An Isolable One-Coordinate Lead(I) Radical with Strong g-Factor Anisotropy.

Lead-based radicals in the oxidation state of +1 are elusive species and are highly challenging to isolate in the condensed phase. In this study, we present the synthesis and characterization of the first isolable free plumbylyne radical 2 bearing a one-coordinate Pb(I) atom. It reacts with an N-heterocyclic carbene (NHC) to afford a two-coordinate NHC-ligated Pb(I) radical 3. 2 and 3 represent the first isolable Pb(I)-based radicals. Theoretical calculations and electron paramagnetic resonance analysis revealed that the unpaired electron mainly resides at the Pb 6p orbital in both radicals. Owing to the unique one-coordinate nature of the Pb atom in 2, it possesses two-fold orbital pseudo-degeneracy and substantial unquenched orbital angular momentum, and exhibits hitherto strongest g-factor anisotropy (gx,y,z=1.496, 1.166, 0.683) amongst main group radicals. Preliminary investigations into the reactivity of 2 unveiled its Pb-centered radical nature, and plumbylenes were isolated as products.

Synthesis and Reactivity of N-Heterocyclic Carbene Coordinated Formal Germanimidoyl-Phosphinidenes.

Treatment of N-heterocyclic carbene (NHC) ligated germylidenylphosphinidene MsFluidtBu-GeP(NHCiPr) (where MsFluidtBu is a bulky hydrindacene substituent, and NHCiPr is 1,3-diisopropyl-4,5-dimethyl-imidazolin-2-ylidene) with mesityl azide and 4-tertbutylphenyl azide afforded NHC coordinated formal germanimidoyl-phosphinidenes, which represent the first compounds bearing both Ge═N double bond and phosphinidene functionalities. Studies of the chemical properties revealed that the reactions preferred to occur at the Ge═N double bond, which underwent [2 + 2] cycloadditions with CO2 and ethyl isocyanate, and coordinated with coinage metals through the nitrogen atom.

Triplet bismuthinidenes featuring unprecedented giant and positive zero field splittings.

Isolation of triplet pnictinidenes, which bear two unpaired electrons at the pnictogen centers, has long been a great challenge due to their intrinsic high reactivity. Herein, we report the syntheses and characterizations of two bismuthinidenes MsFluindtBu-Bi (3) and MsFluind*-Bi (4) stabilized by sterically encumbered hydrindacene ligands. They were facilely prepared through reductions of the corresponding dichloride precursors with 2 molar equivalents of potassium graphite. The structural analyses revealed that 3 and 4 contain a one-coordinate bismuth atom supported by a Bi-C single σ bond. As a consequence, the remaining two Bi 6p orbitals are nearly degenerate, and 3 and 4 possess triplet ground states. Experimental characterizations with multinuclear magnetic resonance, magnetometry and near infrared spectroscopy coupled to wavefunction based ab initio calculations concurred to evidence that there exist giant and positive zero field splittings (>4300 cm-1) in their S = 1 ground states. Hence even at room temperature the systems almost exclusively populate the lowest-energy nonmagnetic Ms = 0 level, which renders them seemingly diamagnetic.

Monosubstituted Doublet Sn(I) Radical Featuring Substantial Unquenched Orbital Angular Momentum.

Due to their intrinsic high reactivity, isolation of heavier analogues of carbynes remains a great challenge. Here, we report the synthesis and characterization of a neutral monosubstituted Sn(I) radical (2) supported by a sterically hindered hydrindacene ligand, which represents the first tin analogue of a free carbyne. Different from all Sn(I/III) species reported thus far, the presence of a sole Sn-C σ bond in 2 renders the remaining two Sn 5p orbitals energetically almost degenerate, of which one is singly occupied and the other is empty. Consequently, its S = 1/2 ground state possesses two-fold orbital pseudo-degeneracy and substantial unquenched orbital angular momentum, as evidenced by one component of its g matrix (1.957, 1.896, and 1.578) being considerably less than 2. Consistent with this unique electronic structure, 2 can bind to an N-heterocyclic carbene to afford a neutral two-coordinate Sn(I) radical and initiate a one-electron transfer to benzophenone to furnish a Sn(II)-ketyl radical anion adduct. As a manifestation of its Sn-centered radical nature, 2 reacts with diphenyl diselenide and p-benzoquinone to form Sn-S and Sn-O bonds, respectively.

