Synthesis, Structure, Bonding, and Reactivity of Metal Complexes Comprising Diborane(4) and Diborene(2): [{Cp*Mo(CO)2}2{μ‐η2:η2‐B2H4}] and [{Cp*M(CO)2}2B2H2M(CO)4], M=Mo,W

Mondal, Bijan; Bag, Ranjit; Ghorai, Sagar; Bakthavachalam, K.; Jemmis, Eluvathingal D.; Ghosh, Sundargopal

doi:10.1002/ange.201803154

Cited by 16 publications

(7 citation statements)

References 70 publications

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“…The corresponding dihedral angle between the planes M 2 M ′ and MB 2 in the reported pileo-trimetallic metallaboranes ranges from 114 to 119 • (Table 1). and Ru-Mo (2.849 Å) bond lengths are in accordance with those reported in molybdaboranes [52,58]. Also, the average Mn-Ru (2.768 Å) and Mn-B (2.236 Å) bond distances in 4 are in the range of those reported for the related clusters [59,60].…”

Section: Synthesis Of the Pileo-heterotrimetallic Clusters [(Cp*ru)2m...supporting

confidence: 87%

“…The orientation in 2 is similar to pileo-[(Cp*Rh) 2 {Cr(CO) 3 }(µ-CO)(µ 3 -BH)B 2 H 4 ] [47], whereas in 4, it is similar to that in pileo- [52]. In 2, the average Mo-B (2.383 Å) and Ru-Mo (2.849 Å) bond lengths are in accordance with those reported in molybdaboranes [52,58]. Also, the average Mn-Ru (2.768 Å) and Mn-B (2.236 Å) bond distances in 4 are in the range of those reported for the related clusters [59,60].…”

Section: Synthesis Of the Pileo-heterotrimetallic Clusters [(Cp*ru)2m...supporting

confidence: 80%

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Metal Rich Metallaboranes: Synthesis, Structure and Bonding of pileo-[(Cp*Ru)2M(CO)3(µ-H)(µ-E)(µ3-BH)B2H5] (M = Mo, W, E = CO, and M = Mn, E = H) Clusters

Pradhan,

Jaiswal,

Cordier

et al. 2023

Inorganics

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The synthesis and structural characterization of a series of heterotrimetallic ruthenaborane clusters are reported. The photolytic reaction of nido-[(Cp*Ru)2(µ-H)2B3H7] (nido-1) (Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl) with [M(CO)5·THF] (THF = tetrahydrofuran, M = Mo and W) yielded the heterotrimetallic clusters pileo-[(Cp*Ru)2{M(CO)3}(µ-CO)(µ-H)(µ3-BH)B2H5], M = Mo (2), W (3) and the known arachno ruthenaboranes [1,2-(Cp*Ru)(Cp*RuCO)(µ-H)B3H8] (I) and [{Cp*Ru(CO)}2B2H6] (II). In an attempt to synthesize the Mn-analog of 2 and 3, we performed a similar reaction of nido-1 with [Mn2(CO)10], which afforded the heterotrimetallic pileo-[(Cp*Ru){Mn(CO)3}(µ-H)2(µ3-BH)B2H5] (4) cluster along with the reported trimetallic hydrido(hydroborylene) species [(Cp*Ru)2{Mn(CO)3}(µ-H)(µ-CO)3(µ-BH)] (III). Ruthenaboranes 2, 3 and 4 are isoelectronic and isostructural. The geometry of 2–4 can be viewed as a triangle face-fused square pyramidal and tetrahedral geometry, in which the apical vertex of the tetrahedron is occupied by a µ3–BH moiety. All of these pileo ruthenaborane clusters obey Mingos’ fusion formalism. Clusters 2–4 were characterized using multinuclear NMR, IR spectroscopies and electrospray ionization mass spectrometry. The single-crystal X-ray diffraction studies of clusters 2 and 4 confirmed their structures. Further, density functional theory (DFT) studies of these pileo ruthenaboranes have been carried out to investigate the nature of bonding, fusion and electronic structures.

