Ferrocene-Based N-Heterocyclic Silylenes: Monomeric Silanechalcogenones, Silanimines, Silirenes, and Insertion Products with P4.

The stable ferrocene-based N-heterocyclic silylenes fc[(N{B})2Si] (A; fc=1,1'-ferrocenylene, {B}=(HCNDipp)2B, Dipp=2,6-diisopropylphenyl) and fc[(NDipp)2Si] (B) are compared in a study focussing on their reactivity towards a range of small to moderately sized molecular substrates, viz. P4, S8, Se8, MesN3 (Mes=mesityl), RC≡CH, and RC≡CR (R=Ph, SiMe3). The Dipp-substituted congener B exhibits a more pronounced ambiphilicity and is sterically less congested than its 1,3,2-diazaborolyl-substituted relative A, in line with the higher reactivity of the former. The difference in reactivity is obviously due more to electronic than to steric reasons, as is illustrated by the fact that both A and B react with the comparatively bulky substrate MesN3 under mild conditions to afford the corresponding silanimine fc[(N{B})2Si=NMes] and fc[(NDipp)2Si=NMes], respectively. The heavier ketone analogues fc[(N{B})2Si=E] (E=S, Se, Te) are readily available from A and the corresponding chalcogen. In contrast, the reaction of the more reactive silylene B with elemental sulfur or selenium is unspecific, affording product mixtures. However, fc[(NDipp)2Si=Se] is selectively prepared from B and (Et2N)3PSe; the Te analogue is also accessible, but crystallises as head-to-tail dimer.

A complete series of N-heterocyclic tetrylenes (Si-Pb) with a 1,1'-ferrocenediyl backbone enabled by 1,3,2-diazaborolyl N-substituents.

The use of bulky 1,3,2-diazaborolyl N-substituents has allowed the synthesis of the complete series of ferrocene-based N-heterocyclic tetrylenes fc[(N{B})2E] (fc = 1,1'-ferrocenediyl, {B} = (HCNC6H3-2,6-iPr2)2B, E = Si-Pb). The silylene fc[(N{B})2Si] is inert towards NH3, CO2 or N2O under ambient conditions and thus significantly less reactive than the N-aryl homologue fc[(NC6H3-2,6-iPr2)2Si]. In accord with its higher reactivity, computational results indicate a more pronounced ambiphilicity of fc[(NC6H3-2,6-iPr2)2Si]. Our computational investigation of the model compound fc[(NBMe2)2Si] suggests that silylenes of this type may be superior to fc[(NC6H3-2,6-iPr2)2Si] in terms of ambiphilicity.

Ferrocene-Based N-Heterocyclic Plumbylenes [Fe{(η5 -C5 H4 )NSiMe2 R}2 Pb:]: Influence of the Steric Demand of the N-Substituents on Their Dimerization via C-H Activation with PbII.

Ferrocene-based N-heterocyclic plumbylenes fc[(NSiMe2 R)2 Pb:] (1; fc=1,1'-ferrocenylene) are easily accessible by transamination from [(Me3 Si)2 N]2 Pb and the corresponding 1,1'-diaminoferrocene derivatives fc(NHSiMe2 R)2 . They may form unconventional dimers 2 by a process, which causes the cleavage of a cyclopentadienyl C-H bond and the formation of a Pb-C and an N-H bond. The monomer-dimer equilibrium (2 1⇆2) has been addressed experimentally and computationally. It critically depends on the steric demand of the N-substituents SiMe2 R, which has been varied systematically by using homologues with aliphatic (R=methyl, ethyl, isopropyl, tert-butyl) and aromatic units (R=phenyl, mesityl, ferrocenyl). Even in the sterically least congested case (R=methyl), dimerization is only slightly exergonic. It eventually becomes prohibitively endergonic with increasingly larger substituents and is thus not observed for R=tert-butyl, mesityl, and ferrocenyl. R=phenyl represents a borderline case, where the dimer is still detectable in the equilibrium mixture, albeit as a very minor component, in accord with the slightly endergonic Gibbs free energy change calculated for its formation. Addition of 4-dimethylaminopyridine (DMAP) to the monomer-dimer equilibrium mixtures cleanly affords the corresponding adducts [1(DMAP)], irrespective of the equilibrium composition.

A crystalline cyclic (alkyl)(amino)carbene with a 1,1'-ferrocenylene backbone.

