Reactivity of Diaryl Bismuth Cations toward a Platinum(0) Complex: Oxidative Aryl Transfer
Reactions of three aryl-substituted bismuth cations, [BiPh2(SbF6)], [BiMes2(SbF6)], and [BiDipp2(SbF6)], with the Pt0 complex Pt(PCy3)2 have been investigated (Mes = 2,4,6-trimethyl-phenyl; Dipp = 2,6-di-iso-propyl-phenyl; Cy = cyclohexyl). Unexpectedly, and in contrast with the reactivity of the recently reported methyl analogue [BiMe2(SbF6)], the formation of isolable metal-only Lewis pairs [(Cy3P)2PtβBiAr2(SbF6)] is not observed (Ar = aryl). Instead, an unprecedented bismuth-to-platinum oxidative aryl transfer is witnessed to give the PtII complexes [PtAr(PCy3)2(SbF6)], along with the suggested bismuthinidene intermediates BiAr. Attempts to trap these fleeting intermediates with an ortho-quinone led to a PtII semiquinone radical complex.
#Bismuth meets platinum (#1): diaryl bismuth cations undergo oxidative aryl transfer to Pt(0)! Attempts to trap the low-valent Bi intermediate yielded a Pt radical complex. Now out in the p-block special issue of #Organometallics, @pubs.acs.org: pubs.acs.org/doi/10.1021/... Congrats to the team!
09.01.2026 10:41 β
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Homoleptic bismuth phosphanides isolated! We are happy to share our recent findings @chemicalscience.rsc.org: pubs.rsc.org/en/content/a.... The title compounds readily release P-radicals, revealing a novel P-inversion pathway and P-radical transfer to external substrates. Congrats to the team!
09.01.2026 10:47 β
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Thank you so much Crispin and many congratulations to all who have been involve.
24.11.2025 08:56 β
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Thank you so much βΊοΈβΊοΈ
24.11.2025 08:52 β
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Wow.. Many Congratulations to the team..
20.11.2025 21:24 β
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A Crystalline Phosphorus-Substituted Borinium Ion: Double Dihydrogen Activation by an Ambiphilic Inorganic Allene ( @chemicalscience.rsc.org ): pubs.rsc.org/en/content/a....
18.11.2025 20:05 β
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Many congratulations to all. very Nice work..
17.11.2025 23:08 β
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Our latest is out now in @angewandtechemie.bsky.social!
Thermochromism, C-H/O activation & redox chem at a planar Bi triamide. Congrats to PhD Will Howlett on leading this @bsky.app initiated collab with @chrisslootweg.bsky.social + @jasonmasuda.bsky.social
@dalchemistry.bsky.social.
bit.ly/480io3T
17.11.2025 15:32 β
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We celebrated the farewell of #JΓΆrgSundermeyer β my GDCh partner in crimeπ₯°π€© whose energy β‘πalways lifted us. βDein strahlendes LΓ€cheln π& deine gute Laune werden uns sehr fehlen.β
Danke fΓΌr alles! β¨β¨β¨β¨β¨β¨β¨β¨#ProfLife
17.11.2025 21:01 β
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very nice work.. Many congratulations to the team ..
17.11.2025 18:54 β
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Heartiest congratulations Crispin. Well deserved..
07.11.2025 22:01 β
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Our manuscript on the first isolable paramagnetic boron tetraradical is now online @jacs.acspublications.org (pubs.acs.org/doi/full/10....)! @heechankim.bsky.social designed and synthesized an unusual B-PAH tetraradical with tetraphenylethene-linked boraphenanthrene-type units! #maingroup
05.09.2025 17:40 β
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Wow .. Many congratulations to you and your team.. wish you very happy birthday π
02.09.2025 00:17 β
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A Crystalline Boravinylidene from an Arrested Hydroboration Reaction ( @boron11.bsky.social ): pubs.acs.org/doi/10.1021/... ( @jacs.acspublications.org ).
30.08.2025 20:22 β
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Round succulents glow in a variety of colors.
These succulents got a glow up from researchers who injected the plants with inorganic phosphor particles. The researchers patented their technology and hope that it could lead to living light features in the future: cen.acs.org/materials/ph...