A germanimidoyl chloride: synthesis, characterization and reactivity.

The first germanimidoyl chloride MsFluindtBu-Ge(Cl)NMes (2, where MsFluindtBu is a bulky hydrindacene skeleton) was synthesized through the reaction of MsFluindtBu-GeCl (1) and mesityl azide (MesN3). In contrast, treatment of 1 with a less bulky azide ArN3 (Ar = 4-tBuC6H4) produced a germatetrazole chloride MsFluindtBu-Ge(Cl)N4Ar2 (3), and a salt [MsFluindtBu-GeN4Ar2]+[BArF4]- (4; ArF = 3,5-(CF3)2C6H3) followed by chloride abstraction with NaBArF4, both bearing a five-membered GeN4 ring. Functionalization of 2 with Ar'Li (Ar' = 3,5-tBu2C6H3) or MeLi furnished a germanimine MsFluindtBu-Ge(Ar')NMes (5) or an amide lithium salt MsFluindtBu-Ge(Me)2-N(Mes)Li(thf) (6).

An isolable germylyne radical with a one-coordinate germanium atom.

Carbynes (R-[Formula: see text]), species that bear a monovalent carbon atom with three non-bonding valence electrons, are important intermediates and potentially useful in organic synthetic chemistry. However, free species of the type R-[Formula: see text] of any group 14 element (E) have eluded isolation in the condensed phase due to their high reactivity. Here we report the isolation, characterization and reactivity of a crystalline germylyne radical by using a sterically hindered hydrindacene ligand. The germylyne radical bears an essentially one-coordinate germanium atom as shown by single-crystal X-ray diffraction analysis. Electron paramagnetic resonance spectroscopic studies and theoretical calculations show that the germylyne radical features a doublet ground state, and the three non-bonding valence electrons at the germanium atom contribute to the lone pair of electrons as the highest occupied molecular orbital-3 and one unpaired electron as the singly occupied molecular orbital.

Diazophosphane HPN2.

Diazophosphane HPN2, a heavy analogue of hydrazoic acid (HN3), has been synthesized at low temperature (10 K) through photolytic reactions of molecular nitrogen (N2) with phosphine (PH3) and phosphaketene (HPCO) under irradiations at 193 and 365 nm, respectively. The characterization of HPN2 and its isotopologues DPN2 and HP15N2 by matrix-isolation IR and UV-vis spectroscopy is supported by quantum chemical calculations at the CCSD(T)-F12a/cc-pVTZ-F12 level of theory. Upon irradiation at 266 nm, the P-N bond in HPN2 breaks, whereas its photolysis at 193 nm generates the elusive phosphinyl radical •PN2.

Phosphine-Stabilized Germylidenylpnictinidenes as Synthetic Equivalents of Heavier Nitrile and Isocyanide in Cycloaddition Reactions with Alkynes.

