Rhodizonate Metal Complexes with a 2D Chairlike M₆ Metal–Organic Framework: [M(C₆O₆)(bpym)(H₂O)]⋅n H₂O

Abstract

Two transition‐metal rhodizonate complexes, [M(C6O6)(bpym)(H2O)]⋅n H2O (M=Cd, n=1; M=Mn, n=2; bpym=2,2′‐bipyrimidine), are reported. Both the rhodizonate and bpym ligands are bis‐bidentate ligands (see the Cd example depicted) which chelate the metal ions, thus forming a novel 2D chairlike M6 metal–organic framework.

μ‐Rhodizonato‐1κO,1:2κO′,2κO′′‐tetra(triphenylphosphine)disilver(I): A Molecular Complex with the [C6O6]2– Ligand Template

“… Coordination mode of literature known rhodizonato complexes [ M = Mn, Cd, L = bipyrimidine, water;8a M = Zn, L = tris(2‐pyridylmethyl)amine] 8b…”

“…Until now only three other examples of rhodizonate transition metal complexes have been published. In 2004 Wang et al presented the first rhodizonate complexes with manganese and cadmium central atoms 8a. The rhodizonate anion acts as bridging ligand in a 1κ 2 O,O',2κ 2 O′′,O′′′ fashion leading to a 2D metal organic framework (under inclusion of bipyrimidine as additional bridging ligand).…”

“…The increased distortion with a torsion angle C1–C2–C3–C4 of –35.9(9)° may be a result of this constrained arrangement and the consequent steric clash of the bulky PPh 3 ligands. The highest torsion angles so far prevail in the structure of the cadmium complex8a (15.0°) and interestingly in the structure of [Pt(mimt) 4 ][C 6 O 6 ] · 4(H 2 O)11a (14.1°), where the rhodizonate anion interacts only in form of hydrogen bonds with the imidazolethione ligands of Pt. However, this has no apparent effect upon the bond lengths in the rhodizonate anion, which are in a well comparable range with the values of the literature known complexes.…”

Isorecticular Synthesis of Dissectible Molecular Bamboo Tubes of Hexarhenium(I) Benzene‐1,2,3,4,5,6‐hexaolate Complexes

“…Interestingly, such a benzenehexaolate (C 6 O 6 6À ) ligand, to our knowledge, has never been reported in any organic compounds or transition-metal complexes and is observed here for the first time. [13] Unlike some similar chelating and bridging organic linkers, the bho 6À and pyridine-derived (Py-R n ) ligands favor the formation of a molecular bamboo-like structure, rather than a gondola, rectangle, or metalloprism. [14] A single-crystal X-ray diffraction analysis revealed that compound 1 crystallizes in the trigonal space group R " 3.…”

Isorecticular Synthesis of Dissectible Molecular Bamboo Tubes of Hexarhenium(I) Benzene‐1,2,3,4,5,6‐hexaolate Complexes

“…Thec ombination of these two ligands (bho 6À and acpy) is chemically and structurally compatible.I np articular, the bho 6À ligand was fortunately captured by six (CO) 3 Re I moieties and six N-donor ligands.Interestingly,such abenzenehexaolate (C 6 O 6 6À )l igand, to our knowledge,h as never been reported in any organic compounds or transition-metal complexes and is observed here for the first time. [13] Unlike some similar chelating and bridging organic linkers,the bho 6À and pyridine-derived (Py-R n )l igands favor the formation of am olecular bamboo-like structure,r ather than ag ondola, rectangle,o rmetalloprism. [14] As ingle-crystal X-ray diffraction analysis revealed that compound 1 crystallizes in the trigonal space group R " 3.…”