Cyclic (alkyl)(amino)carbenes with a 1,1'-ferrocenylene backbone (fcCAACs) are established as an original family by the preparation of a crystalline congener. The Ccarbene bond angle is unprecedentedly wide for a CAAC, causing an exceptionally pronounced ambiphilicity. The redox-active backbone opens the door to unconventional metalloradicals and oligoradicals.

Reactions of Mesityl Azide with Ferrocene-Based N-Heterocyclic Germylenes, Stannylenes and Plumbylenes, Including PPh2 -Functionalised Congeners.

The reactivity of ferrocene-based N-heterocyclic tetrylenes [{Fe(η5 -C5 H4 -NSitBuMe2 )2 }E] (E=Ge, Sn, Pb) towards mesityl azide (MesN3 ) is compared with that of PPh2 -functionalised congeners exhibiting two possible reaction sites, namely the EII and PIII atom. For E=Ge and Sn the reaction occurs at the EII atom, leading to the formation of N2 and an EIV =NMes unit. The germanimines are sufficiently stable for isolation. The stannanimines furnish follow-up products, either by [2+3] cycloaddition with MesN3 or, in the PPh2 -substituted case, by NMes transfer from the SnIV to the PIII atom. Whereas [{Fe(η5 -C5 H4 -NSitBuMe2 )2 }Pb] and other diaminoplumbylenes studied are inert even under forcing conditions, the PPh2 -substituted congener forms an addition product with MesN3 , thus showing a behaviour similar to that of frustrated Lewis pairs. The germylenes of this study afford copper(I) complexes with CuCl, including the first structurally characterised linear dicoordinate halogenido complex [CuX(L)] with a heavier tetrylene ligand L.

Planar-chiral 1,1'-diaminoferrocenes.

Planar-chiral homologues of 1,1'-diaminoferrocene, which bear a single additional substituent adjacent to one of the amino groups, are prepared as racemic mixtures in a few steps and in good yields from ferrocene. Various substituents relevant to steric shielding, coordination and further functionalisation are used, giving access to ferrocene-based planar-chiral diimines and diamines as well as stable N-heterocyclic carbenes and tetrylenes by transformations analogous to procedures established for 1,1'-diaminoferrocene.

Reactivity of an N-heterocyclic silylene with a 1,1'-ferrocenediyl backbone towards carbonyl compounds, including carbon suboxide.

Reactions of a silylene with a ketene and with carbon suboxide are reported, respectively leading to the first silaallene oxide and to a silylketene, whose reaction with water affords the first structurally characterised stable methyleneketene and constitutes a unique type of single-crystal-to-single-crystal transformation of a molecular solid by a stoichiometric gas-solid chemical reaction.

A Stable N-Heterocyclic Silylene with a 1,1'-Ferrocenediyl Backbone.

The N-heterocyclic silylene [{Fe(η5 -C5 H4 -NDipp)2 }Si] (1DippSi, Dipp=2,6-diisopropylphenyl) shows an excellent combination of pronounced thermal stability and high reactivity towards small molecules. It reacts readily with CO2 and N2 O, respectively affording (1DippSiO2 )2 C and (1DippSiO)2 as follow-up products of the silanone 1DippSiO. Its reactions with H2 O, NH3 , and FcPH2 (Fc=ferrocenyl) furnish the respective oxidative addition products 1DippSi(H)X (X=OH, NH2 , PHFc). Its reaction with H3 BNH3 unexpectedly results in B-H, instead of N-H, bond activation, affording 1DippSi(H)(BH2 NH3 ). DFT results suggest that dramatically different mechanisms are operative for these H-X insertions.

d-d Dative Bonding Between Iron and the Alkaline-Earth Metals Calcium, Strontium, and Barium.

Double deprotonation of the diamine 1,1'-(tBuCH2 NH)-ferrocene (1-H2 ) by alkaline-earth (Ae) or EuII metal reagents gave the complexes 1-Ae (Ae=Mg, Ca, Sr, Ba) and 1-Eu. 1-Mg crystallized as a monomer while the heavier complexes crystallized as dimers. The Fe⋅⋅⋅Mg distance in 1-Mg is too long for a bonding interaction, but short Fe⋅⋅⋅Ae distances in 1-Ca, 1-Sr, and 1-Ba clearly support intramolecular Fe⋅⋅⋅Ae bonding. Further evidence for interactions is provided by a tilting of the Cp rings and the related 1 H NMR chemical-shift difference between the Cp α and ß protons. While electrochemical studies are complicated by complex decomposition, UV/Vis spectral features of the complexes support Fe→Ae dative bonding. A comprehensive bonding analysis of all 1-Ae complexes shows that the heavier species 1-Ca, 1-Sr, and 1-Ba possess genuine Fe→Ae bonds which involve vacant d-orbitals of the alkaline-earth atoms and partially filled d-orbitals on Fe. In 1-Mg, a weak Fe→Mg donation into vacant p-orbitals of the Mg atom is observed.

