Prinson P. Samuel

Chemistry of functionalized silylenes

Recent years have witnessed important developments in organosilicon chemistry, courtesy to the high yield access of stable monomeric chlorosilylene (LSiCl, L = PhC(NtBu)2) and N-heterocyclic carbene (NHC) stabilized dichlorosilylene (L1SiCl2, L1 = 1,3-bis(2,6-iPr2C6H3)imidazol-2-ylidene) by dehydrochlorination technique using strong bases such as N-heterocyclic carbenes or LiN(SiMe3)2 as HCl scavenger. The chemistry of functionalized silylenes is markedly different from the previously reported dicoordinate silylenes. Their utility as synthons is well documented which paves the way for several striking compounds, e.g. monosilaoxiranes, CSi2P derivative, CSi3P cation, a dimer of silaisonitrile (Si2N2) with dicoordinate Si atoms etc. This study also unravels that these functionalized silylenes are proficient at activating phosphorus, and the functional group attached to the α-position of the silicon(II) centre plays a key role to determine the final product. The reaction of P4 with LSiCl affords a zwitterionic Si2P2 ring, while with LSiN(SiMe3)2 it gives an acyclic Si2P4 derivative. Another recent achievement in this field is the successful isolation of a valence isomer of disilyne known as the inter-connected bis-silylene. This perspective portrays the chemistry of functionalized silylenes which will attract great attention, heading for the further development of organosilicon chemistry.

Electronic Structure and Slow Magnetic Relaxation of Low-Coordinate Cyclic Alkyl(amino) Carbene Stabilized Iron(I) Complexes

Cyclic alkyl(amino) carbene stabilized two- and three-coordinate Fe(I) complexes, (cAAC)2FeCl (2) and [(cAAC)2Fe][B(C6F5)4] (3), respectively, were prepared and thoroughly studied by a bouquet of analytical techniques as well as theoretical calculations. Magnetic susceptibility and Mössbauer spectroscopy reveal the +1 oxidation state and S = 3/2 spin ground state of iron in both compounds. 2 and 3 show slow magnetic relaxation typical for single molecule magnets under an applied direct current magnetic field. The high-frequency EPR measurements confirm the S = 3/2 ground state with a large, positive zero-field splitting (∼20.4 cm(-1)) and reveal easy plane anisotropy for compound 2. CASSCF/CASPT2/RASSI-SO ab initio calculations using the MOLCAS program package support the experimental results.

Selective aromatic C-F and C-H bond activation with silylenes of different coordinate silicon.

Herein we report on the reaction of stable two-coordinate silylene, L(1)Si [L(1) = CH{(C=CH(2))(CMe)(2,6-iPr(2)C(6)H(3)N)(2)}] (1) and three-coordinate silylene (Lewis base stabilized silylene), L(2)SiCl [L(2) = PhC(NtBu)(2)] (2) with aromatic compounds containing C-F and C-H bonds. The reaction of 1 and 2 with hexafluorobenzene (C(6)F(6)) affords the silicon(IV) fluorides, L(1)SiF(C(6)F(5)) (3) and L(2)SiFCl(C(6)F(5)) (4), respectively. The reaction proceeds through the unprecedented oxidative addition of one of the C-F bonds to the silicon(II) center without any additional catalyst. When 1 and 2 are treated with octafluorotoluene (C(6)F(5)CF(3)), pentafluoropyridine (C(5)F(5)N) regioselective C-F bond activation occurs leading to the formation of L(1)SiF(4-C(6)F(4)CF(3)) (5), L(1)SiF(4-C(5)F(4)N) (6), L(2)SiFCl(4-C(6)F(4)CF(3)) (7), and L(2)SiFCl(4-C(5)F(4)N) (8), respectively. More interestingly, compounds 1 and 2 react with pentafluorobenzene (C(6)F(5)H) under formation of silicon(IV) hydride L(1)SiH(C(6)F(5)) (9) by chemoselective C-H bond activation, in the latter case producing silicon(IV) fluoride L(2)SiFCl(4-C(6)F(4)H) (10) by chemo- as well as regioselective C-F bond activation. Furthermore, the reaction of 1 with 1,3,5-trifluorobenzene (1,3,5-C(6)F(3)H(3)) leads to the chemoselective formation of silicon(IV) hydride L(1)SiH(1,3,5-C(6)F(3)H(2)) (11). The formation of compounds 9 and 11 occurs via oxidative addition of the aromatic C-H bond to the silicon(II) center instead of C-F bond activation. All reported reactions proceed without any additional catalyst. Compounds 3, 4, 5, 6, 7, 8, 9, 10, and 11 were investigated by microanalysis and multinuclear NMR spectroscopy and compounds 3, 7, 8, and 9 additionally by single crystal X-ray structural analyses.

