Inorganic Chemistry Communications (v.8, #10)

Contents List (iii-ix).

An unprecedented environment controlled solid state inter-conversion of a water – chloride hexameric 2-D cluster and a 1-D helical water chloride cluster is reported. It provides us an opportunity to study such system experimentally since, for lack of experimental examples, chloride-water assemblies have, primarily, been studied theoretically.On extrusion of a water molecule from the nano-channels created by the packing of [cis-α-(trien)CoCl2]Cl · 3H2O, an unprecedented dehydration transition occurs that cause the guest water–chloride hexameric clusters to rearrange into a helical modification. The reverse process is achieved by the introduction of an additional water molecule.
Keywords: Cobalt complex; Water–chloride cluster; Hexamer and helical form;

Directly-linked intramolecular donor–acceptor compounds of ferrocene and tetracyanoanthraquinodimethane by Glenn Kelly; Fatemeh Darviche; Neil Robertson; Thomas Gelbrich; Michael B. Hursthouse; Dafydd A. Thomas; Ian R. Butler (874-877).
Ferrocene has been directly linked to tetracyanoanthraquinodimethane in both the 1 (1) and 2 (2) position. Electrochemical and spectroscopic properties indicate significant differences between 1 and 2, revealing the importance of the position of attachment onto the TCNAQ aromatic system. The X-ray structure of 1 is reported.Two new intramolecular donor–acceptor species have been prepared linking ferrocene (Fc) directly to either the 1 (1) or 2 (2) positions of tetracyanoanthraquinodimethane (TCNAQ). Spectroscopic and electrochemical characterisation show significant differences between 1 and 2, revealing the importance of the position of attachment. The Fc part is a poorer donor and the TCNAQ part a poorer acceptor than the respective parent molecules and an intramolecular charge-transfer transition is observed at 604 nm (1) and 634 nm (2). The X-ray structure of 1 shows the TCNAQ component with the typical folded conformation with the ferrocene unit rotated by 38.0° relative to the ring to which it is attached.
Keywords: Metallocene; Donor–acceptor; X-ray structure; Synthesis;

Dicarboxylic acid esters from the carbonylation of unsaturated esters under mild conditions by Cristina Jiménez-Rodriguez; Graham R. Eastham; David J. Cole-Hamilton (878-881).
Palladium complexes are used as catalysts for the methoxycarbonylation of unsaturated esters and acids to α,ω-diesters with very high selectivity. The double bond can be conjugated with the original ester function or even deep in a hydrocarbon chain.The methoxycarbonylation of unsaturated acids or esters catalysed by Pd complexes of bis(ditertiarybutyl-phosphinomethyl)benzene (DTBPMB) produces α,ω-diesters with selectivities >95%, even if the double bond is deep in the chain or conjugated to the carbonyl group; unsymmetrical esters can also be produced with high selectivity.
Keywords: Palladium; Methoxycarbonylation; α,ω-Diesters; Acrylic acids; Phosphine;

A new dinuclear copper(II) complex [Cu21,1-NCO)2(NCO)2(dpyam)2] (dpyam = di-2-pyridylamine) has been synthesized and characterized by X-ray diffraction. Two N-bonded cyanato ligands bridge two copper ions in an end-on fashion and two others act as the N-bonded terminal ligands. The copper ion has a distorted square-pyramidal environment. The magnetic susceptibility, measured from 5 to 300 K, has revealed a weak ferromagnetic interaction between the Cu(II) atoms with a singlet–triplet energy gap (J) of 6.03 cm−1.A new dinuclear copper(II) complex [Cu21,1-NCO)2(NCO)2(dpyam)2] (dpyam = di-2-pyridylamine) has been synthesized and characterized by X-ray diffraction. Two N-bonded cyanato ligands bridge two copper ions in an end-on fashion and two others act as the N-bonded terminal ligands. The copper ion has a distorted square-pyramidal environment.The magnetic susceptibility, measured from 5 to 300 K, has revealed a weak ferromagnetic interaction between the Cu(II) atoms with a singlet–triplet energy gap (J) of 6.03 cm−1. The EPR spectrum, measured as a powdered solid at RT and 77 K, shows an S  = 1/2 signal with g  = 2.08 and an unresolved g of 2.29.
Keywords: Copper(II); Pseudohalides; EPR; Magnetism; Di-2-pyridylamine; Cyanate;

