Synthesis, Chemistry, and Electronic Structures of Group 9 Metallaboranes

Borthakur, Rosmita; Kar, Sourav; Barik, Subrat Kumar; Bhattacharya, Sandip; Kundu, Gargi; Varghese, Babu; Ghosh, Sundargopal

doi:10.1021/acs.inorgchem.6b02626

Cited by 10 publications

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“…As represented in Figure , compound 10 can be considered as a fusion of a trigonal bipyramid {Ir 4 B} and a square pyramid {Ir 4 B} through a triangular face {Ir 2 B}. The mean Ir–Ir and Ir–B bond distances of 10 of 2.737 and 2.153 Å, respectively, are comparable to those of reported iridaboranes. , The unique boron (B1) of 10 can be considered as a μ 5 -boride boron, which is connected to five iridium atoms. Although various metal-rich boride clusters are known with different structural motifs, they are mostly single-cage clusters.…”

Section: Resultsmentioning

confidence: 80%

Synthesis, Structures, and Bonding of Metal-Rich Metallaboranes Comprising Triply Bridging Borylene and Boride Moieties

et al. 2021

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A series of metal-rich metallaboranes of groups 7 and 9 comprising triply bridging borylene and boride units have been isolated and structurally characterized. Thermolysis of nido-[(RhCp*) 2 B 3 H 7 ] (1; Cp* = η 5 -C 5 Me 5 ) with [Co 2 (CO) 8 ] led to the isolation of tetrametallic [(μ 3 -BH)(RhCp*) 2 (μ-CO)(μ 3 -CO){Co 2 (CO) 4 }] (2), featuring a triply bridging borylene unit, and the trimetallic cluster [(μ 3 -BH)(μ-H)(RhCp*) 2 (μ-CO) 3 {Co(CO)}] (3) that contains a triply bridging hydrido(borylene) unit. The borylene {BH} unit of 2 is coordinated to a deltahedral face of a tetrametallic tetrahedron in a μ 3 fashion. Cluster 3 is a rare example of a tetrahedral metallaborane featuring a hydrido(borylene) unit. In an attempt to synthesize the Mn analogues of 2 and 3, a similar reaction was carried out with [Mn 2 (CO) 10 ] that afforded the trimetallic cluster [(μ 3 -BH)(RhCp*) 2 (μ-CO) 3 {MnH(CO) 3 }] (5) having a triply bridging borylene moiety, the two heterometallic μ 9 -boride clusters [(RhCp*) 3 {Rh(CO)} 3 (μ-CO) 3 {MnH(CO) 3 }B 3 H 2 ] (6) and [(RhCp*) 3 {Mn-(CO) 3 } 2 Rh(CO) 2 B 4 H 3 ] ( 7) and the unusual tetrametallic complex [(RhCp*) 2 (μ-CO) 2 (μ 3 -η 3 -CO 2 ){Mn 2 (CO) 9 }] (8). Clusters 6 and 7 are both unusual heterometallic metal-rich boride clusters, where the boride boron atom is encapsulated inside a tricapped trigonal prism depicting a μ 9 -bonding mode. Compound 8 is a unique example of a metal carbonyl compound in which a CO 2 group is bridging two Rh atoms and one Mn atom in a μ 3 -η 3 fashion. To explore this chemistry with a heavier transition metal, we have carried out the thermolysis of arachno-[IrCp*H 2 (B 3 H 7 )] ( 9) with [Mn 2 (CO) 10 ], which afforded the face-fused iridaborane cluster [(IrCp*) 3 {Ir(CO) 2 } 3 (μ-CO)(μ 3 -CO)B] (10). Compound 10 can also be viewed as a boride cluster, where the naked boron is coordinated to iridium centers in a unique μ 5 coordination mode. All of the compounds have been characterized by 1 H, 11 B, and 13 C NMR spectroscopy and mass spectrometry, and the structures of 2, 3, 5, 6, 8, and 10 have been unambiguously established by crystallographic analyses. Computational studies show that a substantial amount of overlap occurs between the metal frameworks and borylene/boride units.

