[(CO)H(PPh3)2-arachno-OsB3H8]

Bould, Jonathan; Rath, N. P.; Barton, Lawrence

doi:10.1107/s0108270195017239

Cited by 4 publications

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“…Refluxing [2,2,2-(PPh 3 ) 2 (CO)- nido -2-OsB 5 H 9 ] ( 1 ) with a slight excess of PPh 3 in CH 2 Cl 2 under N 2 affords a pale-yellow, air-stable crystalline solid [2,2,2-(PPh 3 ) 2 (CO)- nido -2-OsB 4 H 7 -3-BH 2 ·PPh 3 ] ( 2a ) in essentially quantitative yield. The species 2a was first observed in our laboratory as a minor impurity in the preparation of 1 ,11a along with traces of (PPh 3 ) 2 (CO)(H)OsB 3 H 8, (PPh 3 ) 2 (CO)OsB 4 H 8 , 11a,, and [(PPh 3 ) 2 (CO)OsB 9 H 13 ] . Mass spectrometric data for the trace quantities obtained suggested the formulation, but identification of 2a initially eluded us because precedence based on electron counting rules suggested an arachno -type structure 2 and satisfactory elemental analysis data were obtainable only after we discovered how to prepare the species in reasonable quantities.…”

Section: Resultsmentioning

confidence: 99%

Degradation and Modification of Metallaboranes: Reactions of the Hexaborane(10) Analoguenido-(PPh₃)₂(CO)OsB₅H₉with Phosphines and the Crystal and Molecular Structure of [2,2,2-(PPh₃)₂(CO)-nido-2-OsB₄H₇-3-BH₂·PPh₂Me]

et al. 1999

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The reaction between the osmahexaborane [2,2,2-(PPh3)2(CO)-nido-2-OsB5H9] (1) and bases such as PPh3, PPh2Me, and PMe3 in refluxing CH2Cl2 affords unique adducts of the type [2,2,2-(PPh3)2(CO)-nido-2-OsB4H7-3-BH2·PR3] (2) for which spectroscopic data suggest the presence of a pendent boryl group. This was confirmed by a crystal structure determination for the PPh2Me adduct which shows that 2 is a nido-osmapentaborane with a terminal BH2·PPh2Me moiety on a basal boron atom adjacent to the metal. The reaction is reversible in the case of PPh3 and to a lesser extent PPh2Me, but not for PMe3. Heating the PPh3 adduct affords the osmahexaborane 1, liberating PPh3, but degradation to the osmapentaborane [2,2,2-(PPh3)2(CO)-nido-2-OsB4H8] (6) and BH3·PPh3 competes. The tendency to degrade to phosphine·borane increases markedly down the series R3 = Ph3, Ph2Me, and Me3. When the bidentate bases [1,2-(PPh2)2(CH2)2] and [1,3-(PPh2)2(CH2)3] (abbreviated as dppe and dppp, respectively) are used, two major products are observed in each case. One (3a) [2,2,2-(PPh3)2(CO)-nido-2-OsB4H7-3-(BH2·dppe)] (or 3b, BH2·dppp) is analogous to 2 with one end of the bidentate phosphine donor uncoordinated. In the other (4a) [2,2-(PPh3)(CO)-nido-2-OsB4H7-η2-3,2-(BH2·dppe)] (or 4b, BH2·dppp), the free end of the bidentate ligand has replaced a PPh3 group on Os. In the reaction of [(PPh2)2(CH2)] (abbreviated as dppm) with 1, only a species analogous to 3 is observed. The species 3b, the one involving dppp, has been further modified at the free phosphine end of the ligand, to form [2,2,2-(PPh3)(CO)-nido-2-OsB4H7-3-(BH2·dppp·BH3)] (5).

