Structural and DFT/TD-DFT investigation of tris(bidentate) complexes of rhenium(III) synthesized from the cis-[ReO2]+ core and benzenethiol derivatives

Zeitschrift Für Kristallographie - New Crystal Structures

et al. 2015

Source of materialThecompoundwas obtained upon reacting Re(CO) 5 Cl with the pyridine-derived ligand in toluene. Crystals suitable for the diffraction study were obtained upon free evaporation of the solvent at ambient conditions. Experimental detailsCarbon-bound Hatomswere placed in calculated positions (C-H 0.95 Å) and were included in the refinement in the riding model approximation, with U iso (H) setto1.2U eq (C). The Hatoms of the methyl groups were allowed to rotate with afixed angle around the C-C bond to best fit the experimental electron density (HFIX 137 in the SHELX program suite [10]), with U iso (H) sett o 1.5U eq (C). The disorder among the chlorine and carbonyl ligands was modelled applying SADI instructions. DiscussionNext to cardiovascular diseases, cancer has become one of the main fatal diseases in industrialized countries. Apart from classicalsurgery,chemo-and radiotherapeutic treatments have entered the arsenal of possible cures for certain types of cancer. All methods, however, suffer from theirown setofproblematic side-effects and, as ac onsequence, the development of radiopharmaceuticals -combining the advantages of chemotherapy as well as radiation methods while at the sametimeavoiding their unique respective undesiredside-effects -has been atopic of research [1,2].T ailoring andf ine-tuning of thee nvisionedr adiopharmaceuticals' properties such as lipophilicityand,inparticular, inertness is of paramountimportancewithrespect to possible future in vivo applications in contemporary medicine and requires sound knowledge about structural parameters of the ligands applied if a more heuristic approach in the synthesis is to triumph over pure trial-and-error as it is encountered in this specific field of coordination chemistry up to the present day. In addition, the spatial requirements of pharmaceuticals are of importance as this factor influences on their interaction with enzymatic systems and, as a consequence,t he pathway and rate of conjugation, functionalization and secretion from the body. In continuation of our ongoing research on the field of rhenium coordination compounds, the title compound was synthesized and its molecular and crystal structure were elucidated [3]. Thec rystal structures of severalo ther rheniumcoordinationc ompounds featuring parasubstituted pyridine derivatives in the ligand sphere are apparent in the literature [4][5][6][7][8] next to thec ompound derivedf rom unsubstituted pyridine [7]. The title compound is arhenium(I) coordination compound. The central atom is hexacoordinate. The octahedral coordination sphere is comprised of one chlorido ligand and three carbonyl groups in fac configuration as well as two pyridine-derived ligands bearing dimethylamino-substituents in para position to the respective intracyclic nitrogen atom. The coordination of the latter two ligands is effected by the two nitrogen atomsofthe aromatic moieties. The chlorido as well as its trans-configured carbonyl ligand show positional disorder in a ratio of approximately 0.55:0.45. The le...

Section: Discussionmentioning

confidence: 99%

Crystal structure of fac-tricarbonyl-chlorido-bis(para-N’,N’-dimethyl-κ- N-pyridyl)rhenium(I) toluene (1:1), C24H28ClN4O3Re

Schmitt

Zeitschrift Für Kristallographie - New Crystal Structures

et al. 2015

“…Apart fromclassical surgery,chemo-and radiotherapeutic treatments have entered the arsenal of possible cures for certain types of cancer. All methods, however, suffer from theirown setofproblematic side-effects and, as ac onsequence, the development of radiopharmaceuticals -combining the advantages of chemotherapy as well as radiation methods while at the sametimeavoiding their unique respectivendesiredside-effects -has been atopic of research [1,2]. Tailoring and fine-tuning of the envisioned radiopharmaceuticals' properties such as lipophilicity and, in particular, inertness is of paramount importance with respect to possible future in vivo applications in contemporary medicine and requires sound knowledge about structural parameters of the ligands applied if a more heuristic approach in the synthesis is to triumph over pure trial-and-error as it is encountered in this specific field of coordination chemistry up to the present day.…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of tris(ortho-phenylenediamide-N,N’)-rhenium(VII) bromide, C18H18BrN6Re

Habarurema

Zeitschrift Für Kristallographie - New Crystal Structures

et al. 2015

C 18 H 18 BrN 6 Re, monoclinic, P2 1 /n (no. 14), a =11.0894 ( Source of materialThe title compound was prepared upon reacting ReBr 3 (dab)(PPh 3 ) 2 (dab =1 ,2-diaminobenzene) with the symmetric two-fold Schiff-base derived from 1,3-diamino-propan-2-ol and 2-hydroxy-benzaldehyde in ethanol. Crystals suitable for the diffraction study were obtained upon free evaporation of the solvent at ambient conditions. Experimental detailsCarbon-bound Hatomswere placed in calculated positions (C-H 0.95 Å) and were included in the refinementinthe riding model approximation, with U iso (H) setto1.2U eq (C). All nitrogen-bound Ha toms were locatedo nad ifferenceF ourier mapa nd refined freely using DFIX instructions, the N-H distances set to 0.88 Å. DiscussionNext to cardiovascular diseases, cancer has become one of the main fatal diseases in industrialized countries. Apart fromclassical surgery,chemo-and radiotherapeutic treatments have entered the arsenal of possible cures for certain types of cancer. All methods, however, suffer from theirown setofproblematic side-effects and, as ac onsequence, the development of radiopharmaceuticals -combining the advantages of chemotherapy as well as radiation methods while at the sametimeavoiding their unique respectivendesiredside-effects -has been atopic of research [1,2]. Tailoring and fine-tuning of the envisioned radiopharmaceuticals' properties such as lipophilicity and, in particular, inertness is of paramount importance with respect to possible future in vivo applications in contemporary medicine and requires sound knowledge about structural parameters of the ligands applied if a more heuristic approach in the synthesis is to triumph over pure trial-and-error as it is encountered in this specific field of coordination chemistry up to the present day. In addition, the spatial requirements of pharmaceuticalsa re of importance as this factor influences on their interaction with enzymatic systems and, as a consequence, thep athway and rateo fc onjugation, functionalization and secretion from the body. In continuation of our ongoing research on the field of rhenium coordination compounds, the coordination of amultidentate ligand towards arhenium(V) startingm aterial was attempted [3].As tructural analysis of the crystalline reaction product showed the formation of an unexpected product. The crystal structures of two other comparable rhenium coordination compounds as found in the current reaction product are apparent in the literature [4].T he compound is ahomoleptic rhenium(VII) coordination compound featuringt hree chelating ortho-phenylenediamine ligands that are invariably two-folddeprotonated. The positive charge of the coordination unit is balanced by ab romide anionpresent in the crystal structure. Ac onformational analysis of the fivemembered chelate rings according to Cremer &Pople [5]shows the latter to invariably adopt E 1 conformations on the rhenium atom [6].R e-N bond lengthsc over an arrowr ange of 1.991(2)-2.0106(19) Åonly.The least-squares planes as defined by...