(Benz-)imidazolin-2-ylidene-benzimidazolatonickel(II) Chelates: Syntheses, Structures, and Tuning of Noninnocent Chelate Ligand Behavior.

The deprotonation of 1-(1H-benzimidazol-2-yl)-3-methylbenzimidazolium hexafluorophosphate (2MeH2[PF6]) and 1-(1H-benzimidazol-2-yl)-3-isopropylbenzimidazolium hexafluorophosphate (2iPrH2[PF6]) with potassium tert-butoxide in THF afforded the benzimidazolium-benzimidazolates 2MeH and 2iPrH. The "instant carbene" behavior of these conjugated mesomeric betaines was demonstrated by trapping their carbenic tautomers 2'MeH and 2'iPrH with elemental sulfur and selenium, which afforded the corresponding thio- and selenourea derivatives 2'MeHE and 2'iPrHE (E = S, Se). The treatment of 2MeH and 2iPrH with nickelocene furnished the nickel(II) complexes [NiCp(2'Me)] and [NiCp(2'iPr)], which contain an anionic C,Namido-chelating NHC ligand. The electronic structure and redox behavior of the nickel(II) chelates were investigated, as well as those of the closely related chelates [NiCp(1'Me)] and [NiCp(1'iPr)] derived from the corresponding imidazolium-benzimidazolates 1MeH and 1iPrH. According to DFT calculations, the highest occupied molecular orbital (HOMO) is located over the NiCp moiety and the π system of the chelate ligand with a large contribution from the (benz-)imidazolate moiety. Cyclic voltammetry revealed a reversible oxidation to the monocation [NiCp(L)]+ (E1/2 = 0.315, 0.222, 0.396, 0.265 V vs ferrocene/ferrocenium for L = 1'Me, 1'iPr, 2'Me, 2'iPr, respectively) in CH2Cl2/0.1 M n-Bu4N[B(ArF)4] (B(ArF)4- = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate), and isosbestic behavior was found in UV-vis-NIR spectroelectrochemical experiments. The different redox potentials reflect the different donor/acceptor properties of the NHC part of the chelate ligands, with 1'iPr being the strongest and 2'Me the weakest net electron donor. The EPR spectroscopic signature of [NiCp(2'Me)]+ in CH2Cl2/0.1 M n-Bu4N[B(ArF)4] at 100 K is consistent with a chelate-ligand-based radical with strong spin-orbit coupling to the Ni center. In contrast, the EPR spectra of [NiCp(1'Me)]+, [NiCp(1'iPr)]+, and [NiCp(2'iPr)]+ indicate that these monocations are best described as NiIII complexes, the comparatively higher contribution of the NiIII(L) vs the NiII(L•+) valence tautomer being supported by the results of open-shell DFT calculations.

Imidazolium-benzimidazolates as convenient sources of donor-functionalised normal and abnormal N-heterocyclic carbenes.

Imidazolium-benzimidazolates are readily available conjugated mesomeric betaines, whose carbenic tautomers can form C,Nimine-metal chelates containing amino-functionalised normal or abnormal NHC ligands, depending on the degree of steric congestion. Deprotonation of the amino moiety gives rise to imine-functionalised C,Namido-metal chelates, whose Nimine atom can be easily utilised for the construction of heteronuclear complexes.

Stable and Persistent Acyclic Diaminocarbenes with Cycloalkyl Substituents and Their Transformation to ß-Lactams by Uncatalysed Carbonylation with CO.

