Intra- and intermolecular interactions in a series of chlorido-tricarbonyl-diazabutadienerhenium(I) complexes: structural and theoretical studies

2020 ◽  
Vol 76 (3) ◽  
pp. 417-426 ◽  
Author(s):  
Reza Kia ◽  
Azadeh Kalaghchi
Keyword(s):  
Intermolecular Interactions ◽  
Density Functional ◽  
Metal Carbonyl ◽  
Lone Pair ◽  
Carbonyl Complexes ◽  
X Ray Diffraction ◽  
Functional Theory ◽  
X Ray ◽  
Covalent Interaction ◽  
Metal Carbonyl Complexes

A series of new chlorido-tricarbonylrhenium(I) complexes bearing alkyl-substituted diazabutadiene (DAB) ligands, namely N,N′-bis(2,4-dimethylbenzene)-1,4-diazabutadiene (L1), N,N′-bis(2,4-dimethylbenzene)-2,3-dimethyl-1,4-diazabutadiene (L2), N,N′-bis(2,4,6-trimethylbenzene)-2,3-dimethyl-1,4-diazabutadiene (L3) and N,N′-bis(2,6-diisopropylbenzene)-1,4-diazabutadiene (L4), were synthesized and investigated. The crystal structures have been fully characterized by X-ray diffraction and spectroscopic methods. Density functional theory, natural bond orbital and non-covalent interaction index methods have been used to study the optimized geometry in the gas phase and intra- and intermolecular interactions in the complexes, respectively. The most important studied interactions in these metal carbonyl complexes are n→π*, n→σ* and π→π*. Among complexes 1–4, only 2 shows interesting intermolecular n→π* interactions due to lp(C[triple-bond]O)...π* and lp(Cl)...π* (lp = lone pair) contacts.

Quantitative Analysis of Intermolecular Interactions in 3‐Cyano‐2‐Pyridones: Evaluation through Single Crystal X‐ray Diffraction and Density Functional Theory

2018 ◽  
Vol 3 (21) ◽  
pp. 5864-5873
Author(s):  
Sunil K. Rai ◽  
Tomasz Sierański ◽  
Shaziya Khanam ◽  
Krishnan Ravi Kumar ◽  
Balasubramanian Sridhar ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Quantitative Analysis ◽  
Single Crystal ◽  
Intermolecular Interactions ◽  
Density Functional ◽  
X Ray Diffraction ◽  
Functional Theory ◽  
X Ray

Metal carbonyl complexes of potentially ambidentate 2,1,3-benzothiadiazole and 2,1,3-benzoselenadiazole acceptors

2017 ◽  
Vol 72 (11) ◽  
pp. 839-846
Author(s):  
Sebastian Plebst ◽  
Martina Bubrin ◽  
David Schweinfurth ◽  
Stanislav Záliš ◽  
Wolfgang Kaim
Keyword(s):  
Crystal Structure ◽  
Density Functional Theory ◽  
Electron Transfer ◽  
Density Functional ◽  
Metal Carbonyl ◽  
Density Functional Theory Calculations ◽  
Carbonyl Complexes ◽  
Functional Theory ◽  
Metal Carbonyl Complexes ◽  
Reduced Forms

AbstractThe compounds [W(CO)5(btd)], [W(CO)5(bsd] and [Re(CO)3(bpy)(bsd)](BF4), btd=2,1,3-benzothiadiazole and bsd=2,1,3-benzoselenadiazole were isolated and characterized experimentally (crystal structure, spectroscopy, spectroelectrochemistry) and by density functional theory calculations. The results confirm single N-coordination in all cases, binding to Se was calculated to be less favorable. Studies of one-electron reduced forms indicate that the N-coordination is maintained during electron transfer.

