107134-74-7Relevant academic research and scientific papers
"third-Generation"-Type Functional Tris(2-pyridyl)borate Ligands and Their Transition-Metal Complexes
Jeong, So Yi,Lalancette, Roger A.,Lin, Huina,Lupinska, Patrycja,Shipman, Patrick O.,John, Alexandra,Sheridan, John B.,J?kle, Frieder
, p. 3605 - 3615 (2016/05/19)
Phenyltris(2-pyridyl)borates (Tpyb) are a promising class of tripodal "scorpionate"-type ligands with potential utility in the development of transition-metal complexes with interesting optical, electronic, or magnetic properties and as building blocks to metallosupramolecular polymers. We report here a new class of "third-generation"-type Tpyb ligands that contain different functional groups attached to the boron-bound aryl moiety. The synthesis, characterization, and metal-ion complexation behavior of ligands with iodo and trimethylsilyl groups are discussed. The electrochemical and absorption characteristics of the corresponding low-spin iron(II) and ruthenium(II) complexes are compared. We demonstrate the further elaboration of iodo derivatives with alkynes via Sonogashira-Hagihara coupling, a process that proceeds with high yield for the iron(II) and ruthenium(II) complexes but not for the free ligand. Borylation of the silyl-substituted ruthenium(II) complex with BBr3 was also investigated. In addition to the expected borylation product Ru(Tpyb-Bpin)2, the replacement of one (major product) or two phenyl groups is observed, suggesting that electrophilic borylation occurs at both the C(Ph)-Si and the C(Ph)-B aromatic carbon atoms. The successful attachment of a range of different functional groups at the periphery of the Tpyb metal complexes is expected to provide opportunities to access new polymeric materials via C-C coupling or click-type reactions.
Structural characteristics of dibromo-borylated benzene derivatives
Popp, Sebastian,Ruth, Kai,Lerner, Hans-Wolfram,Bolte, Michael
experimental part, p. o226-o230 (2012/07/14)
The crystal structures of five dibromobenzene derivatives, namely dibromoborylbenzene, C6H5BBr2, (I), 1-dibromoboryl-4-(trimethylsilyl)benzene, C9H13BBr 2Si, (II), 4-bromo-1-(dibromoboryl)
Copper complexes of mono- and ditopic [(methylthio)methyl]borates: Missing links and linked systems en route to copper enzyme models
Ruth, Kai,Tuellmann, Sandor,Vitze, Hannes,Bolte, Michael,Lerner, Hans-Wolfram,Holthausen, Max C.,Wagner, Matthias
experimental part, p. 6754 - 6770 (2009/07/30)
TMEDA-free (TMEDA: tetramethylethylenediamine) LiCH2-SMe is a suitable reagent for the selective introduction of (methylthio)methyl groups into PhBBr2 and its p-silylated derivative Me3Si-C6H 4-BBr2. The resulting compounds, R*-C 6H4-B(Br)-(CH2SMe) (R* = H: 2; R* = SiMe3: 7) and PhB(CH2SMe)2 (3), form cyclic dimers through B-S adduct bonds in solution and in the solid state. Compounds 2 and 3 have successfully been used for preparing the (N2S) scorpionate [PhBpZ2(CH2SMe)]- ([5]-) (pz: pyrazol-1-yl) and the (NS2) scorpionate [PhBpz(CH2SMe) 2]-, respectively. Compound 7 proved to be an excellent building block for the heteroditopic poly(pyrazol-l-yl)borate p-[pz 3B-C6H4-Bpz2(CH2SMe)] 2- ([10]2-) that mimics the two ligation sites of the copper enzymes peptidylglycine α-hydroxylating monooxygenase and dopamine ss-monooxygenase. Treatment of the monotopic tripod [5]- with CuCl and CuBr2 results in the formation of complexes K[Cu(5) 2] and [Cu(5)2]. An X-ray crystallography study of K[Cu(5)2] revealed a tetrahedral (N2S2) coordination environment for the Cu1 ion, whereas the CuII ion of [Cu(5)2] possesses a square-pyramidal (N4S) ligand sphere (S-atom in the axial position). The remarkable redox properties of K[Cu(5)2] and [Cu(5)2] have been assessed by cyclic voltammetry and quantum chemical calculations. The reaction of K[Cu(5) 2] with dry air leads to the CuII species [Cu(5) 2] and to a tetranuclear CuII complex featuring [PhB(O)pz2]2- ligands. Addition of CuCl to K 2[10] gives the complex K3[Cu(10)2] containing two ligand molecules per Cu1 center. The Cu1 ion binds to both heteroscorpionate moieties and thereby establishes a coordination environment similar to that of the Cu1 ion in K[Cu(5)2].
Borylation of Arylsilanes, II. - Synthesis and Reactions of Silylated Dihalogenphenylboranes
Kaufmann, Dieter
, p. 901 - 906 (2007/10/02)
Upon treatment with trihaloboranes 4a and 4b the bissilylated benzenes 1, 2, and 3 yield the silylated dihalogenphenylboranes 5a-7b under substitution of one silyl group only.The corresponding difluoroboranes 5c-7c are easily accessible by a new fluorination method under mild reaction conditions by treating the dichloroboranes with lithium fluoride in ether.Upon heating with excess 4 the exchange of the second silyl group occurs, too, yielding the position-isomeric diborylbenzenes 9, 10, and 11.The bromination of the silylated dichlorophenylboranes 5a-7a proceeds with high regioselectivity under desilylation yielding 12, 13, and 14.The dimethoxyboranes 15, 16, and 17, synthesized by methanolysis of the corresponding dichloroboranes, can be coupled with bromobenzene under palladium(0) catalysis to yield the position-isomeric silylated biphenyls 18, 19, and 20.