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Section: Resultsmentioning

confidence: 99%

Degradation and Modification of Metallaboranes: Reactions of the Hexaborane(10) Analoguenido-(PPh₃)₂(CO)OsB₅H₉with Phosphines and the Crystal and Molecular Structure of [2,2,2-(PPh₃)₂(CO)-nido-2-OsB₄H₇-3-BH₂·PPh₂Me]

et al. 1999

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“…Passage of acetylene through a refluxing solution of 1b (25 mg) for 40 min followed by chromatographic separation of the reaction mixture resulted in the isolation of 14.5 mg of a mixture of two crystalline solidsthe pale yellow isonido -type 20 compound [PMe 3 ) 2 HIrC 2 B 8 H 9 Cl] ( 7b ) and the colorless nido -[ 9,9,9-(PMe 3 ) 2 (CO)-9,7,8-IrC 2 B 8 H 10 -(5-Cl)] ( 5b ). The structural characterization of 7b is reported elsewhere …”

Section: Resultsmentioning

confidence: 99%

“…Separation was achieved by manually removing the yellow crystals from the clumps under a microscope giving a small amount (1.5 mg) of the colorless material which was identified as nido -[9,9,9-(PMe 3 ) 2 (CO)-9,7,8-IrC 2 B 8 H 10 -(5-Cl)] { 5b : IR/cm -1 ν(CO) 2006 (s), ν(BH) 2485, 2535, 2577; HRMS showed two equal intensity fragmentation envelopes corresponding to the molecular ion C 9 H 28 B 8 IrP 2 OCl ( m/q 528.1744 (obsd), 528.1731 (calcd)) and the molecular ion minus (CO + H) (499.1715 (obsd), 499.1704 (calcd))}. The yellow crystals identified as the closo -type cluster [(PMe 3 ) 2 HIrC 2 B 8 H 9 Cl]( 7b ) have been characterized by a single-crystal X-ray diffraction study and reported independently …”

Section: Methodsmentioning

confidence: 99%

Metallaborane Heteroatom Incorporation Reactions: Metallacarboranes, Metallathiaboranes, and an Iridaazaborane from Iridanonaborane Precursors

1996

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Formation of metallaheteroboranes by insertion of heteroatoms into an existing metallaborane cluster, rather than adding the metal moiety to the heteroborane which is normally the case, has been achieved in the cases of carbon, nitrogen, and sulfur to produce nine-, ten-, and eleven-vertex metallaheteroborane clusters. Thus passage of acetylene through refluxing p-xylene solutions of either arachno-[(PMe3)2(CO)HIrB8H12] (1a) or nido-[(PMe3)2(CO)IrB8H11] (2a) afforded the 11-vertex cluster nido-[9,9,9-(PMe3)2(CO)-9,7,8-IrC2B8H11] (5a) in up to 44% yield. With the cage substituted species arachno-[(PMe3)2(CO)HIrB8H11Cl] (1b), the analogous product is nido-[5-Cl-9,9,9-(PMe3)2(CO)-9,7,8-IrC2B8H10] (5b) and the position of the Cl substituent in the product suggests that the acetylene moiety attacks across the open face of the intermediate nido-iridanonaborane species and that cage rearrangement does not occur during the course of the reaction. Similarly, reaction of 1a with H2S under identical conditions results in the formation nido-[2,2,2-(PMe3)2H-2,6-IrSB8H10] (9a), closo-[2,2,2-(PMe3)2H-2,1-IrSB8H8] (10), and nido-[(PMe3)2HIrS2B8H8] (11a) in overall yields of 13%, 7%, and 20%, respectively. Additionally, refluxing a solution of 1a and anhydrous hydrazine in xylene afforded a 10% yield of the novel iridaazanonaborane nido-[2,2,2-(PMe3)3-2,9-IrNB7H9] (12). The compound is the first metallaazanonaborane cluster to be described, and its formation indicates that methods similar to those used to generate azaboranes may be used on metallaboranes to generate metallazaboranes. In addition to characterization by a combination of 1H, 31P, and 11B NMR and IR spectroscopy and high-resolution mass spectrometry, single-crystal X-ray diffraction studies were carried out on compounds 5a, 9a, 10, and 12.

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“…The Cambridge Crystallographic Data Centre (CCDC) provides X-ray diffraction analyses for fifteen arachno -metallaboranes, incorporating {ML n }-fragments of Nb [ 7 ], Cr [ 12 ], Mo [ 10 ], W [ 6 , 10 ], Mn [ 13 ], Re [ 8 , 13 ], Ru [ 11 , 14 , 15 ], Os [ 16 ] and Cu [ 17 ]. However, the availability of comparative structural data across the periodic table, for this particular class of four-vertex arachno -metallaboranes, is limited.…”

Section: Resultsmentioning

confidence: 99%

The Synthesis, Characterization, and Fluxional Behavior of a Hydridorhodatetraborane