Reaction of bromopentacarbonylrhenium(I) with ferrocenylcarbaldehyde thiosemicarbazones: the first X-ray diffraction studies of metal carbonyl complexes containing bidentate thiosemicarbazone ligands

2002 ◽  
Vol 656 (1-2) ◽  
pp. 1-10 ◽  
Author(s):  
Rosa Carballo ◽  
José S Casas ◽  
Emilia Garcı́a-Martı́nez ◽  
Gumersindo Pereiras-Gabián ◽  
Agustı́n Sánchez ◽  
...  
Keyword(s):  
Metal Carbonyl ◽  
Carbonyl Complexes ◽  
X Ray Diffraction ◽  
X Ray ◽  
Metal Carbonyl Complexes

N,S-Chelating Amino-ortho-carboranethiolate Complexes of Rhodium and Iridium: Synthesis and Reactivity. X-Ray Crystal Structures of (η4-C8H12)Rh[(NMe2CH2)SC2B10H10] and (CO)2Rh[(NMe2CH2)SC2B10H10]

1999 ◽  
Vol 64 (5) ◽  
pp. 883-894 ◽  
Author(s):  
Seung-Won Chung ◽  
Jaejung Ko ◽  
Kwonil Park ◽  
Sungil Cho ◽  
Sang Ook Kang
Keyword(s):  
Metal Atom ◽  
Metal Carbonyl ◽  
Carbonyl Complexes ◽  
X Ray Diffraction ◽  
X Ray ◽  
Metal Carbonyl Complexes ◽  
Square Planar ◽  
Rhodium Atom ◽  
High Yields ◽  
New Compounds

The reaction of [M(μ-Cl)(cod)]2 (M = Rh, Ir; cod = cycloocta-1,5-diene) with two equivalents of the lithium ortho-carboranethiolate derivative LiCabN,S 2 [LiCabN,S = closo-2-(dimethylaminomethyl)-1-(lithiumthiolato)-ortho-carborane] produced the four-coordinated metallacyclic compounds, CabN,SM(cod) 3 (M = Rh 3a, Ir 3b), in which the metal atom was stabilized via intramolecular N,S-coordination. These new compounds have been isolated in high yields and characterized by IR and NMR spectroscopy. The structure consists of an amino-ortho-carboranethiolate fragment bonded to (cod)Rh(I) via nitrogen and sulfur, so as to give the metal a square-planar environment. Subsequent carbonylation reactions of 3a, 3b result in the quantitative formation of the corresponding (amino-ortho-carboranethiolato)(carbonyl)metal N,S-chelates CabN,SM(CO)2 4 (M = Rh 4a, Ir 4b). The metal carbonyl complexes 4a, 4b have been isolated and characterized by spectroscopic and compound 4a also by X-ray diffraction techniques. The molecular structure of 4a reveals that the rhodium atom is coordinated by nitrogen and sulfur atoms of the amino-ortho-carboranethiolate ligand, and two carbonyl ligands complete the coordination of the metal atom.

scholarly journals Computational Characterization of Bidentate P-Donor Ligands: Direct Comparison to Tolman’s Electronic Parameters

Molecules ◽  
2018 ◽  
Vol 23 (12) ◽  
pp. 3176 ◽  
Author(s):  
Tímea Kégl ◽  
Noémi Pálinkás ◽  
László Kollár ◽  
Tamás Kégl
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Metal Carbonyl ◽  
Donor Ligands ◽  
Carbonyl Complexes ◽  
Electronic Effects ◽  
Functional Theory ◽  
Metal Carbonyl Complexes ◽  
Electronic Parameters

The applicability of two types of transition-metal carbonyl complexes as appropriate candidates for computationally derived Tolman’s ligand electronic parameters were examined with density functional theory (DFT) calculations employing the B97D3 functional. Both Pd(0)L2(CO) and HRh(I)L2(CO) complexes correlated well with the experimental Tolman Electronic Parameter scale. For direct comparison of the electronic effects of diphosphines with those of monophosphines, the palladium-containing system is recommended. The t r a n s influence of various phosphines did not show a major difference, but the decrease of the H-Rh-P angle from linear can cause a significant change.