A new compound featuring bicapped Keggin dimerized polyanion, ( H 2 bpy ) 4 [ Si 2 Mo 16 VI Mo 8 V O 80 ( V IV O ) 4 ] · 2 H 2 O (1) (bpy = 4,4′-bipyridine), has been synthesized under hydrothermal conditions by directly using H4SiMo12O40 as starting materials. It represents the first example of bicapped Keggin dimerized polyanions, constructing from the pre-designed building unit {SiMo12O40}. The electrochemical property of the compound was studied.A new hydrogen-bonded network featuring bicapped dimerized polyanion, ( H 2 bpy ) 4 [ Si 2 Mo 16 VI Mo 8 V O 80 ( V IV O ) 4 ] · 2 H 2 O (1) (bpy = 4,4′-bipyridine), has been synthesized under hydrothermal conditions. The study of electrochemical property of compound 1 shows it undergoes three two-electron redox processes.
Keywords: Bicapped keggin dimer; Polyoxometalate; Hydrothermal synthesis; Electrochemical property;

A layered vanadium selenite has been hydrothermally synthesized and its structure is layered and can be described as vanadium selenite oxide layers with diprotonated piperazine occupying the interlayer space.A layered vanadium selenite, (C4N2H12)0.5[(VO)2(H2O)2(SeO3)2(HSeO3)], has been hydrothermally synthesized and structurally characterized. Its structure is layered and can be described as vanadium selenite oxide layers with diprotonated piperazine occupying the interlayer space. The result of magnetic measurement for the title compound shows a typical antiferromagnetic interaction at low temperature.
Keywords: Vanadium selenite; Hydrothermal synthesis; Layer; Template; Magnetic properties;

Synthesis and characterization of a recoverable rhodium catalyst with a stimulus sensitive polymer ligand by Wendy J. Shaw; John C. Linehan; Anna Gutowska; David Newell; Tom Bitterwolf; John L. Fulton; Yongsheng Chen; Charles F. Windisch (894-896).
A thermally sensitive rhodium catalyst has been prepared by a synthetically straightforward, one step reaction. The catalyst can be precipitated above 34 °C for complete catalyst recovery.We report the synthesis and characterization of a rhodium catalyst attached to a polymer which is designed to control catalyst reactivity in response to an applied stimulus. The catalyst precursor, Rh(Cl)(CO)2(NH2-polymer), was prepared from poly N-isopropylacrylamide (pNIPAAm) and [Rh(Cl)(CO)2]2. The structure of the metal complex was interrogated using IR, Raman, UV/Vis, NMR and XAFS, and catalytic activity was tested using an aqueous hydrogenation reaction.
Keywords: Rhodium catalysis; Recoverable catalysts; Stimulus sensitive catalysts; Stimulus sensitive polymers;

A new photoluminescent open-framework copper (I) bromide polymer, [Cu2Br2(BPP)] n (BPP = 1,3-bis(4-pyridyl)propane) (1), has been hydrothermally synthesized and structurally characterized. The structure of complex 1 features a 2-D inorganic–organic hybrid coordination network with a 1-D copper (I) chain bridged by trans-Br atoms.A new photoluminescent open-framework copper (I) bromide polymer, [Cu2Br2(BPP)] n (BPP = 1,3-bis(4-pyridyl)propane) (1), has been hydrothermally synthesized and structurally characterized. The structure of complex 1 features a 2-D inorganic–organic hybrid coordination network with a 1-D copper (I) chain (Cu(I)⋯Cu(I) separation is 2.849(4) Å) bridged by trans-Br atoms. An intense emission of complex 1 at 486 nm (λ ex  = 370 nm) was observed.
Keywords: Hydro(solvo)thermal synthesis; Copper (I) bromide polymer; Luminescence property; trans-Br atoms;

In a structure of μ-oxo-bis(phthalocyaninato)iron with pyridine and tetrahydrofuran coordination, the conformations of two phthalocyanine skeletons are different, which are dome-like and saddle shapes, respectively.In a μ-oxo-bis(phthalocyaninato)iron prepared from ferrocene and phthalonitrile, one phthalocyaninatoiron is coordinated with pyridine and the other with tetrahydrofuran, respectively. The one with pyridine coordinated exhibits a dome-like conformation and other with tetrahydrofuran exhibits a saddle shape.
Keywords: μ-Oxo-bis(phthalocyaninato)iron; Asymmetry coordination; Distortion;

