Metallaboranes as molecular precursors to thin metal-boride films. Conversion of HFe3(CO)9BH4 to amorphous iron boride(Fe75B25)

Amini, Mostafa M.; Fehlner, Thomas P.; Long, Gary J.; Politowski, Mark

doi:10.1021/cm00010a022

Cited by 22 publications

(9 citation statements)

References 4 publications

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“…42 Crystallographic data have been deposited with the Cambridge Crystallographic Data Center as supplementary publication nos. CCDC 1991441 (2), 2045959 (3), 1984057 (5), 1983844 (6), 2045968 (8), and 2036693 (10). These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…For example, taking advantage of the diffuse orbitals of rhodium, we have recently isolated the 16-vertex metal-rich metallaborane [(RhCp*) 3 B 12 H 12 Rh{RhCp*(B 4 H 9 )}], in which the metals are placed in the higher degree vertices . Fehlner and co-workers have shown previously that under vacuum and mild conditions the iron-rich ferraborane [HFe 3 (CO) 9 BH 4 ] can form an Fe 3 B thin film, which is an amorphous and soft ferromagnetic material …”

Section: Introductionmentioning

confidence: 99%

“…5 Fehlner and co-workers have shown previously that under vacuum and mild conditions the iron-rich ferraborane [HFe 3 (CO) 9 BH 4 ] can form an Fe 3 B thin film, which is an amorphous and soft ferromagnetic material. 6 Two major subclasses of metal-rich metallaboranes are typically clusters having borylene and boride units. Unlike the case for carbenes, the chemistry of borylene (:BR) was less explored until the 1990s due to the instability of free borylene.…”

Section: ■ Introductionmentioning

confidence: 99%

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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: ■ Experimental Sectionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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

et al. 2021

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“…Their chemical and physical properties make them promising candidates for use in different areas such as catalysis [41][42][43][44][45] or materials science etc. [46][47][48][49][50]. With the impetus of Fehlner who started to practice a fruitful synthetic method employing monoborane reagents and cyclopentadienyl metal chlorides [51,52], a large set of new metallaboranes have been characterized.…”

Section: Introductionmentioning

confidence: 99%

Polyhedral [M2B5] Metallaborane Clusters and Derivatives: An Overview of Their Structural Features and Chemical Bonding

2020

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A large number of metallaborane clusters and their derivatives with various structural arrangements are known. Among them, M2B5 clusters and derivatives constitute a significant class. Transition metals present in these species span from group 4 to group 7. Their structure can vary from oblatonido, oblatoarachno, to arachno type open structures. Many of these clusters appear to be hypoelectronic and are often considered as ‘rule breakers’ with respect to the classical Wade–Mingos electron counting rules. This is due to their unique highly oblate (flattened) deltahedral structures featuring a cross-cluster M−M interaction. Many theoretical calculations were performed to elucidate their electronic structure and chemical bonding properties. In this review, the synthesis, structure, and electronic aspects of the transition metal M2B5 clusters known in the literature are discussed. The chosen examples illustrate how, in synergy with experiments, computational results can provide additional valuable information to better understand the electronic properties and electronic requirements which govern their architecture and thermodynamic stability.

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“…ReB 2 can be grown as single crystals at high temperature using floating-zone or aluminum-flux methods − or deposited as a thin-film by pulsed-laser deposition onto a hot substrate (570 °C) under high vacuum at very low deposition rates . A wide variety of metal boride compositions have been prepared using chemical vapor deposition (CVD) synthesis strategies, − although formation of crystalline metal borides by CVD usually requires depositing material on heated surfaces ( T ≥ 500 °C) or by postdeposition thermal annealing of amorphous material at high temperatures.…”

Section: Introductionmentioning

confidence: 99%

Confined-Plume Chemical Deposition: Rapid Synthesis of Crystalline Coatings of Known Hard or Superhard Materials on Inorganic or Organic Supports by Resonant IR Decomposition of Molecular Precursors

2009

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A one-step process for preparing microcrystalline coatings of known superhard, very hard, or ultraincompressible ceramic compositions on either inorganic or organic supports is reported. Midinfrared pulsed-laser irradiation of preceramic chemical precursors layered between IR-transmissive hard/soft supports under temporal and spatial confinement at a laser wavelength resonant with a precursor vibrational band gives one-step deposition of crystalline ceramic coatings without incurring noticeable collateral thermal damage to the support material. Reaction plume formation at the precursor/laser beam interface initiates confined-plume, chemical deposition (CPCD) of crystalline ceramic product. Continuous ceramic coatings are produced by rastering the laser beam over a sample specimen. CPCD processing of the Re-B single-source precursor, (B(3)H(8))Re(CO)(4), the dual-source mixtures, Ru(3)(CO)(12)/B(10)H(14) or W(CO)(6)/B(10)H(14), and the boron/carbon single-source precursor, o-B(10)C(2)H(12), confined between Si wafer or NaCl plates gives microcrystalline deposits of ReB(2), RuB(2), WB(4), or B(4)C, respectively. CPCD processing of Kevlar fabric wetted by (B(3)H(8))Re(CO)(4) produces an oriented, microcrystalline coating of ReB(2) on the Kevlar fabric without incurring noticeable thermal damage of the polymer support. Similarly, microcrystalline coatings of ReB(2) can be formed on IR-transmissive IR2, Teflon, or Ultralene polymer films.

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Metallaboranes as molecular precursors to thin metal-boride films. Conversion of HFe3(CO)9BH4 to amorphous iron boride(Fe75B25)

Cited by 22 publications

References 4 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

Polyhedral [M2B5] Metallaborane Clusters and Derivatives: An Overview of Their Structural Features and Chemical Bonding

Confined-Plume Chemical Deposition: Rapid Synthesis of Crystalline Coatings of Known Hard or Superhard Materials on Inorganic or Organic Supports by Resonant IR Decomposition of Molecular Precursors

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