The reactions of chlorogermylene MsFluindtBu-GeCl 1, supported by a sterically encumbered hydrindacene ligand MsFluindtBu, with NaPCO(dioxane)2.5 and NaAsCO(18-c-6) in the presence of trimethylphosphine afforded trimethylphosphine-stabilized germylidenyl-phosphinidene 2 and -arsinidene 3, respectively. Structural and computational investigations reveal that the Ge-E' bond (E' = P and As) features a multiple-bond character. 2 and 3 exhibit diverse reactivity toward trimethylsilylacetylene and 4-tetrabutylphenylacetylene. Specifically, 2 underwent cycloadditions with both alkynes affording the first six-membered aromatic phosphagermabenzen-1-ylidenes 4 and 5, respectively, through the heavier isocyanide intermediate MsFluindtBu-PGe. In contrast, 3 could serve as a synthetic equivalent of heavier isocyanides and nitriles when treated with trimethylsilylacetylene and 4-tetrabutylphenylacetylene yielding arsagermene 6 and arsolylgermylene 7, respectively. The reaction mechanisms for the cycloadditions were investigated through density functional theory calculations. The reactivity studies highlight the potential of 2 and 3 in accessing heavy main-group element-containing heterocycles.

The cis/trans conformation approach for tuning the magnetic coupling in a diradical: isolation of pure pyridine-based diradical dianions.

Two-electron reductions of 3,3'-bis(2,6-dimesitylpyridin-4-yl)-1,1'-biphenyl 1 with elemental potassium in the absence and presence of 18-c-6 afforded the diradical dianion salts [K+]2˙[trans-1]˙˙2- and [K(18-c-6)]+2˙[cis-1]˙˙2-, which exhibit trans and cis configurations, respectively. The transoid conformer could be converted to the cisoid one through reacting with 18-c-6.

Vibrational spectrum and photochemistry of phosphaketene HPCO.

The vibrational spectra of the simplest phosphaketene HPCO and its isotopologue DPCO in solid Ar-matrices at 12.0 K have been analyzed with the aid of the computations at the CCSD(T)-F12a/cc-pVTZ-F12 level using configuration-selective vibrational configuration interaction (VCI). In addition to the four IR fundamentals, four overtone and ten combination bands have been unambiguously identified. Furthermore, the photochemistry of HPCO in the matrix has been investigated for the first time. Upon UV-light irradiation (365 or 266 nm), CO-elimination occurs by forming the parent phosphinidene HP that can be trapped by ˙NO to yield the elusive phosphinimine-N-oxyl radical HPNO˙. In contrast, an excimer laser (193 nm) irradiation of HPCO causes additional decomposition to H˙ and ˙PCO with concomitant formation of the long-sought phosphaethyne HOCP.

A stable tetrazagallole and its radical anion dimer.

The reaction of the carbazole ligand supported Ga(I) compound LGa(THF) (3) and 1-azido-4-(tert-butyl)benzene (ArN3) afforded the first stable tetrazagallole LGaN4Ar2 (4) bearing a three-coordinate Ga atom. Reduction of 4 with elemental potassium resulted in the radical dimer {[K(18-c-6)]+[4]˙-}2, featuring a strong antiferromagnetic interaction between the spin centers.

A bis(imino)carbazolate pincer ligand stabilized mononuclear gallium(I) compound: synthesis, characterization, and reactivity.

The first bis(imino)carbazolate pincer ligand supported mononuclear Ga(I) compound LGa: (3) was synthesized and fully characterized. Oxidation of 3 with elemental selenium afforded the dinuclear Ga(III) compound [LGa(µ-Se)]2 (4) bearing two bridging Se atoms. Ligand substitution of Cr(CO)6 with 3 under UV light irradiation afforded the gallylene-chromium complex LGa: → Cr(CO)5 (5). In addition, the attempted synthesis of the aluminium analogue LAl: through reduction of LAlI2 (7) only led to isolation of the dinuclear Al(III) compound (LAlI)2 (8), most probably formed through the C-C coupling of two imino radicals.

A high-spin diradical dianion and its bridged chemically switchable single-molecule magnet.