Titanium complexes supported by a sterically encumbering N-anchored tris-arylphenoxide ligand by Sara A. Cortes; Miguel A. Muñoz Hernández; Hidetaka Nakai; Ingrid Castro-Rodriguez; Karsten Meyer; Alison R. Fout; Deanna L. Miller; John C. Huffman; Daniel J. Mindiola (903-907).
Neutral and cationic Ti(IV) complexes supported by the sterically demanding and trianionic ligand (O3N)3− (O3N3−  = tris(2-O,3-Ad,5-tBubenzyl)amine, Ad = 1-adamantyl) have been prepared and fully characterized. Molecular structures for the neutral complexes (O3N)TiCl (left) and (O3N)Ti(OTf) (right, SO2CF3 omitted) are reported.A family of neutral and cationic Ti(IV) complexes supported by the sterically demanding and trianionic ligand (O3N)3− (O3N3−  = tris(2-O,3-Ad,5-tBubenzyl)amine, Ad = 1-adamantyl) have been prepared from the hydrolysis of TiCl4(THF)2 with the free base (O3N)H3 and excess NEt3, followed by anion exchange reactions. These (O3N)Ti+ cores are resistant to moisture and air, are mononuclear, and possess C3 symmetry on the NMR timescale.
Keywords: Tripodal ligands; N-anchored; Titanium complexes; Trianionic-amines; X-ray structure;

The synthesis and characterization of nickel(II) complexes with N2O2 donor ligands containing a polymerisable group by spectral, electrochemical, thermal and structural studies have been described.The free Schiff base ligands H2MABCE, H2MABCP, and H2MABCT and their complexes [Ni(MABCE)], [Ni(MABCP)], and [Ni(MABCT)] have been synthesized and characterized by spectroscopic and cyclic voltammetric studies. The coordination geometry around the nickel atom is a square planar with N2O2 donor atoms. Cyclic voltammetric studies of the complexes show one electron quasi-reversible waves corresponding to Ni(II)/Ni(I) and Ni(II)/Ni(III) processes. The electronic spectra of the complexes reveal a four coordinate geometry. The crystal structure of one of the ligands (H2MABCE) has also been reported.
Keywords: Schiff bases; Nickel (II) complexes; Crystal structure; Cyclic voltammetry;

A new sodium zinc 1,4-butylenediphosphonate with polar pillar-like open-framework by Ruibiao Fu; Shengmin Hu; Huishuang Zhang; Longsheng Wang; Xintao Wu (912-915).
A new high thermal stability sodium zinc 1,4-butylenediphosphonate [NaZn3(HO3P(CH2)4PO3)(O3P(CH2)4PO3)] (1) possesses a 3D polar pillar-like open-framework containing 1,4-butylenediphosphonates, tri-metal building units and 18-atom 1D channels.A new high thermal stability sodium zinc 1,4-butylenediphosphonate [NaZn3(HO3P(CH2)4PO3)(O3P(CH2)4PO3)] (1), which possesses a 3D polar pillar-like open-framework containing 1,4-butylenediphosphonates, tri-metal building units and 18-atom 1D channels, has been successfully hydrothermal synthesized under very acid condition.
Keywords: Hydrothermal synthesis; Single crystal structure; Zinc 1,4-butylenediphosphonate;

A solvent stabilized cyclic dimer complex of platinum(II) with S2O2 macrocycle by Joobeom Seo; Il Yoon; Ji-Eun Lee; Mi Ryoung Song; So Young Lee; Sun Hong Park; Tae Ho Kim; Ki-Min Park; Bong Gon Kim; Shim Sung Lee (916-919).
Assembly of L 2 (5,8-dioxa-2,11-dithia[12]-m-cyclophane) with K2PtCl4 followed by recrystallization from CH2Cl2 afforded a cyclic dimer complex [Pt2(L 2 )2Cl4]CH2Cl2 (2). Interestingly, one CH2Cl2 molecule found in the cyclic dimmer cavity stabilizes the whole structure of 2 by hydrogen bonds.Assembly reaction of L 2 (5,8-dioxa-2,11-dithia[12]-m-cyclophane) with K2PtCl4 afforded a unique cyclic dimer complex [Pt2(L 2 )2Cl4] (1) but its whole conformation is disordered except two metal centers. Recrystallization of the same compound from dichloromethane afforded an isostructural product [Pt2(L 2 )2Cl4]CH2Cl2 (2) but without such disorder. In 2, each Pt atom is four-coordinated in a square-planar environment with two S atoms from different two L 2 s and to two Cl ions in a cis arrangement showing a basket-like conformation. Very interestingly, one dichloromethane molecule found in the cyclic dimmer cavity stabilizes the whole structure of 2 by hydrogen bonds.
Keywords: S2O2 macrocycle; Platinum(II); Cyclic dimer complex; Crystal structure; Entrapped dichloromethane; Hydrogen bond;

