Synthese von [LRe(CO)_{3]⁺-Komplexen mit makrocyclischen Liganden Die Kristallstrukturen von 1,4,7-Triazacyclononan-tricarbonylrhenium( I)-thiocyanat und 1,4,7-Trithiacyclononan-tricarbonylrhenium( I) -bromid-hemihydrat / Synthesis of [LRe(CO)3]⁺ Complexes with Macrocyclic Ligands The Crystal Structures of 1,4,7-Triazacyclononane-tricarbonyl-rhenium(I) Thiocyanate and of 1,4,7-Trithiacyclononane-tricarbonyl-rhenium(I) Bromide Hemihydrate}

Abstract

<jats:p>The tridentate macrocyclic ligands 1,4,7-triazacyclononane, its thia analogue 1,4,7-trithiacyclononane, 1-oxa-4,7-diazacyclononane, and N,N′,N″-trimethyl-1 ,4,7-triazacyclononane react with Re(CO)<jats:sub>5</jats:sub>Br in dimethylformamide to yield colorless, air-stable [LRe(CO)<jats:sub>3</jats:sub>]Br complexes (L = tridentate macrocycle). With Mn(CO)<jats:sub>5</jats:sub>Br only the cyclic amines react to afford yellow-orange [LMn(CO)<jats:sub>3</jats:sub>]Br complexes whereas 1,4,7-trithiacyclononane does not give stable complexes of manganese. The crystal structures of [([9]aneN<jats:sub>3</jats:sub>)Re(CO)<jats:sub>3</jats:sub>](NCS) and [([9]aneS<jats:sub>3</jats:sub>)Re(CO)<jats:sub>3</jats:sub>]Br · 1/2 H<jats:sub>2</jats:sub>O have been determined. The former crystallizes in the orthorhombic space group P bca (a = 12/763(4), b = 12.662(5), c = 17.472(9) Å; Z = 8); whereas the latter crystallizes in the monoclinic space group P2<jats:sub>1</jats:sub>/c (a = 9.444(1). b = 11.797(2), c = 28.095(3) Å. β = 90,86(1); Z = 8).</jats:p>

Synthesis and structural characterization of rhenium(I) tricarbonyl complexes with the bidentate ligands o-(diphenylphosphino)benzaldehyde (P∩O) and o-[(diphenylphosphino)benzylidene]analine (P∩N)

“…2035, 1940 and 1935 cm −1 ). This can undoubtedly be explained by the stronger metal-to-carbonyl back-bonding in the imine phosphine complexes [37]. The appreciable coupling t o the phosphorus atom [38] exhibited by the aldehyde proton (complexes 1 and 2) and imine proton (complexes 3 and 4) expected as doublets) is the most remarkable aspect of the 1 H NMR spectra.…”

Cation Exchange Strategy for the Encapsulation of a Photoactive CO-Releasing Organometallic Molecule into Anionic Porous Frameworks

“…(1,4,7-Triazacyclononane)­tricarbonylmanganese­(I) bromide, [Mn­(C 6 N 3 H 15 )­(CO) 3 ]Br (ALF472), was prepared by Alfama Ltd. according to the method previously described by Wieghardt . The analytically pure compound has two strong absorptions in the FITR spectrum at ν CO 2017 and 1895 cm –1 (Figure ).…”

“…Taking into account all the above information, here we present the encapsulation of the photoactive, nontoxic, water-soluble, and air-stable cationic CORM [Mn­(tacn)­(CO) 3 ]Br (tacn = 1,4,7-triazacyclononane), also known as ALF472, into different inorganic porous matrixes, namely, the metal-organic framework bio-MOF-1, (NH 2 (CH 3 ) 2 ) 2 ­[Zn 8 (adeninate) 4 ­(BPDC) 6 ]·8DMF·11H 2 O (BPDC = 4,4′-biphenyldicarboxylate), and the functionalized mesoporous silicas MCM-41-SO 3 H and SBA-15-SO 3 H (Figure ), by means of a simple ion exchange strategy. We have selected the above porous materials as they are biocompatible and exhibit anionic frameworks with adequate pore size (0.52, 3.91, and 5.83 nm in bio-MOF-1, MCM-41-SO 3 H, and SBA-15-SO 3 H, respectively) , in which the loading and retention of the cationic CORM [Mn­(tacn)­(CO) 3 ] + (ALF472 + ) can be optimized by a cation exchange strategy in order to study the kinetics of CO release by activation with visible light.…”

Investigation of Cyclam Based Re‐Complexes as Potential Electrocatalysts for the CO2Reduction Reaction

“…The IR spectra of complexes Re{N 4 }, Re{N 2 S 2 }, Re{i-N 4 }, Re{i-SN 3 } and Re{i-ON 3 } reveal a similar band structure in the carbonyl region, with a sharp band over 2000 cm À 1 and a broad band around 1900 cm À 1 , which is characteristic for [Re(L)(CO) 3 ] + fac-isomers (Figure 2). [46] However, within the different rhenium complexes there are small alterations in the general band structure, that can be explained by the different donor atom sets and the differently distorted octahedron geometries. While for all k 3 -N complexes Re{N 4 }, Re{i-N 4 } and Re{i-ON 3 } the sharp CO band is observed at~2014 cm À 1 , for the k 3 -S/N complexes Re{i-SN 3 } (2019 cm À 1 ) and Re{N 2 S 2 } (2027 cm À 1 ) the same CO band is observed at higher wavenumbers with increasing sulfur content.…”

“…Notably, besides the synthesis and characterization of [Re(tacn)(CO) 3 ] + (3, tacn = 1,4,7-triaazacyclo-nonane) and its N/S or N/O heteroatom replaced derivatives, there are no studies on rhenium tricarbonyl complexes comprising azamacrocyclic ligands (Scheme 1). [45][46][47] We thus herein present the synthesis and characterization of a novel series of cyclam based rhenium tricarbonyl complexes and their electrochemical properties.…”