Surface-grafted lanthanoid complexes of the tungstosilicate polyanion [SiW12O40]4−: a synthetic, structural and computational investigation

2018 ◽  
Vol 74 (11) ◽  
pp. 1300-1309 ◽  
Author(s):  
Shadi Derakhshanrad ◽  
Masoud Mirzaei ◽  
Atefeh Najafi ◽  
Chris Ritchie ◽  
Antonio Bauzá ◽  
...  
Keyword(s):  
Dicarboxylic Acid ◽  
Intermolecular Interactions ◽  
Density Functional ◽  
Molecular Electrostatic Potential ◽  
Three Dimensional ◽  
Computational Investigation ◽  
X Ray Diffraction ◽  
Functional Theory ◽  
X Ray ◽  
Supramolecular Architectures

As an extension of our continued interest in the preparation of inorganic–organic hybrids, we report the successful hydrothermal synthesis of sodium tris[triaqua(μ-1,10-phenanthroline-2,9-dicarboxylato)dysprosium(III)] silicododecatungstate dodecahydrate, {[DyNa(C14H6N2O4)3(H2O)9(SiW12O40)]·12H2O}nor Na[Dy(PDA)(H2O)3]3[SiW12O40]·12H2O (1), and sodium aqua tris[tetraaqua(μ-4-hydroxypyridine-2,6-dicarboxylato)praseodymium(III)] silicododecatungstate dodecahydrate, {[NaPr(C7H3NO5)3(H2O)13(SiW12O40)]·12H2O}nor Na(H2O)[Pr(pydc-OH)(H2O)4]3[SiW12O40]·12H2O (2) (in which H2PDA is 1,10-phenanthroline-2,9-dicarboxylic acid and H2pydc-OH is 4-hydroxypyridine-2,6-dicarboxylic acid or chelidamic acid). Both compounds have been characterized using elemental analysis, IR spectroscopy and X-ray diffraction methods. Structural characterization by single-crystal X-ray diffraction reveals that these compounds consist of [SiW12O40]4−Keggin-type polyoxometalates (POMs), where a single {W3O13} triad is decorated with a trinuclear Ln complex. Moreover, the decorated polyanions are involved in a series of intermolecular interactions, such as hydrogen bonds and anion–π interactions, resulting in three-dimensional supramolecular architectures. Density functional theory (DFT) studies were conducted to support these intermolecular interactions in both1and2, and have been rationalized using molecular electrostatic potential (MEP) surface calculations.

scholarly journals Photoactivatable metal complexes: from theory to applications in biotechnology and medicine

2013 ◽  
Vol 371 (1995) ◽  
pp. 20120519 ◽  
Author(s):  
Nichola A. Smith ◽  
Peter J. Sadler
Keyword(s):  
Metal Complexes ◽  
Density Functional ◽  
Metal Carbonyl ◽  
Short Review ◽  
Photochemical Reactions ◽  
Carbonyl Complexes ◽  
Functional Theory ◽  
Metal Carbonyl Complexes ◽  
Recent Developments ◽  
Novel Strategy

This short review highlights some of the exciting new experimental and theoretical developments in the field of photoactivatable metal complexes and their applications in biotechnology and medicine. The examples chosen are based on some of the presentations at the Royal Society Discussion Meeting in June 2012, many of which are featured in more detail in other articles in this issue. This is a young field. Even the photochemistry of well-known systems such as metal–carbonyl complexes is still being elucidated. Striking are the recent developments in theory and computation (e.g. time-dependent density functional theory) and in ultrafast-pulsed radiation techniques which allow photochemical reactions to be followed and their mechanisms to be revealed on picosecond/nanosecond time scales. Not only do some metal complexes (e.g. those of Ru and Ir) possess favourable emission properties which allow functional imaging of cells and tissues (e.g. DNA interactions), but metal complexes can also provide spatially controlled photorelease of bioactive small molecules (e.g. CO and NO)—a novel strategy for site-directed therapy. This extends to cancer therapy, where metal-based precursors offer the prospect of generating excited-state drugs with new mechanisms of action that complement and augment those of current organic photosensitizers.

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