Triplet diradicals have attracted tremendous attention due to their promising application in organic spintronics, organic magnets and spin filters. However, very few examples of triplet diradicals with singlet-triplet energy gaps (ΔE ST) over 0.59 kcal mol-1 (298 K) have been reported to date. In this work, we first proved that the dianion of 2,7-di-tert-butyl-pyrene-4,5,9,10-tetraone (2,7-tBu2-PTO) was a triplet ground state diradical in the magnesium complex 1 with a singlet-triplet energy gap ΔE ST = 0.94 kcal mol-1 (473 K). This is a rare example of stable diradicals with singlet-triplet energy gaps exceeding the thermal energy at room temperature (298 K). Moreover, the iron analog 2 containing the 2,7-tBu2-PTO diradical dianion was isolated, which was the first single-molecule magnet bridged by a diradical dianion. When 2 was doubly reduced to the dianion salt 2K2, single-molecule magnetism was switched off, highlighting the importance of diradicals in single-molecule magnetism.

Si(II) Cation-Promoted Formation of an Abnormal NHC-Bound Silylene and a cAAC-Silanyl Radical Ion.

The reaction of amidinatosilylene LSi(:)Cl [L = PhC(NtBu)2] with N-heterocyclic carbene IAr [:C{N(Ar)CH}2, where Ar = 2,6-iPr2C6H3] and NaOTf in tetrahydrofuran (THF) facilely afforded a silicon(II) cation [LSi(:)-aIAr]+OTf- (1+OTf-), where IAr isomerizes to abnormal N-heterocyclic carbene aIAr, coordinating to the silicon(II) center. Its Ge homologue, [LGe(:)-aIAr]+OTf- (2+OTf-), was also accessed via the same protocol. For the formation of 1+, we propose that an in situ-generated Si(II) cation [LSi(:)]+ under the treatment of LSi(:)Cl with NaOTf may isomerize IAr in THF. In contrast, the replacement of IAr with cyclic alkyl(amino) carbene (cAAC) furnished a cAAC-silanyl radical ion [LSi(H)-cAAC]•+(LiOTf2)- [3•+(LiOTf2)-], which may undergo an abstraction of the H radical from THF. All of the products were characterized by nuclear magnetic resonance spectroscopy, electron paramagnetic resonance, and X-ray crystallography, and their bonding scenarios were investigated by density functional theory calculations. These studies provide new perspective on carbene-silicon chemistry.

Yttrium germole dianion complexes with Y-Ge bonds.

The reactions of dipotassium 3,4-dimethyl-2,5-bis(trimethylsilyl)-germole dianion K2[1] with YCl3 and Cp*YCl2 (Cp* = cyclopentadienyl) in THF at room temperature afforded the dianion salt [(K-cryptand-222)2][1-YCl3] (K2[2]) and the dimeric complex [1-Y-Cp*]2 (3), respectively. While the polymeric complex {[(1)2-Y-K(toluene)]2}n (4) was obtained from the reaction of K2[1] and half molar equivalent of YCl3(THF)3.5 in toluene at 80 °C. The germole dianions in complexes 3 and 4 feature η5/η1 coordination interactions with the yttrium atoms. They represent the first examples of rare earth (RE) complexes containing RE-Ge bonds other than the RE-GeR3 structural type.

Stable Radical Cation and Dication of a 1,4-Disilabenzene.

The reaction of (LSi:)2 (1; L = PhC(NtBu)2) with 2 equiv of Me3SiC2C2SiMe3 resulted in the formation of (Me3SiC2)2(Me3Si)2C4Si2(L)2 (2). 2 exhibited a one-electron transfer when treated with 1 equiv of [Ph3C]+[B(C6F5)4]- to yield [(Me3SiC2)2(Me3Si)2C4Si2(L)2]·+[B(C6F5)4]- (3) and Ph3CCPh3, respectively. When compound 2 was treated with 2 equiv of AgOSO2CF3 a transfer of two electrons occurred to produce [(Me3SiC2)2(Me3Si)2C4Si2(L)2]2+·2[OSO2CF3]- (4) and elemental silver. The 1,4-disilabenzene 2 is disclosed of an open-shell singlet diradical character, and 3 and 4 are, respectively, the elusive stable radical cation and dication species of the 1,4-disilabenzene (2). Furthermore, 2 reacted with group 16 elements of O, S, and Se by oxidative addition to form (Me3SiC2)2(Me3Si)2C4Si2(L)2(µ-O2) (5) and (Me3SiC2)2(Me3Si)2C4Si2(L)2(µ-E) (E = S (6) and Se (7)), respectively.

