119072-54-7Relevant articles and documents
Facile access to a Ge(II) dication stabilized by isocyanides
Swamy,Yadav, Sandeep,Pal, Shiv,Das, Tamal,Vanka, Kumar,Sen, Sakya S.
, p. 7890 - 7892 (2016)
Herein, we introduce isocyanide as a ligand in main group chemistry and describe the facile isolation of a Ge(ii) dication. The reaction of 2,6-dimethylphenylisocyanide with GeCl2 leads to the formation of a Ge(ii) dication with two [GeCl3]- molecules as counter anions. The dicationic Ge(ii) center is bound to four isocyanide ligands and also holds a lone pair of electrons. DFT calculations reveal that the dication is stabilized only by σ-donation from the four isocyanide ligands. Natural population analysis gives a charge of +0.74 on the Ge(ii) center, indicating that the positive charge is shared by the isocyanide substituents.
Reversible switching between housane and cyclopentanediyl isomers: An isonitrile-catalysed thermal reverse reaction
Beer, Henrik,Bresien, Jonas,Michalik, Dirk,Schulz, Axel,Villinger, Alexander
, p. 13986 - 13992 (2020)
The photo-isomerization of an isolable five-membered singlet biradical based on C, N, and P ([TerNP]2CNDmp, 2a) selectively afforded a closed-shell housane-type isomer (3a) by forming a transannular P-P bond. In the dark, the housane-type species re-isomerized to the biradical, resulting in a fully reversible overall process. In the present study, the influence of tBuNC on the thermal reverse reaction was investigated: The isonitrile acted as a catalyst, thus allowing control over the thermal reaction rate. Moreover, tBuNC also reacted with the biradical to form an adductspecies ([TerNP]2CNDmp·CNtBu, 4a), which can be regarded as the resting state of the system. The reactive species 2a and 3a could be re-generated in situ by irradiation with red light. The results of this study extend our understanding of this new class of molecular switches.
The Roles of Aminocarbyne Intermediates and Intramolecular Electron Transfer in the Formation od Carbon-Carbon Bonds by the Coupling of Isocyanides
Wu, Jianxin,Fanwick, Phillip E.,Kubiak, Clifford P.
, p. 7812 - 7823 (1989)
The binuclear iridium complex Ir2(CNR)4(dmpm)2, 1, (R = 2,6-Me2C6H3, dmpm = Me2PCH2PMe2) was prepared by reduction of 2 with Na amalgam in benzene.The structure of 1, determined by X-ray diffraction, consists of two iridium atoms bridged by two cis,cis dmpm ligands and two μ-2,6-xylyl isocyanide ligands.The Ir-Ir bond length is 2.5998 (7) Angstroem.The nonbonded distance between the carbon atoms of the μ-isocyanide ligands is 2.37 (2) Angstroem.The potential coupling of the two μ-isocyanide ligands of 1, promoted by Lewis acids, wasinvestigated.Addition of 2 equiv of BH3*THF to 1 affords Ir2(μ-CN(BH3)R)2(CNR)2(dmpm)2, 2, which contains two μ-CN(BH3)R aminocarbyne groups which are not coupled.Addition of Al2Et6 to 1 in toluene gives Ir2(C2(NR)2AlEt2)(CNR)2(dmpm)2, 3, which contains a new carbon-carbon bond, d(C-C) = 1.48 (1) Angstroem, between two coupled isocyanides.The AlEt2 fragment bridges two isocyanide N atoms to form an essentially planar five-membered C2N2Al ring.The C2N2Al ring is coplanar with the two iridium atoms.Complex 3 is paramagnetic and exhibits an isotropic EPR powder spectrum, g = 2.005 at -150 deg C.Complex 3 is reversibly oxidized electrochemically to form the diamagnetic species (CNR)2(dmpm)2>, 4.E1/2(4/3) = -0.22 V vs SCE.The mechanism of isocyanide coupling leading to 3 involves electronic reconfiguration of the d9-d9 Ir02 core of 1 to the d8-d8 IrI2 "A-frame" species 4.Paramagnetic 3 is formed by single-electron transfer to 4 by AlEt4(-), formed in situ during isocyanide coupling.Crystal data for 1: space group P21; a = 10.615 (2), b = 16.883 (3), c = 15.044 (3) Angstroem; β = 94.23 (1)0; V = 2689 (2) Angstroem3; Z = 2; R = 0.033, Rw = 0.044 for 528 variables and 3229 unique data with I > 3?(I), Mo Kα radiation.Crystal data for 2: space group P21212; a = 15.905 (2), b = 16.286 (2), c = 10.528 (3) Angstroem; Z = 2; V = 2727 (1) Angstroem3; R = 0.048, Rw =0.062 for 282 variables and 2263 unique data with I > 3?(I), Mo Kα radiation.Crystal data for 3: space group P21/c; a = 11.44 (1), b = 19.072 (1), c = 25.602 (3) Angstroem; β = 102.910; V = 5446 (2) Angstroem3; Z = 4; R = 0.035, Rw = 0.040 for 550 variables and 5330 unique data with I > 3?(I), Mo Kα radiation.
Heterocyclopentanediyls vs heterocyclopentadienes: A question of silyl group migration
Beer, Henrik,Bresien, Jonas,Michalik, Dirk,R?lke, Anne-Kristin,Schulz, Axel,Villinger, Alexander,Wustrack, Ronald
, p. 14435 - 14445 (2020)
The reaction of the singlet biradical [P(μ-NHyp)]2 (Hyp = hypersilyl, (Me3Si)3Si) with different isonitriles afforded a series of five-membered N2P2C heterocycles. Depending on the steric bulk of the substituent at the isonitrile, migration of a Hyp group was observed, resulting in two structurally similar but electronically very different isomers. As evidenced by comprehensive spectroscopic and theoretical studies, the heterocyclopentadiene isomer may be regarded as a rather unreactive closed-shell singlet species with one localized N=P and one C=P double bond, whereas the heterocyclopentanediyl isomer represents an open-shell singlet biradical with interesting photochemical properties, such as photoisomerization under irradiation with red light to a [2.1.0]- housane-type species.
Mild C?F Activation in Perfluorinated Arenes through Photosensitized Insertion of Isonitriles at 350 nm
Weidlich, Frauke,Esumi, Naoto,Chen, Dongyang,Mück-Lichtenfeld, Christian,Zysman-Colman, Eli,Studer, Armido
supporting information, p. 376 - 383 (2019/11/19)
Fluorinated compounds have become important in the fields of agrochemical industry, pharmaceutical chemistry and materials sciences. Accordingly, various methods for their preparation have been developed in the past. Fluorinated compounds can be accessed via conjugation with fluorinated building blocks, via C?H fluorination or via selective activation of perfluorinated compounds to give the partially fluorinated congeners. Especially the direct activation of C?F bonds, one of the strongest σ-bonds, still remains challenging and new strategies for C?F activation are desirable. Herein a method for the photochemical activation of aromatic C?F bonds is presented. It is shown that isonitriles selectively insert into aromatic C?F bonds while aliphatic C?F bonds remain unaffected. Mechanistic studies reveal the reaction to proceed via the indirect excitation of the isonitrile to its triplet state by photoexcited acetophenone at 350 nm. Due to the relatively mild light used, the process shows high functional group tolerance and various compounds of the class of benzimidoyl fluorides are accessible from aryl isonitriles and commercially available perfluorinated arenes. (Figure presented.).