C4 Cumulene and the Corresponding Air‐Stable Radical Cation and Dication

A neutral C4 cumulene 1 that includes a cyclic alkyl(amino) carbene (cAAC), its air-stable radical cation 1(·+) , and dication 1(2+) have been synthesized. The redox property of 1(·+) was studied by cyclic voltammetry. EPR and theoretical calculations show that the unpaired electron in 1(·+) is mainly delocalized over the central C4 backbone. The commercially available CBr4 is utilized as a source of dicarbon in the cumulene synthesis.

A Singlet Biradicaloid Zinc Compound and Its Nonradical Counterpart

Metal ions with radical centers in their coordination sphere are key participants in biological and catalytic processes. In the present study, we describe the synthesis of the cAAC:ZnCl2 adduct (1) using a cyclic alkylaminocarbene (cAAC) as donor ligand. Compound 1 was treated with 2 equiv of KC8 and LiB(sec-Bu)3H to yield a deep blue-colored dicarbene zinc compound (cAAC)2Zn (2) and the colorless hydrogenated zinc compound (cAACH)2Zn (3), respectively. Compounds 2 and 3 were well characterized by spectroscopic methods and single-crystal X-ray structural analysis. Density functional theory calculations were performed for 2 which indicate that this molecule possesses a singlet biradicaloid character. Moreover, we show the application of 2 in CO2 activation, which yields a zwitterionic cAAC·CO2 adduct.

Easy Access to Silicon(0) and Silicon(II) Compounds

Two different synthetic methodologies of silicon dihalide bridged biradicals of the general formula (L(n)•)2SiX2 (n = 1, 2) have been developed. First, the metathesis reaction between NHC:SiX2 and L(n): (L(n): = cyclic akyl(amino) carbene in a 1:3 molar ratio leads to the products 2 (n = 1, X = Cl), 4 (n = 2, X = Cl), 6 (n = 1, X = Br), and 7 (n = 2, X = Br). These reactions also produce coupled NHCs (3, 5) under C-C bond formation. The formation of the coupled NHCs (L(m) = cyclic alkyl(amino) carbene substituted N-heterocyclic carbene; m = 3, n = 1 (3) and m = 4, n =2 (5)) is faster during the metathesis reaction between NHC:SiBr2 and L(n): when compared with that of NHC:SiCl2. Second, the reaction of L(1):SiCl4 (8) (L(1): =:C(CH2)(CMe2)2N-2,6-iPr2C6H3) with a non-nucleophilic base LiN(iPr)2 in a 1:1 molar ratio shows an unprecedented methodology for the synthesis of the biradical (L(1)•)2SiCl2 (2). The blue blocks of silicon dichloride bridged biradicals (2, 4) are stable for more than six months under an inert atmosphere and in air for one week. Compounds 2 and 4 melt in the temperature range of 185 to 195 °C. The dibromide (6, 7) analogue is more prone to decomposition in the solution but comparatively more stable in the solid state than in the solution. Decomposition of the products has been observed in the UV-vis spectra. Moreover, compounds 2 and 4 were further converted to stable singlet biradicaloid dicarbene-coordinated (L(n):)2Si(0) (n = 1 (9), 2 (10)) under KC8 reduction. Compounds 2 and 4 were also reduced to dehalogenated products 9 and 10, respectively when treated with RLi (R = Ph, Me, tBu). Cyclic voltametry measurements show that 10 can irreversibly undergo both one electron oxidation and reduction.

Experimental Charge Density Study of a Silylone

An experimental and theoretical charge density study confirms the interpretation of (cAAC)2Si as a silylone to be valid. Two separated VSCCs present in the non-bonding region of the central silicon are indicative for two lone pairs. In the experiment, both the two crystallographically independent Si-C bond lengths and ellipticities vary notably. It is only the cyclohexyl derivative that shows significant differences in these values, both in the silylones and the germylones. Only by calculating increasing spheres of surrounding point charges we were able to recover the changes in the properties of the charge density distribution caused by weak intermolecular interactions. The nitrogen-carbene-carbon bond seems to have a significant double-bond character, indicating a singlet state for the carbene carbon, which is needed for donor acceptor bonding. Thus the sum of bond angles at the nitrogen atoms seems to be a reasonable estimate for singlet versus triplet state of cAACs.

One-electron-mediated rearrangements of 2,3-disiladicarbene.