Four new acyclic diaminocarbenes (ADACs), viz. [(cyclo-Cn H2n-1 )2 N]2 C (n=5-7) and iPr2 N-C-N(cyclo-C6 H11 )2 , were synthesised by reacting the corresponding formamidinium hexafluorophosphates with NaN(SiMe3 )2 . Their nucleophilicities and electrophilicities were respectively judged from the 1 JCH values determined for the N2 CH unit of the corresponding formamidinium cations and from the 77 Se NMR chemical shifts of the selenourea derivatives obtained from the reaction of elemental selenium with the corresponding ADACs. An ambiphilic profile essentially identical to that of the "Alder carbene" (iPr2 N)2 C was found in each case. Similar to the latter carbene, the new ADACs undergo a well-defined thermal decomposition by ß-fragmentation, affording an alkene and a formamidine. The stabilities of [(cyclo-Cn H2n-1 )2 N]2 C depend strongly on the value of n, following the order 6>5>7, with the latter congener being too unstable for isolation. [(cyclo-C6 H11 )2 N]2 C shows no thermal decomposition at room temperature in solution and is thus significantly more stable than (iPr2 N)2 C. The stability of iPr2 N-C-N(cyclo-C6 H11 )2 is intermediate between that of (iPr2 N)2 C and [(cyclo-C6 H11 )2 N]2 C, its ß-fragmentation selectively affording propene and iPrN=CH-N(cyclo-C6 H11 )2 . [(cyclo-Cn H2n-1 )2 N]2 C (n=5-7) react readily with CO under mild conditions, selectively affording trisubstituted spirocyclic ß-lactam derivatives with an antimicrobial activity spectrum similar to that of penicillin G.

Reactive Dimerization of an N-Heterocyclic Plumbylene: C-H Activation with PbII.

The N-heterocyclic plumbylene [Fe{(η5 -C5 H4 )NSiMe3 }2 Pb:] is in equilibrium with an unprecedented dimer in solution, whose formation involves the cleavage of a strong C-H bond and concomitant formation of a Pb-C and an N-H bond. According to a mechanistic DFT assessment, dimer formation does not involve direct PbII insertion into a cyclopentadienyl C-H bond, but is best described as an electrophilic substitution. The bulkier plumbylene [Fe{(η5 -C5 H4 )NSitBuMe2 }2 Pb:] shows no dimerization, but compensates its electrophilicity by the formation of an intramolecular Fe-Pb bond.

Synthesis and characterization of 1'-(diphenylphosphino)-1-isocyanoferrocene, an organometallic ligand combining two different soft donor moieties, and its Group 11 metal complexes.

The development of a practical synthesis of 1'-(diphenylphosphino)-1-aminoferrocene (2) and its P-borane adduct (2B) allowed the facile preparation of 1'-(diphenylphosphino)-1-isocyanoferrocene (1). This compound combining two specific soft-donor moieties was studied as a ligand for univalent Group 11 metal ions. The reactions of 1 with AgCl at 1 : 1 and 2 : 1 molar ratios only led to the coordination polymer [Ag2(µ-Cl)2(µ(P,C)-1)]n (6), while those with Ag[SbF6] provided the dimer [Ag2(Me2CO-κO)2(µ(P,C)-1)2][SbF6]2 and the quadruply-bridged disilver complex [Ag2(µ(P,C)-1)4][SbF6]2 (8), respectively. Addition of 1 to [AuCl(tht)] (tht = tetrahydrothiophene) afforded the mono- and the digold complex, [AuCl(1-κP)] (9) and [(µ(P,C)-1)(AuCl)2] (10), depending on the reaction stoichiometry. Finally, the reaction of 1 with [Au(tht)2][SbF6] or halogenide removal from 9 with AgNTf2 led to cationic dimers [Au2(µ(P,C)-1)2]X2 (11, X = SbF6 (a) or NTf2 (b)). Catalytic tests in the Au-mediated isomerization of (Z)-3-methylpent-2-en-4-yn-1-ol to 2,3-dimethylfuran revealed that 11a and 11b are substantially less catalytically active than their analogues containing 1'-(diphenylphosphino)-1-cyanoferrocene as the ligand, most likely due to a stronger coordination of the isonitrile moiety, which prevents dissociation of the dimeric complexes into catalytically active monomeric species.

Coinage Metal Complexes of the Carbenic Tautomer of a Conjugated Mesomeric Betaine Akin to Nitron.