Synthesis and characterisation of a bis(silyloxy)tin(IV) porphyrin by Steven J. Langford; Melissa J. Latter; Jens Beckmann (920-923).
Bis(hydroxy)tin(IV) tetraphenylporphyrin 2 condenses with two equivalents of tris(tert-butoxy)silanol 3 to form complex 2.3 2 in toluene. The product, which is air and moisture stable, has been characterised by 1H, 29Si and 119Sn NMR spectroscopy and mass spectrometry. Application of this reaction in producing novel photochromic glasses is also discussed.Bis(hydroxy)tin(IV) tetraphenylporphyrin (Sn(IV)TPP(OH)2, 2) condenses with two equivalents of tris(tert-butoxy)silanol (HOSi(O t Bu)3, 3) to form complex 2.3 2 in toluene. The product, which is air and moisture stable, has been characterised by 1H, 29Si and 119Sn NMR spectroscopy and mass spectrometry. Application of this reaction in producing novel photochromic glasses is also discussed.
Keywords: Sn(IV) porphyrins; Silanols; Complexations; NMR spectroscopy;

The first one-dimensional lanthanopolyoxotungstoborate by Filipa L. Sousa; Filipe A. Almeida Paz; Carlos M.C.E. Granadeiro; Ana M.V. Cavaleiro; João Rocha; Jacek Klinowski; Helena I.S. Nogueira (924-927).
A novel one-dimensional zigzag lanthanopolyoxotungstoborate, H2(NH4)10[Ce2(BW11O39)2(H2O)6] · 21H2O, was synthesised under ambient conditions. It is the first example of a one-dimensional polymer, where Keggin-type anions containing a central boron atom are bridged by Ce3+ cations.A novel one-dimensional zigzag lanthanopolyoxotungstoborate, H2(NH4)10[Ce2(BW11O39)2(H2O)6] · 21H2O, was synthesised under ambient conditions. It is the first example of a one-dimensional polymer where Keggin-type anions containing a central boron atom are bridged by Ce3+ cations.
Keywords: Polyoxometalates; Boron; Lanthanides; Crystal structure;

A highly diastereoselective synthesis (>99%) of a novel chiral dimer obtained from 3,4,5,6-tetrahydro-8-hydroxy-1H,6H-naphtho[1,2-h]pyrrolo[2,1-e][1,3,6,2]dioxaza-boronin-6-one is described and details of the dimer crystal structure are presented.A highly diastereoselective synthesis (>99%) of a novel chiral dimer obtained from 3,4,5,6-tetrahydro-8-hydroxy-1H,6H-naphtho[1,2-h]pyrrolo[2,1-e][1,3,6,2]dioxaza-boronin-6-one is described and details of the dimer crystal structure are presented.
Keywords: β-Naphthol; L-Proline; Boron; Diastereoselectivity; Crystal structure;

Ni(II), Co(II) and Mn(II) tris(pyrazolyl)borate complexes with 2,6-di-tert-butyl-4-carboxy-phenol: Formation of coordinated phenoxyl radical by Anastasiya V. Yakovenko; Sergey V. Kolotilov; Anthony W. Addison; Swiatoslaw Trofimenko; Glenn P.A. Yap; Victoria Lopushanskaya; Vitaly V. Pavlishchuk (932-935).
It was found that coordination of Ni and Co complexes to 2,6-di-tert-butyl-4-carboxy-phenoxyl led to stabilization of this radical.Ni(II), Co(II) and Mn(II) tris(pyrazolyl)borate complexes with 2,6-di-tert-butyl-4-carboxy-phenol were synthesized and characterized crystallographically (Ni and Co complexes), spectroscopically and electrochemically. It was found that oxidation of Ni and Co complexes resulted in the formation of coordinated phenoxyl radical and diphenoquinone, whereas only quinone formed in the case of Mn complex and free 2,6-di-tert-butyl-4-carboxy-phenol.
Keywords: 3d-metals; Phenoxyl radical; Tris(pyrazolyl)borates; X-ray structure; ESR spectra; Redox properties;