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Section: Synthesis Of the Pileo-heterotrimetallic Clusters [(Cp*ru)2m...supporting

confidence: 87%

Section: Synthesis Of the Pileo-heterotrimetallic Clusters [(Cp*ru)2m...supporting

confidence: 80%

Metal Rich Metallaboranes: Synthesis, Structure and Bonding of pileo-[(Cp*Ru)2M(CO)3(µ-H)(µ-E)(µ3-BH)B2H5] (M = Mo, W, E = CO, and M = Mn, E = H) Clusters

Pradhan,

Jaiswal,

Cordier

et al. 2023

Inorganics

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“…17 18 Recently we have reported the first bimetallic diborane(4) compound [{Cp*Mo(CO) 2 } 2 {μ-η 2 :η 2 -B 2 H 4 }] from the reaction of [(Cp*Mo) 2 (μ-Cl) 2 B 2 H 6 ] with carbon monoxide gas at ambient temperature. 19 In a different strategy, with the objective of isolating a heterometallic lower borane species, we explored the reaction of arachno-[2-{Cp*Ru(PPh 3 )B 3 H 8 }] (PPh 3 = triphenylphosphine) (2) with [Fe 2 (CO) 9 ]. The reaction afforded a triborane(6) analogue (3), confined in Ru and Fe templates.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Using this strategy, we have isolated a saturated linear triborane(7) species, [{Cp*Mo(CO)} 2 {μ-η 3 :η 3 -B 3 H 7 }] (Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl) stabilized by two Cp*Mo fragments from the reaction of in situ generated intermediate, synthesized from the reaction of [Cp*Mo(CO) 3 Me] and [LiBH 4 ·THF] (THF = tetrahydrofuran) with an excess of [BH 3 ·THF] . Recently we have reported the first bimetallic diborane(4) compound [{Cp*Mo(CO) 2 } 2 {μ-η 2 :η 2 -B 2 H 4 }] from the reaction of [(Cp*Mo) 2 (μ-Cl) 2 B 2 H 6 ] with carbon monoxide gas at ambient temperature . In a different strategy, with the objective of isolating a heterometallic lower borane species, we explored the reaction of arachno -[2-{Cp*Ru(PPh 3 )B 3 H 8 }] (PPh 3 = triphenylphosphine) ( 2 ) with [Fe 2 (CO) 9 ].…”

Section: Introductionmentioning

confidence: 99%

Diborane and Triborane Species in the Coordination Sphere of Group-8 Transition Metals

Pradhan,

Bairagi,

Ghosh

2023

Inorg. Chem.

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The synthesis and structural elucidation of a series of ruthenium diborane and triborane compounds are described. Treatment of [Cp*Ru(PPh 3 ) 2 Cl] (1) (Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl; PPh 3 = triphenylphosphine) with [BH 3 •THF] (THF = tetrahydrofuran) at 60 °C led to the formation of the hydrogen-rich ruthena-octahydrotetraborane arachno-[2-{Cp*Ru(PPh 3 )B 3 H 8 }] (2). The chemistry of 2 is explored with [Fe 2 (CO) 9 ] at room temperature, which resulted in the formation of a metal-stabilized triborane species, [{Cp*Ru(PPh 3 )}(μ 3η 1 :η 2 :η 2 -B 3 H 6 ){Fe 2 (CO) 7 }] (3). Compound 3 can be considered as a triborane analogue [B 3 H 6 ] 3− that stabilizes in the coordination sphere of two iron and one ruthenium atoms. Further, the photolysis of nido-[1,2-(Cp*Ru) 2 (μ-H) 2 (B 3 H 7 )] (4) with [M(CO) 5 •THF] (M = Mo and W) afforded an arachno-[1,2-(Cp*Ru)(Cp*RuCO)(μ-H)(B 3 H 8 )] (5), in which the [M(CO) 5 •THF] acted as a CO source. In an attempt to convert arachno-5 into a closo or nido species, we have pyrolyzed arachno-5 in toluene at 90 °C for 20 h that afforded nido-[2,3-(Cp*Ru) 2 (μ-CO)(μ 3 -H)(B 3 H 6 )] (6) having two ruthenium atoms at the basal position. Irradiation of arachno-5 with an intermediate generated from CS 2 and [LiBH 4 •THF] in THF afforded the diborane(5) species [(Cp*RuCO)(Cp*Ru)(μ-H)(μ-η 1 :η 2 -B 2 H 4 )(CS 2 H)] ( 7) in which a dithioformato ligand (SHC�S) is attached to one Ru−B bond. Compound 7 can be considered as a diborane(5) species, which is stabilized by a dithioformato ligand. All the synthesized compounds have been characterized by employing electrospray ionization-mass spectrometry, multinuclear NMR, and IR spectroscopy techniques. The single-crystal X-ray diffraction studies of compounds 2, 3, 6, and 7 helped to establish the structural integrity of these compounds. Further, density functional theory studies were performed to provide insight into the bonding of these metal-stabilized diborane and triborane species.