“…Apart fromclassical surgery,chemo-and radiotherapeutic treatments have entered the arsenal of possible cures for certain types of cancer. All methods, however, suffer from theirown setofproblematic side-effects and, as ac onsequence, the development of radiopharmaceuticals -combining the advantages of chemotherapy as well as radiation methods while at the sametimeavoiding their unique respectiveundesiredside-effects -has been atopic of research [1,2].T ailoring andf ine-tuning of thee nvisionedr adiopharmaceuticals' properties such as lipophilicityand,inparticular, inertness is of paramountimportancewithrespect to possible future in vivo applications in contemporary medicine and requires sound knowledge about structural parameters of the ligands applied if a more heuristic approach in the synthesis is to triumph over pure trial-and-error as it is encountered in this specific field of coordination chemistry up to the present day. In addition, the spatial requirements of pharmaceuticalsa re of importance as this factor influences on their interaction with enzymatic systems and, as a consequence,t he pathway andr ateo fc onjugation, functionalizationand secretionfromthe body.…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of (μ2-acetato-κ2O,O’)-(μ2-bromido)-(μ2-oxido)-tetrabromido- triphenylphosphane-κP-triphenylphosphaneoxide-κOdirhenium( IV)), C38H33Br5O4P2Re2

Mukiza

Zeitschrift Für Kristallographie - New Crystal Structures

et al. 2015

C 38 H 33 Br 5 O 4 P 2 Re 2 ,triclinic, P1 (no.2), a =10.7759(5) Å, b =13.4635(6) Å, c =14.7580(7) Å, a =93.642(2)°, b =108.372(2)°, g =91.303(2)°, V =2025.8Å 3 ,Z=2, R gt (F) =0.0207, wR ref (F 2 ) =0.0492, T =200 K. Source of materialThec ompoundw as obtained upon reacting 1,2,3,6-tetrahydro-2,6-dioxopyrimidine-4-carboxylic acid with ReBr 3 O(PPh 3 ) 2 in benzene/acetonitrile.C rystalss uitablef or thed iffractions tudy were obtained upon free evaporation of thes olvent at ambient conditions. Experimental detailsCarbon-bound Hatomswere placed in calculated positions (C-H 0.95 Å) and were included in the refinementinthe riding model approximation, with U iso (H) setto1.2U eq (C). The Hatoms of the methyl group were allowed to rotate with afixed angle around the C-C bond to best fit the experimental electron density (HFIX 137 in the SHELX program suite [12]), with U iso (H) setto1.5U eq (C). DiscussionNext to cardiovascular diseases, cancer has become one of the main fatal diseases in industrialized countries. Apart fromclassical surgery,chemo-and radiotherapeutic treatments have entered the arsenal of possible cures for certain types of cancer. All methods, however, suffer from theirown setofproblematic side-effects and, as ac onsequence, the development of radiopharmaceuticals -combining the advantages of chemotherapy as well as radiation methods while at the sametimeavoiding their unique respectiveundesiredside-effects -has been atopic of research [1,2].T ailoring andf ine-tuning of thee nvisionedr adiopharmaceuticals' properties such as lipophilicityand,inparticular, inertness is of paramountimportancewithrespect to possible future in vivo applications in contemporary medicine and requires sound knowledge about structural parameters of the ligands applied if a more heuristic approach in the synthesis is to triumph over pure trial-and-error as it is encountered in this specific field of coordination chemistry up to the present day. In addition, the spatial requirements of pharmaceuticalsa re of importance as this factor influences on their interaction with enzymatic systems and, as a consequence,t he pathway andr ateo fc onjugation, functionalizationand secretionfromthe body. In continuation of our ongoingresearchonthe fieldofrheniumcoordinationcompounds [1, 2],t he coordination of am ultidentate ligand towards ar henium(V) starting material was attempted. Astructural analysis of the crystalline reaction product showed the formation of an unexpected product. Thecrystalstructures of three very similar compounds -namelythe chloroform solvate of achlorido compound [3] as well as the pertaining mono-propionato [4]a nd the dipropionato version of the latter [5]-are apparent in the literature. The title compound is adinuclear rhenium(IV) complex. Excluding the Re-Re bond, the coordination sphere around both central atomsi so ctahedral and consists of one triphenylphosphane ligand and two bromido ligands -that exclusively act as monodentate ligands -a sw ell as one bridging oxido, ab ridging bromido and abri...