This work describes the first successful synthesis of a novel beryllium amide complex containing trimethyl stannylamide moities. The title compound exists as a dimer in the solid state and possesses bridging stannylamide and terminal chloride ligands. The isolation of this compound presents a potential route towards extension of this class of compounds.The reaction of the homoleptic lithium stannylamide, [(Me3Sn)2NLi · (THF)]2, with BeCl2 yields the beryllium amide, [(Me3Sn)2NBe(Cl) · (THF)]2. X-ray structural analysis reveals that the complex is comprised of a beryllium dimer possessing bridging amide moieties and terminal chloride ligands. This product represents the first compound containing nitrogen-bridged Be(II) and Sn(IV) metal centers.
Keywords: Beryllium; Metal amide; Molecular precursor; MOCVD; Stannylamine;

Appreciable coordination occurs at Ni⋯O contacts almost equal to the sum of the van der Waals radii of the two atoms in the two entities reported here. The very weak coordination bonds link the trinuclear units into coordination polymer chains in crystal 1 and 2.Two new entities [Co(NiL)2(SCN)2] n (1) and [Mn(NiL)2(NCS)2] n (2) were prepared by using a macrocyclic oxamido mononuclear complex ligand NiL, and characterized by X-ray single crystal analyses. L denotes the dianion of dimethyl 5,6,7,8,15,16-hexahydro-6,7-dioxodibenzo[1,4,8,11]tetraazacyclotetradecine-13,18-dicarboxylate. Ni⋯O contacts (3.092 Å) almost equal to the sum of the van der Waals radii of the two atoms were observed both in 1 and 2, and IR spectra support that appreciable coordination occurs at such long contacts. 1 and 2 are 1D coordination polymers incorporating bimetallamacrocycles with the very long Ni⋯O coordination bonds as a kind of linking interaction.
Keywords: Weak coordination; Macrocyclic compound; Coordination polymer; Crystal structure;

New pentaammine(alkyl)cobalt(III) cations decompose in neutral aqueous solution to give alkyl radicals. The compounds are robust in the presence of excess ammonia.Amminecobalt(III) compounds with a coordinated primary alkyl group (ethyl, n-propyl, n-butyl, 2-phenylethyl, 3-aminopropyl) have been prepared using monoalkylhydrazines as alkylating agents. The identities have been established using solution 1H and 13C NMR spectroscopy and elemental analysis. The pentaammine(alkyl)cobalt(III) cations decompose in neutral aqueous solution to give alkyl radicals.
Keywords: Alkylcobalt(III); Pentaamminecobalt(III); Alkyl radicals; NMR;

3-[2-(2-Quinoxalinyl)benzoxazol-5-yl]alanine derivative – A specific fluoroionophore for Ni(II) by Magda Milewska; Agnieszka Skwierawska; Katarzyna Guzow; Dagmara Szmigiel; Wiesław Wiczk (947-950).
3-[2-(2-Quinoxalinyl)benzoxazol-5-yl]alanine derivatives were synthesized. N-Boc-3-[2-(2-quinoxalinyl)benzoxazol-5-yl]alanine methyl ester (1) is a selective fluoroionophore for Ni(II) ion which as a very weak base in the ground and excited state is applicable at a wide range of pH.The synthesis of N-Boc-3-[2-(2-quinoxalinyl)benzoxazol-5-yl]alanine methyl ester (1) and 3-[2-(2-quinoxalinyl)benzoxazol-5-yl]alanine (2), useful in peptide chemistry, are described. The influence of metal ions and pH on spectroscopic properties of compounds studied is presented. The compounds studied are very weak bases in the ground state and their basicity increases in the excited state. Among ions studied, in the ground state only Cu(II) and Al(III) and Pb(II) ions form stable complexes with (1), whereas in the excited state – only Ni(II) ion. Contrary to the most fluoroionophores the fluorescence intensity of ligand (1) in acetonitrile increases with the increase of Ni(II) ion concentration, whereas the fluorescence intensity of (2) in water is totally quenched by H3O+ ion.
Keywords: Benzoxazole; Chemosensor; Aromatic amino acid; Fluorescence;