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Section: Resultsmentioning

confidence: 80%

Synthesis, Structures, and Bonding of Metal-Rich Metallaboranes Comprising Triply Bridging Borylene and Boride Moieties

et al. 2021

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Boron: Polyhedral Metallaboranes

Pathak

Mishra

Ghosh

2022

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Metallaborane clusters and their related chemistry were initially developed as a variant of metal–ligand coordination chemistry much along the lines of organometallic chemistry. However, owing to the insight imparted by the electron counting rules and isolobal analogy principle, the interconnections between apparently distinct molecules like polyhedral boranes and transition metal clusters were established. This certainly defined the scope of the area and notable advances toward the improvement of synthetic routes were witnessed. The advent of improved routes for synthesis widened the purview further by extending the limits of attainable sizes and geometries of polyhedral metallaboranes from diborane analogs to polyhedral cages of up to 12‐vertices to supraicosahedral and condensed cage macro‐polyhedral clusters. Wade–Mingos rules and Jemmis mno rule helped at gaining perspective about the unique structure and bonding present in this class of compounds. This article provides a brief overview of the syntheses and structural aspects in the context of electron counting rules of the most noted structural motifs assumed by polyhedral metallaboranes.

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Metal‐Rich Metallaboranes: Structures and Geometries of Heterometallic µ₉‐Boride Clusters

et al. 2018

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Treatment of a dirhodium analogue of pentaborane(9), [(Cp*Rh) 2 B 3 H 7 ] (nido-1; Cp* = η 5 -C 5 Me 5 ), with [Fe 2 (CO) 9 ] at room temperature led to the formation of [(Cp*Rh) 2 -Fe(CO) 3 (μ-CO)B 3 H 2 Cl] (2) and the metal-rich metallaborane [(Cp*Rh) 2 Fe(CO) 3 Fe(CO) 2 (μ-CO) 2 B 2 H 2 ] (3). When the same reaction was carried out at moderate temperature, two metal-rich metallaboranes, [(Cp*Rh) 3 Fe(CO) 2 (μ 3 -CO) 2 B 2 HX] 4 (X = H) and 5 (X = Cl), and a heterometallic μ 9 -boride cluster, [(Cp*Rh) 3 -(RhCO) 3 Fe(CO) 3 (μ-CO) 3 B 3 H 2 ] (6), were obtained. Compounds 4 and 5 can be viewed as cubane clusters with 62 cluster valence [a] Scheme 1. Synthesis of heterometallic clusters 2-8 and mixed-metal clusters 10 and 11. display a single resonance for the two B-H t protons at δ = 9.16 ppm and a downfield chemical shift at δ = 111.9 ppm for the two chemically inequivalent boron atoms. The IR spectra of 2 and 3 show characteristic bands for B-H t at 2486 and 2454 cm -1 , respectively, which is consistent with previously reported compounds. [15][16][17][18] In addition, the IR spectra show absorption bands for the terminal and bridging carbonyl ligands.The structural compositions of both 2 and 3 were confirmed by single-crystal X-ray crystallographic analysis (Figure 1). Crystals of 2 and 3 were grown by the slow evaporation of hexane under argon. The core structures (octahedral) of 2 and 3 are very similar to those of [(μ 3 -CO)(η 5 of 3 consists of two iron and two boron atoms and the axial positions are occupied by two rhodium atoms. All the metalmetal distances in 3, for example, Fe1-Fe2 of 2.581(3) Å, Fe1-Eur.

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Synthesis, Chemistry, and Electronic Structures of Group 9 Metallaboranes

Cited by 10 publications

References 90 publications

Synthesis, Structures, and Bonding of Metal-Rich Metallaboranes Comprising Triply Bridging Borylene and Boride Moieties

Synthesis, Structures, and Bonding of Metal-Rich Metallaboranes Comprising Triply Bridging Borylene and Boride Moieties

Boron: Polyhedral Metallaboranes

Metal‐Rich Metallaboranes: Structures and Geometries of Heterometallic µ₉‐Boride Clusters

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Synthesis, Chemistry, and Electronic Structures of Group 9 Metallaboranes

Cited by 10 publications

References 90 publications

Synthesis, Structures, and Bonding of Metal-Rich Metallaboranes Comprising Triply Bridging Borylene and Boride Moieties

Synthesis, Structures, and Bonding of Metal-Rich Metallaboranes Comprising Triply Bridging Borylene and Boride Moieties

Boron: Polyhedral Metallaboranes

Metal‐Rich Metallaboranes: Structures and Geometries of Heterometallic µ9‐Boride Clusters

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Metal‐Rich Metallaboranes: Structures and Geometries of Heterometallic µ₉‐Boride Clusters