This study was motivated by our recent observation that the analytical reagent Nitron (2) is an "instant carbene", whose reaction with coinage metal salts MX afforded complexes of its carbenic tautomer 1,4-diphenyl-3-phenylamino-1,2,4-triazol-5-ylidene (2'). Our aim was to establish an alkyl homologue of 2 in order to achieve a carbenic tautomer of higher donicity. For this purpose 1-tert-butyl-4-methyl-1,2,4-triazol-4-ium-3-tert-butylaminide (6) was synthesized. Its reactions with MX afforded complexes of the carbenic tautomer 1-tert-butyl-3-tert-butylamino-4-methyl-1,2,4-triazol-5-ylidene (6'). With a stoichiometric ratio of 1:1 complexes of the type [MX(6')] were obtained. A ratio of 2:1 furnished complexes of the type [MX(6')2] or [M(6')2]X. 6' is a better σ-donor and less electrophilic than 2' according to NMR spectroscopic data of 6H[BF4] and 6' = Se, respectively, and IR spectroscopic data of [RhCl(6')(CO)2] confirm that its net electron donor capacity is superior to that of 2'. A comparison of the complexes of 2' and 6' reveals two pronounced structural differences. [CuX(6')2] (X = Cl, Br) exhibit more acute C‒Cu‒C bond angles than [CuX(2')2]. In contrast to [CuCl(2')], [CuCl(6')] aggregates through Cu···Cu contacts of ca. 2.87 Å, compatible with cuprophilic interactions. These differences may be explained by the complementary steric requirements of the t-Bu and the Me substituent of 6'.

Phosphido complexes derived from 1,1'-ferrocenediyl-bridged secondary diphosphines.

This paper focuses on ferrocene-based secondary diphosphines of the type [Fe{η5-C5H4(PHR)}2] with P-substituents of distinctly different steric and electronic properties, namely methyl, neopentyl (Np), tert-butyl, phenyl and 3,5-bis(trifluoromethyl)phenyl (XyF). The reaction of [Fe{η5-C5H4(PHPh)}2] (H21a) and [Fe{η5-C5H4(PHt-Bu)}2] (H21b) with n-BuLi in the presence of TMEDA afforded lithium diphosphides of the type [Li2(µ-1)(TMEDA)2], which contain a cyclic non-planar Li2P2 core. The analogous reactions of [Fe{η5-C5H4(PHMe)}2] (H21c) and [Fe{η5-C5H4(PHNp)}2] (H21d) furnished dimeric aggregates exhibiting a ladder-type Li4P4 motif, viz. [Li4(µ-1c)2(TMEDA)3] and [Li2(µ-1d)(TMEDA)]2. H21e (R = XyF) did not afford a stable lithium diphosphide. A Brønsted metathesis with Zr(NMe2)4 was possible with the aryl-substituted compounds H21a and H21e, leading to products of the type [{Zr(NMe2)3}2(µ-1)]. In contrast, the alkyl-substituted congeners H21b-H21d were inert towards Zr(NMe2)4. The reaction of [Fe{η5-C5H4(PHR)}2] with nickelocene afforded intractable mixtures of numerous products in the case of H21c and H21e. In the other three cases, compounds of the type [(NiCp)2(µ-1)] were isolated. For H21b and H21d a two-stepped reaction via a phosphino-phosphido intermediate of the type [NiCp(H1)] was observed, which could be isolated and fully characterised in the case of [NiCp(H1b)].

Redox-Active N-Heterocyclic Germylenes and Stannylenes with a Ferrocene-1,1'-diyl Backbone.

We describe ferrocene-based N-heterocyclic germylenes and stannylenes of the type [Fe{(η5 -C5 H4 )NR}2 E:] (1 RE; E=Ge, Sn; R=neopentyl (Np), mesityl (Mes), trimethylsilyl (TMS)), which constitute the first examples of redox-functionalised N-heterocyclic tetrylenes (NHTs). These compounds are thermally stable and were structurally characterised by means of X-ray diffraction studies, except for the neopentyl-substituted stannylene 1 NpSn, the decomposition of which afforded the aminoiminoferrocene [fc(NHCH2 tBu)(N=CHtBu)] (2) and the spiro tin(IV) compound (1 Np)2 Sn (3). DFT calculations show that the HOMO of the NHTs of our study is localised on the ferrocenylene backbone. A one-electron oxidation process affords ions of the type 1 RE+. . In contrast to the NHC system 1 RC, the localised ferrocenium-type nature of the oxidised form does not compromise the fundamental tetrylene character of 1 RE+. .

Magnetic Field Landscapes Guiding the Chemisorption of Diamagnetic Molecules.

It is shown that the self-assembly of diamagnetic molecule submonolayers on a surface can be influenced by magnetic stray field landscapes emerging from artificially fabricated magnetic domains and domain walls. The directed local chemisorption of diamagnetic subphthalocyaninatoboron molecules in relation to the artificially created domain pattern is proved by a combination of surface analytical methods: ToF-SIMS, X-PEEM, and NEXAFS imaging. Thereby, a new method to influence self-assembly processes and to produce patterned submonolayers is presented.