Crystalline Diradical Dianions of Pyrene-Fused Azaacenes.

Although diradicals and azaacenes have been greatly attractive in fundamental chemistry and functional materials, the isolable diradical dianions of azaacenes are still unknown. Herein, we describe the first isolation of pyrene-fused azaacene diradical dianion salts [(18-c-6)K(THF)2 ]+ [(18-c-6)K]+ ⋅12-.. and [(18-c-6)K(THF)]2+ ⋅22-.. by reduction of the neutral pyrene-fused azaacene derivatives 1 and 2 with excess potassium graphite in THF in the presence of 18-crown-6. Their electronic structures were investigated by various experiments, in conjunction with theoretical calculations. It was found that both dianions are open-shell singlets in the ground state and their triplet states are thermally readily accessible owing to the small singlet-triplet energy gap. This work provides the first examples of crystalline diradical dianions of azaacenes with considerable diradical character.

Stable, yet "naked", azo radical anion ArNNAr- and dianion ArNNAr2- (Ar = 4-CN-2,6-iPr2-C6H2) with selective CO2 activation.

Azo radical anion 1˙- and dianion 12- have been isolated by one- and two-electron reduction of the azo compound 1 (ArNNAr, Ar = 4-CN-2,6-iPr2-C6H2) with alkali metals, respectively. The reduced species have been characterized by single-crystal X-ray analysis, EPR, UV and FT-IR spectroscopy, as well as SQUID measurements. The filling of one and two electrons in the π* orbital of the N-N double bond of 1 leads to a half-double N-N bond in 1˙- and a single N-N bond in 12-. The uncoordinated nature of these reduced species enables them to activate CO2. The exposure of 1˙- solution to CO2 led to the formation of oxalate anion C2O42-, while that of 12- solution to CO2 afforded the hydrazine dicarboxylate dianion [1-2CO2]2-, which reversibly dissociated back to 1 and CO2 upon oxidation.

Isolable cyclic radical cations of heavy main-group elements.

One-electron oxidation of 1,3-digerma-2,4-dipnictacyclobutadiene [LHGeE]2 (LH = CH[CHNDipp]2, dipp = 2,6-iPr2C6H3; 1: E = P; 2: E = As) with Ag[Al(ORF)4] (RF = C(CF3)3) afforded the stable radical cation salts 1˙+·[Al(ORF)4]- and 2˙+·[Al(ORF)4]-, respectively. The radical cation salts have been fully characterized, in conjunction with theoretical calculations. The EPR spectroscopic studies and DFT calculations reveal that the spin density mainly resides at the heavy pnictogen atoms, rather than delocalizes over the Ge2E2 ring. They represent the first structurally characterized cyclic radical species composed of both heavy group 14 and 15 elements.

Stable Radical Cation and Dication of an N-Heterocyclic Carbene Stabilized Digallene: Synthesis, Characterization and Reactivity.

One- and two-electron oxidation of a digallene stabilized by an N-heterocyclic carbene afforded the first stable gallium-based radical cation and dication salts, respectively. Structural analysis and theoretical calculations reveal that the oxidation occurs at the Ga=Ga double bond, leading to removal of π electrons of the double bond and a decrease of the bond order. The spin density of the radical cation mainly locates at the two gallium centers as demonstrated by EPR spectroscopy and theoretical calculations. Moreover, the reactivity of the radical cation salt toward nBu3 SnH and cyclo-S8 was studied; a digallium-hydride cation salt containing a Ga-Ga single bond and a gallium sulfide cluster bearing an unprecedented ladder-like Ga4 S4 core structure were obtained, respectively.