A disiladicarbene, (Cy-cAAC)2Si2 (2), was synthesized by reduction of Cy-cAAC:SiCl4 adduct with KC8. The dark-colored compound 2 is stable at room temperature for a year under an inert atmosphere. Moreover, it is stable up to 190 °C and also can be characterized by electron ionization mass spectrometry. Theoretical and Raman studies reveal the existence of a Si═Si double bond with a partial double bond between each carbene carbon atom and silicon atom. Cyclic voltammetry suggests that 2 can quasi-reversibly accept an electron to produce a very reactive radical anion, 2(•-), as an intermediate species. Thus, reduction of 2 with potassium metal at room temperature led to the isolation of an isomeric neutral rearranged product and an anionic dimer of a potassium salt via the formation of 2(•-).

Stable silaimines with three- and four-coordinate silicon atoms.

The reactions of silylenes with organic azides are quite diverse, depending on the substituents of the silylene center and on the nature of the azide employed. Elusive silaimine with three-coordinate silicon atom L(1)SiN(2,6-Triip(2)-C(6)H(3)) (5) {L(1) = CH[(C═CH(2))(CMe)(2,6-iPr(2)C(6)H(3)N)(2)] and Triip = 2,4,6-triisopropylphenyl} was synthesized by treatment of the silylene L(1)Si (1) with a sterically demanding 2,6-bis(2,4,6-triisopropylphenyl)phenyl azide (2,6-Triip(2)C(6)H(3)N(3)). The reaction of Lewis base-stabilized dichlorosilylene L(2)SiCl(2) (2) {L(2) = 1,3-bis(2,6-iPr(2)C(6)H(3))imidazol-2-ylidene} with Ph(3)SiN(3) afforded four-coordinate silaimine L(2)(Cl(2))SiNSiPh(3) (6). Treatment of 2,6-Triip(2)C(6)H(3)N(3) with L(3)SiCl (3) (L(3) = PhC(NtBu)(2)) yielded silaimine L(3)(Cl)SiN(2,6-Triip(2)-C(6)H(3)) (7) possessing a four-coordinate silicon atom. The reactions of L(3)SiN(SiMe(3))(2) (4) with adamantyl and trimethylsilyl azide furnished silaimine compounds with a four-coordinate silicon atom L(3)(N(Ad)SiMe(3))SiN(SiMe(3)) (8) (Ad = adamantyl) and L(3)(N(SiMe(3))(2))SiN(SiMe(3)) (9). Compound 8 was formed by migration of one of the SiMe(3) groups. Compounds 5-9 are stable under inert atmosphere and were characterized by elemental analysis, NMR spectroscopy, and single-crystal X-ray studies.

Phenalenyl-Based Organozinc Catalysts for Intramolecular Hydroamination Reactions: A Combined Catalytic, Kinetic, and Mechanistic Investigation of the Catalytic Cycle

Herein, we report the synthesis and characterization of two organozinc complexes that contain symmetrical phenalenyl (PLY)-based N,N-ligands. The reactions of phenalenyl-based ligands with ZnMe(2) led to the formation of organozinc complexes [N(Me),N(Me)-PLY]ZnMe (1) and [N(iPr),N(iPr)-PLY]ZnMe (2) under the evolution of methane. Both complexes (1 and 2) were characterized by NMR spectroscopy and elemental analysis. The solid-state structures of complexes 1 and 2 were determined by single-crystal X-ray crystallography. Complexes 1 and 2 were used as catalysts for the intramolecular hydroamination of unactivated primary and secondary aminoalkenes. A combined approach of NMR spectroscopy and DFT calculations was utilized to obtain better insight into the mechanistic features of the zinc-catalyzed hydroamination reactions. The progress of the catalysis for primary and secondary aminoalkene substrates with catalyst 2 was investigated by detailed kinetic studies, including kinetic isotope effect measurements. These results suggested pseudo-first-order kinetics for both primary and secondary aminoalkene activation processes. Eyring and Arrhenius analyses for the cyclization of a model secondary aminoalkene substrate afforded ΔH(≠) =11.3 kcal mol(-1) , ΔS(≠) =-35.75 cal K(-1)  mol(-1) , and E(a) =11.68 kcal mol(-1) . Complex 2 exhibited much-higher catalytic activity than complex 1 under identical reaction conditions. The in situ NMR experiments supported the formation of a catalytically active zinc cation and the DFT calculations showed that more active catalyst 2 generated a more stable cation. The stability of the catalytically active zinc cation was further supported by an in situ recycling procedure, thereby confirming the retention of catalytic activity of compound 2 for successive catalytic cycles. The DFT calculations showed that the preferred pathway for the zinc-catalyzed hydroamination reactions is alkene activation rather than the alternative amine-activation pathway. A detailed investigation with DFT methods emphasized that the remarkably higher catalytic efficiency of catalyst 2 originated from its superior stability and the facile formation of its cation compared to that derived from catalyst 1.