ABSTRACT
A stable aluminum tris(dithiolene) triradical (3) was experimentally realized through a low-temperature reaction of the sterically demanding lithium dithiolene radical (2) with aluminum iodide. Compound 3 was characterized by single-crystal X-ray diffraction, UV-vis and EPR spectroscopy, SQUID magnetometry, and theoretical computations. The quartet ground state of triradical 3 has been unambiguously confirmed by variable-temperature continuous wave EPR experiments and SQUID magnetometry. Both SQUID magnetometry and broken-symmetry DFT computations reveal a small doublet-quartet energy gap [ΔEDQ = 0.18 kcal mol-1 (SQUID); ΔEDQ = 0.14 kcal mol-1 (DFT)]. The pulsed EPR experiment (electron spin echo envelop modulation) provides further evidence for the interaction of these dithiolene-based radicals with the central aluminum nucleus of 3.
ABSTRACT
While the dithiolene-based N-heterocyclic silane (4) reacts with two equivalents of BX3 (X = Br, I) to give zwitterionic Lewis adducts 5 and 8, respectively, the parallel reaction of 4 with BCl3 results in 10, a dithiolene-substituted N-heterocyclic silane, via the Si-S bond cleavage. Unlike 5, the labile 8 may be readily converted to 9via BI3-mediated cleavage of the Si-N bond. The formation of 5 and 8 confirms that 4 uniquely possesses dual nucleophilic sites: (a) the terminal sulphur atom of the dithiolene moiety; and (b) the backbone carbon of the N-heterocyclic silane unit.
ABSTRACT
The 1:1 reaction of the carbene-stabilized dithiolene zwitterion 1 with BH3·SMe2 gave the dithiolene-based hydroborane 2 and the doubly hydrogen-capped CAAC species 3 via hydride-coupled reverse electron transfer processes. The mechanism of this transformation was probed computationally using density functional theory. The subsequent 2:1 reaction of 2 with 1 resulted in 4 and 3, suggesting that 1 can mediate the B-H bond activation not only for BH3 but also for monohydroboranes. In the presence of BH3·SMe2, 2 was unexpectedly converted to the corresponding diborane(4) complex 5 through a dehydrocoupling reaction at an elevated temperature.
ABSTRACT
The 1 : 2 reaction of the imidazole-based dithiolate (2) with GeCl2 ⢠dioxane in THF/TMEDA gives 3, a TMEDA-complexed dithiolene-based germylene. Compound 3 is converted to monothiolate-complexed (5) and N-heterocyclic carbene-complexed (7) germanium(II) dithiolene complexes via Lewis base ligand exchange. A bis-dithiolene-based germylene (8), involving a 3c-4e S-Ge-S bond, has also been synthesized through controlled hydrolysis of 7. The bonding nature of 3, 5, and 8 was investigated by both experimental and theoretical methods.
ABSTRACT
A carbene-stabilized dithiolene zwitterion (3) activates ammonia, affording 4⢠and 5, through both single-electron transfer (SET) and hydrogen atom transfer (HAT). Reaction products were characterized spectroscopically and by single-crystal X-ray diffraction. The mechanism of the formation of 4⢠and 5 was probed by experimental and computational methods. This discovery is the first example of metal-free ammonia activation via HAT.
Subject(s)
Ammonia , Hydrogen , Electron Transport , Hydrogen/chemistry , Methane/analogs & derivativesABSTRACT
A series of reactions between Lewis bases and an imidazole-based dithione dimer (1) has been investigated. Both cyclic(alkyl)(amino)carbene (CAAC) (2) and N-heterocyclic carbene (NHC) (4), in addition to N-heterocyclic silylene (NHSi) (6), demonstrate the capability to cleave the sulphur-sulphur bonds in 1, giving carbene-stabilized dithiolene (L0 ) zwitterions (3 and 5) and a spirocyclic silicon-dithiolene compound (7), respectively. The bonding nature of 3, 5, and 7 are probed by both experimental and theoretical methods.
ABSTRACT
While the 1 : 1 reaction of 3 with an N-heterocyclic carbene ({(Me)CN(i-Pr)}2C:) in THF resulted in ligand-substituted product 4, the corresponding 1 : 2 reaction (in the presence of H2O) gives the first structurally characterized germanium tris(dithiolene)dianion 5 as the major product and the "naked" dithiolene radical 6Ë as a minor by-product. The structure and bonding of 4 and 5 were probed by experimental and theoretical methods. Our study suggests that carbene-mediated partial hydrolysis may represent a new method to access tris(dithiolene) complexes of main-group elements.