#FluorescenceFriday #CENChemPics #chemsky π§ͺ
29.08.2025 18:08 β
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Congratulations to Professor Alex Radosevich and Professor @alisonwendlandt.bsky.social, who were named recipients of 2026 Arthur C. Cope Scholar Awards by the American Chemical Society. These awards recognize and encourage excellence in organic chemistry.
chemistry.mit.edu/chemistry-ne...
20.08.2025 19:13 β
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Reversible Electron Transfer in the Formation of Radical Anionic and Dianionic 1,4-Diborabutatrienes ( @jacs.acspublications.org ): pubs.acs.org/doi/10.1021/....
17.08.2025 12:40 β
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After our 2025 Research Retreat where we discussed our research plans for the academic year, we had a nice dinner at
Lucca in Boston!
15.08.2025 09:20 β
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Very nice work..Many congratulations to the team
13.08.2025 19:25 β
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From @heechankim.bsky.social @rjgilliard.bsky.social a range of boron helices @jacs.acspublications.org.
This double-stranded diborahelicate could be transformed into luminescent borahelicates and cationic boron coordination complexes.
π CSD Entry CABXAJ: bit.ly/46xskm6
#FeaturedStructureFriday
04.07.2025 10:21 β
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In this Graduate Student Spotlight, Chonghe Zhang shares his inspiration for studying chemistry and reveals the movie heβd watch on a loop for 27 hours, the food he craves most often, the best thing he could reasonably expect to find in a cave, and more!
chemistry.mit.edu/chemistry-ne...
27.06.2025 21:19 β
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The Hudnall lab is hiring a Postdoctoral Fellow! Applicants excited about joining our recently relocated research group and interested in the synthesis of exotic main-group molecules, materials and heterodiatomics can email Dr. Hudnall directly. Please share!
25.06.2025 21:00 β
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Magnesium-Catalyzed Primary, Secondary, and Tertiary Amide Hydroboration
Catalytic hydroboration of amides is highly important because the resultant amines are commonly found in natural products, pharmaceuticals, agrochemicals, dyes, and other applications. In comparison to the conventional reduction of amides using (over)stoichiometric reductants, hydroboration of amides using magnesium compounds represents a green and sustainable approach because magnesium is both Earth abundant and environmentally benign. However, there is only one report on magnesium-catalyzed deoxygenative hydroboration of secondary and tertiary amides. Here, we describe the synthesis and structural authentication of two new magnesium compounds (1 and 2) featuring a flexible PNP ligand and the utilization of 2 as a catalyst for the pinacolborane-mediated reduction of primary, secondary, and tertiary amides to amines. The reaction scope is explored, and a mechanism is proposed based on experimental and theoretical insights.
This time it's magnesium! Our latest at Inorganic Chemistry reports a Mg-catalyst that reduces all amides. Kudos to Biplab for the lead with solid support from Soumya, Devaraj, Kumar, Rajesh! Grateful to CSIR_IND for funds!
#MagnesiumCatalysis
#SustainableChemistry
pubs.acs.org/doi/10.1021/...
19.06.2025 07:13 β
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Manganese(I)-catalyzed dehydrogenative borylation of terminal alkynes
Compounds containing carbonβboron bonds serve as valuable intermediates for constructing more complex molecules by transforming these bonds into other carbonβelement bonds. The catalytic dehydrogenati...
This time we work on Mn (it's not Mg) when Biswajit Saha helps us! A great collaborative work on C-H borylation led by Prateeksha and duly supported by Rinu, Deboshree, Kumar.
Just published @daltontrans.rsc.org
Thanks CSIR-NCL, CSIR-NEIST
& ANRF, India for support
pubs.rsc.org/en/content/a...
17.06.2025 12:54 β
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Our manuscript on unlocking the ambiphilicity of boryl anions is now published in JACS @jacs.acspublications.org (pubs.acs.org/doi/full/10....)! Chonghe, Junyi, Xibao, and coworkers report the synthesis and reactivity of the first anionic diazoborane! #maingroup #boron @gilliardgroup.bsky.social
10.06.2025 19:13 β
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We are excited to welcome Dr. Gargi Kundu @gargis.bsky.social to our lab as a Fulbright Postdoctoral Fellow!
06.06.2025 07:43 β
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