36600-83-6Relevant articles and documents
Internal B-O Bond-Facilitated Photoisomerization of Boranes: Ring Expansion Versus Oxyborane Elimination/Intramolecular Diels-Alder Addition
Hu, Guo-Fei,Li, Hai-Jun,Zeng, Chao,Wang, Xiang,Wang, Nan,Peng, Tai,Wang, Suning
, p. 5285 - 5289 (2019)
Boron compounds (1-4) containing an internal B-O bond have been found to undergo facile multistructural transformations upon irradiation at 365 or 410 nm, generating rare 8-membered B,O-heterocycles (1c-4c). In addition, 2 and 3 also undergo an intramolecular Diels-Alder addition and oxyborane elimination concomitantly, via intermediates 2b/3b, producing 2d/3d. The pathways to isomer c and product d were found to be a thermal process and a photo process, respectively.
Dimesitylzinc: A strictly 2-coordinate, homoleptic diarylzinc compound
Cole, Sarah C.,Coles, Martyn P.,Hitchcock, Peter B.
, p. 3663 - 3664 (2003)
Unprecedented aryl transfer from boron to zinc generated Zn(mes)2, the structure of which revealed a linear, two coordinate metal in which there is no stabilisation by interor intramolecular interactions.
Directly observed transmetalation from boron to rhodium. β-aryl elimination from Rh(I) arylboronates and diarylborinates
Zhao, Pinjing,Incarvito, Christopher D.,Hartwig, John F.
, p. 1876 - 1877 (2007/10/03)
Transmetalation from boron to rhodium in the absence of basic activators is reported to proceed by β-aryl elimination from a series of triethylphospine-ligated rhodium(I) arylboronates and diarylborinates. [Rh(PEt3)3OB(OH)Ar] were prepared by treating {Rh(PEt3)2[N(SiMe3)2} with the corresponding arylboronic acid, ArB(OH)2, in the presence of added PEt3. One example of these complexes was characterized by X-ray diffraction. [Rh(PEt3)3OB(mesityl)2] and [Rh(PEt3)2OB(mesityl)2] were prepared by analogous methods from dimesitylborinic acid in the presence and absence of added PEt3. Heating of the trisphosphine boronate complexes in cyclohexane generated the rhodium aryl complexes, [(PEt3)3RhAr] and boroxin in good to high yields. [Rh(PEt3)3OB(mesityl)2] also underwent aryl migration to form [(PEt3)3Rh(mesityl)] and a cyclic boroxine. Kinetic studies showed that migration of more electron-poor aryl groups from the boronate complexes was slightly faster than migration of more electron-poor aryl groups and that migration of the o-anisyl group was particularly fast. Kinetic results are most consistent with a ligand dissociation pathway with a rate-limiting β-aryl elimination from a 14-electron, bis(phosphine) intermediate. Copyright
Phosphino[tris(trimethylsilyl)methyl]boranes and 2,4- bis[tris(trimethylsilyl)methyl]-1,3,2,4-diphosphadiboretanes [1]
Jetzfellner,Noeth,Paine
, p. 548 - 556 (2008/10/09)
The reaction of tris(trimethylsilyl)methylboron dihalides (Me 3Si)3CBX2 (X = Cl, F) with the lithium phosphides LiPHtBu and LiPHmes leads to the phosphinoboranes (Me 3Si)3CBX-(PHR), (Me3Si)3CB(PHR) 2 or the 1,3,2,4-diphosphadiboretanes [(Me3Si) 3CB(PR)]2, depending on the ratio of the reagents, the reaction temperature and concentration. High dilution and low temperatures are required for the synthesis of (Me3Si)3CB(Hal)PHR (1-3) in order to prevent the formation of (Me3Si)3CB(PHR) 2 (4 and 5). The latter compounds are best prepared in a two step phosphination from (Me3Si)3CBHal2 and LiPHR. At higher temperatures the four-membered 1,3,2,4-diphosphadiboretanes [(Me 3Si)3CB(PR)]2 6 and 7 are the most stable compounds. On the other hand, compounds of type (Me3Si) 3CB(Hal)PR2, 8 and 9, are thermally more stable than the monophosphinoboranes 1-3. Phosphinoboranes of type (Me3Si) 3CB(PR2)2 (R = tBu, mes) could not be prepared. NMR and mass spectral data are in accord with the monomeric nature of compounds 1 to 9.