ABSTRACT
Reaction of the lithium dithiolene radical 2⢠with the imidazolium salt [{(Me)CN(i-Pr)}2CH]+[Cl]- (in a 1:1 molar ratio) gives the first stable naked anionic dithiolene radical 3â¢, which, when coupled with hexasulfide, [{(Me)CN(i-Pr)}2CH]+2[S6]2- (4), and N-heterocyclic silylene 5, unexpectedly results in synergic THF ring-opening via a radical mechanism.
Subject(s)
Heterocyclic Compounds/chemistry , Imidazoles/chemistry , Sulfhydryl Compounds/chemistry , Sulfides/chemistry , Anions/chemistry , Free Radicals/chemistry , Furans/chemistry , Models, Molecular , Molecular Structure , Solvents/chemistryABSTRACT
Reaction of carbene-stabilized disilicon (1) with the lithium-based dithiolene radical (2. ) affords the first dianionic silicon tris(dithiolene) complex (3). Notably, the formation of 3 represents the unprecedented utilization of carbene-stabilized disilicon (1) as a silicon-transfer agent. The nature of 3 was probed by multinuclear NMR spectroscopy, single-crystal X-ray diffraction, and DFT computations.
ABSTRACT
The first magnesium-based dithiolene, 2, was prepared by reaction of the lithium dithiolene radical, 1Ë, with 2-mesitylmagnesium bromide. Reaction of 2 with N-heterocyclic carbenes (in toluene) gave a carbene-stabilized magnesium monodithiolene complex, 3. Complex 3, in turn, is readily converted to a THF-solvated magnesium bis-dithiolene dianion, 4, via partial hydrolysis in polar solvents (i.e., THF/CH3CN). Compounds 2, 3 and 4 have been spectroscopically and structurally characterized and probed by DFT computations.
ABSTRACT
The redox chemistry of the first stable anionic dithiolene radical 1Ë was investigated by both reactivity and cyclic voltammetry studies. While one-electron reduction of 1Ë by Cp2Co or KC8 affords the corresponding dithiolate dimers 2 and 3, respectively, one-electron oxidation of 1Ë by Ph3C+BF4- (or O2) conveniently gives 4, the neutral dithiolene dimer.
ABSTRACT
Whereas low-temperature (-78 °C) reaction of the lithium dithiolene radical 1. with boron bromide gives the dibromoboron dithiolene radical 2. , the parallel reaction of 1. with (C6 H11 )2 BCl (0 °C) affords the dicyclohexylboron dithiolene radical 3. . Radicals 2. and 3. were characterized by single-crystal X-ray diffraction, UV/Vis, and EPR spectroscopy. The nature of these radicals was also probed computationally. Under mild conditions, 3. undergoes unexpected thiourea-mediated B-C bond activation to give zwitterion 4, which may be regarded as an anionic dithiolene-modified carbene complex of the sulfenyl cation RS+ (R=cyclohexyl).
ABSTRACT
Reaction of thiolate 1 with carbene-stabilized diiodo-bis-silylene (2) (in a 2:1 ratio) in THF unexpectedly gives both the first five-membered, sulfur-containing, zwitterionic silylene ring (3) via insertion of the "SiI2" unit of 2 into the olefinic C-H bond of the imidazole ring of 1 and four-membered cyclic silylene (4) via insertion of a silicon(I) atom of 2 into the Cphenyl-N bond of the carbene ligand. The parallel reaction in toluene only gives 3 as the major product. The nature of the bonding in isomeric 3 and 4 was probed by experimental and theoretical methods.
ABSTRACT
Reaction of 2-bromo-1,3,2-diazaborole (1) with excess BBr3 induces 1,2-hydrogen migration, giving 1,3,2-diazaborole-derived carbene complexes of boron bromide (2). Compound 2 exists in a dynamic solution equilibrium with 1. The 1H NMR study shows that the equilibrium lies to the right side of the dissociation reaction of 2. Parallel reaction of 1 with excess BI3 gives the corresponding 1,3,2-diazaborole-derived carbene boron iodide complex (3). Notably, in contrast to 2, the dissociation reaction of 3 largely lies to the left side, favouring the formation of 3. The dynamic solution equilibrium behaviours of 2 and 3 are probed by both experimental and theoretical methods.