New Stable and Persistent Acyclic Diaminocarbenes.

The portfolio of acyclic diaminocarbenes (ADACs) has been substantially expanded, owing to the synthesis of eleven new formamidinium salts, mostly of the type [(iPr2N)CH(NRR')][PF6], for use as immediate carbene precursors. The corresponding ADACs (iPr2N)C(NRR') were sufficiently stable for isolation in the case of NRR' = 2-methylpiperidino (13), 3-methylpiperidino (14), 4-methylpiperidino (15), morpholino (17) and NiPrPh (20), but had to be trapped in situ in the case of NRR' = 2,2,6,6-tetramethylpiperidino (12) and NiPrMe (19). The tetraaryl-substituted ADACs (Ph2N)2C (22) and (Ph2N)C[N(C6F5)2] (24) also could only be generated and trapped in situ. Trapping with elemental selenium was particularly efficient, affording the corresponding selenourea derivative in all cases, whereas trapping with [{Rh(µ-Cl)(cod)}2] did not work for 12 and 24. The (77)Se NMR chemical shifts, δ((77)Se), of the selenourea compounds derived from the new ADACs lie in the range 450-760 ppm, which indicates a much higher electrophilicity and π-accepting capability of ADACs in comparison with NHCs, which typically exhibit δ((77)Se)<200 ppm. The extreme low-field shift of 758 ppm observed for 12Se can be rationalised by the results of DFT calculations, which revealed that ADAC 12 has a minimum energy conformation with the 2,2,6,6-tetramethylpiperidino unit perpendicular to the N2C plane, which suppresses the π donation of this amino group and causes an unusually low LUMO energy and high electrophilicity.

A Stable Planar-Chiral N-Heterocyclic Carbene with a 1,1'-Ferrocenediyl Backbone.

This paper focuses on the stable, ferrocene-based N-heterocyclic carbene (NHC) rac-[Fe{(η(5)-t-BuC5H3)NpN}2C:] (A'-Np, Np = neopentyl), which is planar-chiral due to the two tert-butyl substituents in 3,3'-positions. A'-Np was synthesized in nine steps starting from 1,1'-di-tert-butylferrocene (1), the first step being its 3,3'-dilithiation to afford rac-[Fe(η(5)-t-BuC5H3Li)2] (rac-fc'Li2, 2). The structures of rac-fc'(SiMe3)2 (3), rac-fc'Br2 (4), rac-fc'(N3)2 (5), and the immediate carbene precursor [A'-NpH]BF4 were determined by single-crystal X-ray diffraction (XRD). The chemical properties of A'-Np were found to be very similar to those of its tert-butyl-free congener A-Np, both being ambiphilic NHCs with rather high calculated HOMO energies (ca. -4.0 eV) and low singlet-triplet gaps (ca. 35 kcal/mol). A Tolman electronic parameter value of 2050 cm(-1) was derived from IR data of cis-[RhCl(A'-Np)(CO)2], indicating the high donicity of A'-Np as a ligand. Consistent with its ambiphilic nature, A'-Np was found to react readily with carbon monoxide, affording the betainic enolate (A'-Np)2CO as four stereoisomers, viz. (RpRp-A'-Np)═C(O(-))(RpRp-A'-Np(+)), (SpSp-A'-Np)═C(O(-))(SpSp-A'-Np(+)), (RpRp-A'-Np)═C(O(-))(SpSp-A'-Np(+)), and (SpSp-A'-Np)═C(O(-))(RpRp-A'-Np(+)). The former two isomers were structurally characterized as a racemic compound by single-crystal XRD. A'-Np was found to react swiftly with dichloromethane, affording the addition product A'-NpH-CHCl2 in a reaction that is unprecedented for diaminocarbenes. A-NpH-CHCl2 was obtained analogously. Both compounds were structurally characterized by single-crystal XRD. An electrochemical investigation of A'-Np by cyclic and square wave voltammetry revealed a reversible oxidation of the carbene at a half-wave potential of -0.310 vs ferrocene/ferrocenium (THF/NBu4PF6). The electrochemical data previously published for A-Np were identified to be incorrect, since unnoticed hydrolysis of the NHC had taken place, affording A-Np(H2O). The hydrolysis products of A-Np and A'-Np were found to be reversibly oxidized at half-wave potentials of -0.418 and -0.437 V, respectively.