Octamolybdate-supported tricarbonyl metal derivatives: [{H2Mo8O30}{M(CO)3}2]8− (M = MnI and ReI)

Abstract

Two novel octamolybdate-based tricarbonyl metal derivatives have been successfully synthesized and characterized, which represent the first two examples of tricarbonyl metal groups attached to a new {Mo(8)O(30)} building block.

A Monomeric Tricobalt(II)-Substituted Dawson-Type Polyoxometalate Decorated by a Metal Carbonyl Group: [P2W15O56Co3(H2O)3(OH)3Mn(CO)3]8–

“…The {Mn­(CO) 3 } unit and Co 3 O 6 “crown” are connected by three bridged O atoms, notably, forming a mixed-metal cubane motif, {MnCo 3 O 4 } (Figure e). The {MnCo 3 O 4 } cubane is similar to that of the {MnM 3 O 4 } subunit of the {H 2 M 8 O 30 (Mn­(CO) 3 ) 2 } (M = Mo/W) polyanion reported by our group. , The special structure is related to the kinetically stable d 6 low-spin octahedral 18-electron moieties fac -[(OC) 3 ML 3 ] + (M = Mn/Re), containing metal tricarbonyl units bonded to a trigonal adjacent O atoms on the surface of POMs. It is worth mentioning that, like the capping WO 6 in the Ni-containing Dawson-type analogue [Ni 3 ­(OH) 3 ­(H 2 O) 3 ­P 2 W 16 ­O 59 ] 9– , reported by Hill’s group in 2016, the Mn­(CO) 3 fragment also plays a role of the stabilizing the Dawson-like {P 2 W 15 Co 3 O 62 } unit, which is the key factor of the constitution of monomeric low-valent transition-metal-substituted POMs with the well-known [P 2 W 15 O 56 ] 12– ligand.…”

Facile CO2 Cycloaddition to Epoxides by Using a Tetracarbonyl Metal Selenotungstate Derivate [{Mn(CO)3}4(Se2W11O43)]8–

“…Interestingly, this grafting fashion of a [Mn­(CO) 3 ] + pendant (Mn2, Mn3, Mn4) connecting to a POM unit via bridging oxygen atoms is different from the most reported compounds . As previously researched, the [M­(CO) 3 ] + (M = Mn, Re, and Rh) moiety is generally attached to a trigonal adjacent O atoms on the surface of POMs, forming kinetically stable d 6 low-spin octahedral 18-electron moiety fac -[(OC) 3 ML 3 ] + (L = ligand). , The bonding of the [M­(CO) 3 ] + fragment to a triangle of bridging oxygen atoms is usually the rule within PMCDs. , In this structure, only Mn1 is bonded to a POM unit via three μ 3 -O atoms (O4, O17, and O26) in a similar way to the reported compounds.…”

Spontaneous Resolution upon Crystallization of 3D, Chiral Inorganic Networks Assembled from Achiral, Polyoxometallate Units and Metal Ions

“…Polyoxometalates (POMs) are compounds which constitute a unique class of metal oxide clusters with interesting properties, finding applications in medicine, biology, magnetism, materials science, and catalysis as well as acting as precursors for synthesis of organometallic derivatives . The assembly of purely inorganic POM-based frameworks occupies high potentiality for the synthesis of new porous materials which combine the thermodynamic stability of zeolites and mesoporous silicas .…”