ABSTRACT
Sulfurization of anionic N-heterocyclic dicarbene, [:C{[N(2,6-Pri2C6H3)]2CHCLi}]n (2), with elemental sulfur (in a 1:2 ratio) in Et2O at low temperature gives 3 by inserting two sulfur atoms into the Li-C (i.e., C2 and C4) bonds in polymeric 2. Further reaction of 3 with 2 equiv of elemental sulfur in THF affords 4⢠via unexpected C-H bond activation, which represents the first anionic dithiolene radical to be structurally characterized in the solid state. Alternatively, 4⢠may also be synthesized directly by reaction of 1 with sulfur (in a 1:4 ratio) in THF. Reaction of 4⢠with GeCl2·dioxane gives an anionic germanium(IV)-bis(dithiolene) complex (5). The nature of the bonding in 4⢠and 5 was probed by experimental and theoretical methods.
Subject(s)
Sulfhydryl Compounds/chemistry , Anions/chemistry , Free Radicals/chemistry , Molecular StructureABSTRACT
While the 1 : 1 reaction of C4-trichlorosilyl-functionalized N-heterocyclic carbene (NHC) (2) with [(η5-C5H4Li)2Fe]3[TMEDA]2 (3) gives C4-sila[1]ferrocenophane-substituted NHC (4), C4-ferrocenylsilyl-bridged bis-NHC (6) is synthesized by combining 3 with C4-chlorodimethylsilyl-functionalized NHC (5) in a 1 : 2 ratio, (compound 5 is prepared by reaction of the anionic N-heterocyclic dicarbene (NHDC) [:C{[N(2,6-Pri2C6H3)]2CHCLi}]n (1) with Me2SiCl2). In addition, ligand 4- and 6-based GeCl2 complexes (7 and 8) are also synthesized. Compounds 4-8 have been characterized by 1H, 13C, and 29Si NMR spectroscopy and single crystal X-ray diffraction.
ABSTRACT
While reaction of carbene-stabilized disilicon L:SiâSi:L (L: = C{N(2,6-(i)Pr2C6H3)CH}2) (8) with HCl·NC5H5 results in carbene-stabilized Si2Cl2 (2) and substituted 1H-imidazole (9), combination of the corresponding Fe(CO)4-modified disilicon carbene complex L:SiâSi[Fe(CO)4]:L (6) with pyridine hydrochloride gives a species containing two push-pull-stabilized parent monochlorosilylenes that are bridged by an Fe(CO)3 unit (7). The nature of 7 was further elucidated by spectroscopic, crystallographic, and computational methods. Spectroscopic data suggest that 7 exists as two diastereoisomers.
ABSTRACT
Reaction of carbene-stabilized diphosphorus, L:P-P:L (5) (L: = :C{N(2,6-Pr(i)2C6H3)CH}2) with pyridine hydrochloride yields [L:(H)P-P:L]Cl (6), a salt containing the HP2(+) cation--the elusive phosphorus analogue of the well known diazonium cation, HN2(+). In addition to reporting the synthesis and structure, the nature of (6) was further probed by DFT computations. Interestingly, carbenes may be employed to deprotonate (6), affording the starting material (5).
ABSTRACT
Reaction of the anionic N-heterocyclic dicarbene (NHDC), [:C{[N(2,6-Pr(i)2C6H3)]2CHCLi}]n (1), with SiCl4 gives the trichlorosilyl-substituted (at the C4 carbon) N-heterocyclic carbene complex (7). Abnormal carbene-SiCl4 complex (8) may be conveniently synthesized by combining 7 with HCl·NEt3. In addition, 7 may react with CH2Cl2 in warm hexane, giving the abnormal carbene-complexed SiCl3(+) cation (9). The nature of the bonding in 9 was probed with complementary DFT computations.
ABSTRACT
The first carbene-stabilized silicon-carbon mixed oxide, (SiO2)2CO2 (4), was synthesized by CO2 oxidation of either carbene-stabilized disilicon, L:SiâSi:L (L: = :C{N(2,6-Pr(i)2C6H3)CH}2) (1), or carbene-stabilized Si2O3 (2) (which can be obtained via N2O oxidation of 1). The structure and bonding of 4 was probed by both experimental and computational methods.