New Trinuclear Complexes of Group 6, 8, and 9 Metals with a Triply Bridging Borylene Ligand

Yuvaraj, K.; Bhattacharyya, Moulika; Prakash, Rini; Ramkumar, V.; Ghosh, Sundargopal

doi:10.1002/chem.201600637

Cited by 19 publications

(19 citation statements)

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“…In this connection, we have found that the reactions of preformed nido- and arachno- metallaboranes with metal carbonyls are the most effective ways to synthesize metal-rich metallaboranes featuring boride and borylene units. Using this synthesis approach, we have isolated a series of metal-rich metallaboranes. ,, As a result, we have explored the reactivity of nido -[(RhCp*) 2 (B 3 H 7 )] and arachno -[IrCp*H 2 (B 3 H 7 )] with metal carbonyls, such as [Co 2 (CO) 8 ] and [Mn 2 (CO) 10 ], that yielded metal-rich metallaboranes with diverse geometries and bonding features. Herein, we account for the synthesis, structure, and bonding of various clusters having borylene and boride units.…”

Section: Introductionmentioning

confidence: 99%

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: Introductionmentioning

confidence: 99%

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

et al. 2021

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“…The average Ru–B lengths observed in the known μ 3 -borylene ligand on Ru 3 clusters (average 2.12 Å) is close to the sum of the covalent radii. ,,− The averages of the Ru–Al and Ru–Ga lengths in congeneric [{Cp*Ru(μ-H)} 3 (μ 3 -AlEt)] (2.481 Å) , and [{Cp*Ru(μ-H)} 3 (μ 3 -GaMe)] (2.475 Å) also correspond to the sum of the covalent radii, respectively (RuAl 2.51 Å, RuGa 2.49 Å) …”

Section: Results and Discussionmentioning

confidence: 67%

Synthesis and Properties of a Triruthenium Hydrido Complex Capped by a μ₃-Oxoboryl Ligand

et al. 2019

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A triruthenium hydrido complex in which one of the Ru3 planes is capped by a μ3-BO ligand, [{Cp*Ru(μ-H)}3(μ3-BO)(μ3-H)] (3; Cp* = η5-C5Me5), was synthesized by the reaction of the μ3-borylene complex [{Cp*Ru(μ-H)}3(μ3-BH)] (2a) with water in the presence of Et2NH. The face-capping coordination of the oxoboryl ligand was unambiguously established by X-ray diffraction and exhibited short B–O (1.231(6) Å) and long Ru–B bonds (average 2.31 Å). Density functional theory (DFT) calculations of 3 reproduced the observed structure well, and the multiplicity of the BO bond suggested by the value of the Wiberg bond index is 1.62. The four hydrido ligands in 3, three μ-hydrides and one μ3-hydride, underwent site exchange on the NMR time scale via the formation of a μ3-hydroxyborylene intermediate, [{Cp*Ru(μ-H)}3(μ3-BOH)] (2c). The DFT calculations showed that 2c lies above 3 by 10.5 kcal mol–1 at 25 °C. The basic oxygen atom in 3 allowed the formation of a B(C6F5)3 adduct, [{Cp*Ru(μ-H)}3{μ3-BO···B(C6F5)3}(μ3-H)] (5), in which the site exchange of hydrides was retarded considerably. Complex 3 reacted with PMe3 and CO to afford [(Cp*Ru)3(μ-BO)(μ-H)3(μ3-H)(PMe3)] (6) and [{Cp*Ru(CO)}3(μ-BO)(μ-H)2] (7), respectively, which demonstrated that the coordination mode of the BO ligand changed from a face-capping to an edge-bridging mode at the Ru3 site.

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“…The mass spectrum of 4 shows a molecular ion peak at m/z = 944.9796 ([M + K] + ), which is 18 mass units less than that of 5 ( m/z = 962.9697; [M + Na] + ). The downfield 11 B{ 1 H} chemical shifts of 4 ( δ = 116.6 and 110.3 ppm) and 5 ( δ = 111.8 and 94.7 ppm) indicate the presence of a triply bridging borylene unit , . Apart from the Cp* protons, the 1 H NMR spectra also reveal the characteristic signals of B–H t protons ( 4 : δ = 9.34 and 10.04 ppm; 5 : δ = 9.91 ppm).…”

Section: Resultsmentioning

confidence: 98%

“…Hence, chemists are often interested in isolating discrete, closed transition‐metal boride clusters in a systematic synthetic way. It is evident that cluster expansion reactions of transition‐metal carbonyl compounds with metallaboranes have often yielded interesting compounds , , , , , , , . To study the effect of metal carbonyl fragments in metallaborane clusters, we performed the thermolysis of nido ‐ 1 with [Fe 2 (CO) 9 ] at a moderate temperature, which led to the isolation of 6 together with the formation of 4 and 5 (Scheme a).…”

Section: Resultsmentioning

confidence: 99%

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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New Trinuclear Complexes of Group 6, 8, and 9 Metals with a Triply Bridging Borylene Ligand

Cited by 19 publications

References 107 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

Synthesis and Properties of a Triruthenium Hydrido Complex Capped by a μ₃-Oxoboryl Ligand

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

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New Trinuclear Complexes of Group 6, 8, and 9 Metals with a Triply Bridging Borylene Ligand

Cited by 19 publications

References 107 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

Synthesis and Properties of a Triruthenium Hydrido Complex Capped by a μ3-Oxoboryl Ligand

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

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Synthesis and Properties of a Triruthenium Hydrido Complex Capped by a μ₃-Oxoboryl Ligand

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