Diaw-Ndiaye,

Sanz Miguel,

Rodríguez

et al. 2023

Molecules

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The octahydridotriborate anion plays a crucial role in the field of polyhedral boron chemistry, facilitating the synthesis of higher boranes and the preparation of diverse transition metal complexes. Among the stable forms of this anion, CsB3H8 (or (n-C4H9)4N)[B3H8] have been identified. These salts serve as valuable precursors for the synthesis of metallaboranes, wherein the triborate anion acts as a ligand coordinating to the metal center. In this study, we have successfully synthesized a novel rhodatetraborane dihydride, [Rh(η2-B3H8)(H)2(PPh3)2] (1), which represents a Rh(III) complex featuring a bidentate chelate ligand fasormed by B3H8−. Extensive characterization of this rhodatetraborane complex has been performed using NMR spectroscopy in solution and X-ray diffraction analysis in the solid state. Notably, the complex exhibits intriguing fluxional behavior, which has been investigated using NMR techniques. Moreover, we have explored the reactivity of complex 1 towards pyridine (py) and dimethylphenylphosphine (PMe2Ph). Our findings highlight the labile nature of this four-vertex rhodatetraborane as it undergoes disassembly upon attack from the corresponding Lewis base, resulting in the formation of borane adducts, LBH3, where L = py, PMe2Ph. Furthermore, in these reactions, we report the characterization of new cationic hydride complexes, such as [Rh(H)2(PPh3)2 (py)]+ (2) and [Rh(H)2(PMe2Ph)4]+. Notably, the latter complex has been characterized as the octahydridotriborate salt [Rh(H)2(PMe2Ph)4][B3H8] (3), which extends the scope of rhodatetraborane derivatives.

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[(CO)H(PPh3)2-arachno-OsB3H8]

Cited by 4 publications

References 2 publications

Degradation and Modification of Metallaboranes: Reactions of the Hexaborane(10) Analoguenido-(PPh₃)₂(CO)OsB₅H₉with Phosphines and the Crystal and Molecular Structure of [2,2,2-(PPh₃)₂(CO)-nido-2-OsB₄H₇-3-BH₂·PPh₂Me]

Degradation and Modification of Metallaboranes: Reactions of the Hexaborane(10) Analoguenido-(PPh₃)₂(CO)OsB₅H₉with Phosphines and the Crystal and Molecular Structure of [2,2,2-(PPh₃)₂(CO)-nido-2-OsB₄H₇-3-BH₂·PPh₂Me]

Metallaborane Heteroatom Incorporation Reactions: Metallacarboranes, Metallathiaboranes, and an Iridaazaborane from Iridanonaborane Precursors

The Synthesis, Characterization, and Fluxional Behavior of a Hydridorhodatetraborane

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[(CO)H(PPh3)2-arachno-OsB3H8]

Cited by 4 publications

References 2 publications

Degradation and Modification of Metallaboranes: Reactions of the Hexaborane(10) Analoguenido-(PPh3)2(CO)OsB5H9with Phosphines and the Crystal and Molecular Structure of [2,2,2-(PPh3)2(CO)-nido-2-OsB4H7-3-BH2·PPh2Me]

Degradation and Modification of Metallaboranes: Reactions of the Hexaborane(10) Analoguenido-(PPh3)2(CO)OsB5H9with Phosphines and the Crystal and Molecular Structure of [2,2,2-(PPh3)2(CO)-nido-2-OsB4H7-3-BH2·PPh2Me]

Metallaborane Heteroatom Incorporation Reactions: Metallacarboranes, Metallathiaboranes, and an Iridaazaborane from Iridanonaborane Precursors

The Synthesis, Characterization, and Fluxional Behavior of a Hydridorhodatetraborane

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Product

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Degradation and Modification of Metallaboranes: Reactions of the Hexaborane(10) Analoguenido-(PPh₃)₂(CO)OsB₅H₉with Phosphines and the Crystal and Molecular Structure of [2,2,2-(PPh₃)₂(CO)-nido-2-OsB₄H₇-3-BH₂·PPh₂Me]

Degradation and Modification of Metallaboranes: Reactions of the Hexaborane(10) Analoguenido-(PPh₃)₂(CO)OsB₅H₉with Phosphines and the Crystal and Molecular Structure of [2,2,2-(PPh₃)₂(CO)-nido-2-OsB₄H₇-3-BH₂·PPh₂Me]