The synthesis and structural characterization of novel zinc and cadmium complexes of chelating alcohol by Barbara Barszcz; Agnieszka Jabłońska-Wawrzycka; Katarzyna Stadnicka; Stanisław A. Hodorowicz (951-954).
Novel [Zn(1-Bz-2-CH2OHIm)4]2+, and [Cd(1-Bz-2-CH2OHIm)4]2+ complexes have been prepared and structurally characterized. Both structural and spectroscopic (NMR, IR) data suggest 1-Bz-2-CH2OHIm as a potentially good chelator for the removal of toxic cadmium from the body.Reaction of Zn(II) and Cd(II) ion with 1-benzyl-2-hydroxymethylimidazole (1-Bz-2-CH2OHIm) afforded two novel complexes [Zn(1-Bz-2-CH2OHIm)4](NO3)2  · 1.5H2O (1) and [Cd(1-Bz-2-CH2OHIm)4](NO3)2(H2O)2 (2). The structures of compounds are very interesting and different from each other. The shape of the coordination polyhedron of Zn(II) is very rare for six-coordinated complexes and can be described as a distorted trigonal antiprism (space group C2/c). The cadmium complex exhibits an unusual eight-coordinate structure (CdN4O4) and the coordination polyhedron can be described as a pseudo-tetragonal antiprism distorted to C2 symmetry. Both structural and spectroscopic (NMR, IR) data suggest 1-Bz-2-CH2OHIm as a potentially good chelator for the removal of toxic cadmium from the body.
Keywords: N,O ligand; Cadmium and zinc complexes; Trigonal antiprism; Tetragonal antiprism;

Thiolation of iodobenzene catalyzed by fluorinated bis-imino nickel NNN pincer complexes by Oscar Baldovino-Pantaleón; Simón Hernández-Ortega; David Morales-Morales (955-959).
Fluorinated bis-imino nickel NNN pincer complexes [NiCl2{C5H3N-2,6-(CHNAr f )2}] efficiently catalyze the synthesis of methyl phenyl sulfide by cross coupling of (RS)2 and iodobenzene promoted by zinc.The synthesis of bis-imino nickel(II) NNN pincer complexes of the type [NiCl2{C5H3N-2,6-(CHNAr f )2}]; Ar f  = C6H3-2,3-F2 (1), C6H3-2,5-F2 (2), C6H3-3,4-F2 (3), C6H3-3,5-F2 (4), C6H2-2,3,4-F3 (5), C6H2-2,3,6-F3 (6), C6H2-2,4,5-F3 (7), and C6H2-2,4,6-F3 (8), has been achieved and its reactivity explored proving these compounds to be efficient in the alkyl and aryl thiolation of iodobenzene.
Keywords: Thiolation; C–S coupling reactions; Pincer complexes; Nickel complexes; Catalysis; Crystal structures;

The reaction of [ReBr3(NO)(PPh3)2] complex with pyrazole (pzH) has been examined and a new rhenium nitrosyl – [ReBr3(NO)(PPh3)(pzH)] – has been obtained. The X-ray structure of the [ReBr3(NO)(PPh3)(pzH)] complex has been determined and its electronic structure has been calculated with the density functional theory (DFT) method with the use of B3LYP functional. Additional information about binding in the [ReBr3(NO)(PPh3)(pzH)] complex has been obtained by NBO analysis. The [ReBr3(NO)(PPh3)2] complex has also been investigated by IR and UV–Vis spectroscopy. The spin-allowed doublet–doublet electronic transitions of [ReBr3(NO)(PPh3)(pzH)] have been calculated with the time-dependent DFT method (TDDFT method) and the UV–Vis spectrum of the title complex has been discussed on this basis.The reaction of [ReBr3(NO)(PPh3)2] complex with pyrazole (pzH) has been examined and a new rhenium nitrosyl – [ReBr3(NO)(PPh3)(pzH)] – has been obtained. The X-ray structure of the [ReBr3(NO)(PPh3)(pzH)] complex has been determined and its electronic structure has been calculated with the density functional theory (DFT) method with the use of B3LYP functional. Additional information about binding in the [ReBr3(NO)(PPh3)(pzH)] complex has been obtained by NBO analysis. The time-dependent DFT method (TDDFT) has been used for calculations of spin-allowed doublet–doublet electronic transitions of [ReBr3(NO)(PPh3)(pzH)], and on this basis the UV–Vis spectrum has been discussed.
Keywords: Rhenium nitrosyl complexes; Pyrazole; Phosphine ligands; X-ray structure; DFT calculations;