OH dinuclear complexes, [{(ON)MoL2}2(μ-OH)2] (L = pymt 3 and pyt 4). The central molybdenum ion circumference turns from six-coordination into seven-coordination, and oxidation number also varies with this reaction from 0 to +II.
Keywords: Molybdenum-nitrosyl complexes; Thiolato complexes; Photo-denitrosyl reaction; Dinuclearizing reaction;

Reaction of the symmetrical proligand HL4 with zinc(II) salts has given mono- and di-nuclear metal complexes. The structure of a mononuclear complex, [ZnL4], which crystallises in the triclinic space group P 1 (C i 1, No. 2) with unit cell parameters a=9.3910(10), b=9.4959(10), c=15.9380(16)  A ̊ , α=96.938(2)°, β=97.097(2)°, γ=100.082(2)°, has been determined.
Keywords: Crystal structure; Zinc(II) complex;

The reaction of nickel(II) salts with unsymmetrical Schiff base compartmental proligands has induced cleavage of the iminic pendant arm to give dinuclear complexes of the corresponding aldehydes.
Keywords: Crystal structure; Dinuclear nickel(II) complex;

Thiirane is transformed catalytically into the symmetric thiacrowns: 1,4,7,10-tetrathiacyclododecane, 12S4; 1,4,7,10,13-pentathiacyclopentadecane, 15S5; and 1,4,7,10,13,16-hexathiacyclooctadecane, 18S6, when treated with the manganese carbonyl monocations: [Mn(CO)4(L)(NCMe)]+, L=CO, PPh3, PMe2Ph and PEt3 at room temperature. 12S4 is the major thiacrown product. Considerable amounts of polymer are also formed. The phosphine-substituted catalysts are considerably more active and give better yields of the thiacrowns than the parent carbonyl, but they also give more polymer side product.
Keywords: Thiacrown; Thiirane; Manganese carbonyl; Catalysis;

Assembly of a novel cyclic dimer encapsulating PF 6 into the brick wall network by Jun Liu; Hong-Ke Liu; Xiao-Long Feng; Hua-Xin Zhang; Zhong-Yuan Zhou; Albert S.C. Chan; Bei-Sheng Kang (674-677).
The cyclic silver (I) dimer [Ag(m-bitmb)]2(PF6)2·2MeCN of 1,3-bis(imidazolylmethyl)-2,4,6-trimethylbenzene (m-bitmb) was prepared and its structure characterized by X-ray crystallography. An PF 6 anion is encapsulated within the macrocyclic cation [Ag(m-bitmb)]2 2+ with weak Ag⋯F and CH⋯F interactions. Two types of intermolecular π–π interactions lead to a brick wall network.
Keywords: Silver cyclic dimer; Anion encapsulation; π–π interaction; Brick wall network;

An oxidation reaction route under hydrothermal conditions afforded a novel mixed-valent-copper coordination polymer with unprecedented mutual-face-insertion layered open-framework displaying graphite-like properties.
Keywords: Mixed-valence copper; Coordination polymer; Layered compound; Graphite property; Hydrothermal; Oxidation reaction;

Ferrocenophane-ring opening in (ferrocene-1,1-diyl)phenylphosphine with phenyl lithium followed by reaction with N,N-dimethylformamide affords 1-(diphenylphosphino)ferrocenecarboxaldehyde (1) in good yield. Aldehyde 1 and 1-(diphenylphosphino)ferrocenecarboxylic acid are nearly quantitatively reduced to {1-(diphenylphosphino)ferrocenyl}methanol (2). Compounds 1 and 2 have been characterized by IR, NMR and electron-impact mass spectroscopy and their structures determined by single-crystal X-ray diffraction. The molecular structures of 1 and 2 in the solid state do not differ significantly. However, whereas the packing of aldehyde 1 is essentially molecular, alcohol 2 forms supramolecular structures via extensive hydrogen O–H⋯O bonding.
Keywords: Ferrocenes; Synthesis; Hydrogen bonds; X-ray diffraction; Mass spectrometry;