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Boryl-Dihydrideborate Osmium Complexes: Preparation, Structure, and Dynamic Behavior in Solution

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NIAID Data Ecosystem2026-03-08 收录
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https://figshare.com/articles/dataset/Boryl_Dihydrideborate_Osmium_Complexes_Preparation_Structure_and_Dynamic_Behavior_in_Solution/2188873
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The metal fragment Os­(CO)­(PiPr3)2 stabilizes boryl-dihydrideborate species, which can be viewed as snapshots of states of B–H oxidative addition of a R2BH molecule and frustrated B–H bond activation of a second one. Complex OsH2(η2-CH2CHEt)­(CO)­(PiPr3)2 (2) shows a tendency to dissociate the olefin. The resulting dihydride OsH2(CO)­(PiPr3)2 (3) rapidly coordinates catecholborane (HBcat) and pinacolborane (HBpin) to give the corresponding σ-borane derivatives OsH2(η2-HBR2)­(CO)­(PiPr3)2 (BR2 = Bcat (4), Bpin (5)). Complex 4 reacts with a second molecule of HBcat to release H2 and to afford the octahedral boryl dihydride borate derivative Os­(Bcat)­(κ2-H2Bcat)­(CO)­(PiPr3)2 (6), which undergoes a thermally activated Bcat site exchange process in solution. Borane displaces catecholborane from the dihydride-borate of 6 to generate the boryl-tetrahydrideborate Os­(Bcat)­(κ2-H2BH2)­(CO)­(PiPr3)2 (7). This compound and the Bpin counterpart Os­(Bpin)­(κ2-H2BH2)­(CO)­(PiPr3)2 (8) have also been prepared by reaction of the corresponding Os­(BR2)­Cl­(CO)­(PiPr3)2 with Na­[BH4].
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2016-02-14
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