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“…To the best of our knowledge, the numbers of linear triboranes are very limited except for some structurally characterized B 3 H 8 -metal clusters. To isolate such a kind of species, transition metal coordination spheres are considered to be one of the key templates that can stabilize the unstable reactive motifs. , For example, recently we have isolated a classical [B 2 H 5 ] − ion stabilized by a binuclear tantalum template . Subsequently, we have isolated a triborane analogue {B 3 H 6 SePh} which is also stabilized in the coordination sphere of {Cp*Ta} 2 .…”

Section: Introductionmentioning

confidence: 99%

Structures and Bonding of Early Transition Metallaborane Clusters

et al. 2022

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Structures and bonding of various homo and heterometallic metallaborane clusters are described which are stabilized in the coordination sphere of early transition metals. For example, the bimetallic triborane species, [{Cp*Mo(CO)}2{µη 3 :η 3 -B3H7}], 2 has been synthesized from the pyrolysis of an in situ generated intermediate, produced from the reaction of [Cp*Mo(CO)3Me], 1 and [LiBH4•THF], with an excess amount of [BH3•THF]. Superficially cluster 2 is isostructural but not isoelectronic with [(Cp*MoCl)2B3H7] (I). Both clusters 2 and I contain a bimetallic template bridged by {B3H7} moiety. Cluster 2 is denoted as a unique saturated and unsubstituted closo bimetallic B3H7 cluster. Theoretical output implies that saturation in such clusters brings thermodynamic stability. Further, we have developed a new strategy for the synthesis of various heterometallic metal-rich metallaborane clusters. For example, pyrolysis of an intermediate, obtained from the reaction of [Cp*MoCl4], 4 and [LiBH4•THF], with cobalt and iron carbonyl compounds yielded triply bridging hydrido(hydroborylene), [{Cp*Mo(CO)2}2Co(CO)3BH(μ-H)], 5, tetrametallic μ4-boride, [{Cp*Mo(CO)2}2(μ4-B)(μ-H){Co2(CO)5}], 6, triple decker complex, [(Cp*Mo)2{µ-η 6 :η 6 -B4H4Co2(CO)5}(μ-H)2], 7, metal-rich dimolybdaborane cluster, [(Cp*Mo)2Co2(CO)3(μ-CO)3B3H3(μ-H)2], 8 and mixed-metal cluster, [(Cp*Mo)2B4H8Fe(CO)3], 9. All the molecules have been characterized by 1 H, 11 B{ 1 H}, and 13 C{ 1 H} NMR spectroscopy; mass spectrometry; infrared (IR) spectroscopy and single-crystal X-ray diffraction studies for clusters 2 and 5-9. The electron counting rules and density functional theory (DFT) calculations provided further insight into the bonding and electronic structures of these clusters.

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Synthesis, Structure, Bonding, and Reactivity of Metal Complexes Comprising Diborane(4) and Diborene(2): [{CpMo(CO)₂}₂{μ‐η²:η²‐B₂H₄}] and [{CpM(CO)₂}₂B₂H₂M(CO)₄], M=Mo,W

Cited by 16 publications

References 70 publications

Metal Rich Metallaboranes: Synthesis, Structure and Bonding of pileo-[(Cp*Ru)2M(CO)3(µ-H)(µ-E)(µ3-BH)B2H5] (M = Mo, W, E = CO, and M = Mn, E = H) Clusters

Metal Rich Metallaboranes: Synthesis, Structure and Bonding of pileo-[(Cp*Ru)2M(CO)3(µ-H)(µ-E)(µ3-BH)B2H5] (M = Mo, W, E = CO, and M = Mn, E = H) Clusters

Diborane and Triborane Species in the Coordination Sphere of Group-8 Transition Metals

Structures and Bonding of Early Transition Metallaborane Clusters

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