No abstract

Synthesis of the remarkably air- and thermally stable 2,6-diisocyano-1,3-diethoxycarbonylazulene linker from 2-amino-1,3-diethoxycarbonylazulene in 57% cumulative yield was developed. Incorporation of the ester "arms" in the design of this first diisocyanoazulene bridge permitted fully controlled stepwise installation and complexation of its isocyano junction groups. The -CO(2)Et arms in 2,6-diformamido-1,3-diethoxycarbonylazulene effectively suppress the rate of dehydration of its 2-NHCHO end relative to that of the 6-NHCHO end leading to practically exclusive formation of 6-isocyano-2-formamido-1,3-diethoxycarbonylazulene upon treatment of the above diformamide with an equimolar amount of POCl(3). This crystallographically characterized 6-isocyano-2-formamidoazulene derivative was employed to access mono- and heterobimetallic complexes of the 2,6-diisocyanoazulene scaffold with controlled orientation of the azulenic dipole. A complete series of monometallic, homobimetallic, and isomeric heterobimetallic ([M] = M(CO)(5), M = Cr and/or W) complexes of the 2,6-diisocyanoazulene motif was isolated and studied by a variety of techniques, including X-ray crystallography. The metal-to-bridge charge transfer in mono- and dinuclear adducts of 2,6-diisocyanoazulene, the assignment of which was corroborated by time-dependent density functional theory calculations, occurs at a dramatically lower energy as compared to the analogous systems featuring the 1,4-diisocyanobenzene scaffold. Moreover, the metal-to-diisocyanide charge transfer exhibits a substantially greater red shift upon binucleation of the mononuclear [M(CO)(5)] adducts of the nonbenzenoid 2,6-diisocyanoazulene linker versus the 1,4-diisocyanobenzene bridge.

The first homoleptic paramagnetic transition metal isocyanide, V(CNXyl)6 (2, Xyl = 2,6-dimethylphenyl), can be isolated in high yield by reacting bis(naphthalene)vanadium(0) (1a) or bis(1-methylnaphthalene)vanadium(0) (1b) with 6 equiv of CNXyl in tetrahydrofuran/heptane. Reduction of 2 with excess cesium graphite in THF affords excellent yields of [V(CNXyl)6]- (3) as an unsolvated Cs+ salt, the first homoleptic octahedral isocyanide metalate. Cs3 reacts with 2 equiv of 18-Crown-6 to give [Cs(18-Crown-6)2]3. Anion 3 can also be isolated as a practically insoluble [K(Crypt{2.2.2.})]+ salt by reducing 2 with potassium naphthalenide in the presence of Crypt{2.2.2.}. Complex 3 reduces [Et3NH]Cl to form paramagetic 2. Oxidation of 2 by ferricinium hexafluorophosphate in THF provides nearly quantitative yields of the 16-electron paramagnetic [V(CNXyl)6][PF6] (4[PF6]), analogous to the exceedingly unstable [V(CO)6]+. Interaction of V(CO)6 with excess CNXyl in heptane results in the efficient formation of trans-[V(CO)2(CNXyl)4] (5). Such a substitution reaction is highly unusual for V(CO)6. Oxidation of compound 5 by ferricinium hexafluorophosphate in THF affords homoleptic 4[PF6]. Complexes 2, 3, 4, and 5 were characterized by a variety of spectroscopic methods and X-ray crystallography. Spectroscopic, magnetic, and structural features of these novel electron rich vanadium isocyanides are discussed in detail. The average V−CN bond length increases in the series [V(CNXyl)6]- < V(CNXyl)6 < trans-V(CO)2(CNXyl)4 < [V(CNXyl)6]+. Well-resolved 1H and 13C NMR spectra were obtained for paramagnetic 2 and its chromium congener, [Cr(CNXyl)6]+. The importance of back-bonding in the mechanism of unpaired spin delocalization within 2 was demonstrated. Contrary to the previous prediction for dπ(M)−pπ*(L) unpaired spin delocalization in low-spin d5 octahedral complexes, negative spin appears to be induced on the CNXyl ligands of 2 by means of dπ(V)−pπ*(CNXyl) back-bonding.

A new trinuclear iron(II) complex involving two isocyanoferrocene ligands axially coordinated to iron(II) phthalocyanine, (FcNC)2FePc [Fc = ferrocenyl; Pc = phthalocyaninato(2-) anion], was isolated and characterized using a variety of spectroscopic methods as well as single-crystal X-ray diffraction. The redox behavior of the above molecular wire was investigated through electrochemical, spectroelectrochemical, and chemical oxidation approaches and compared to that of the bis(tert-butylisocyano)iron(II) phthalocyanine reference compound, (t-BuNC)2FePc. For both complexes, the first oxidation involves the phthalocyanine ligand and results in the formation of a red phthalocyanine cation-radical-centered [(RNC)2FePc](+) species, as evidenced by their UV-vis and electron paramagnetic resonance spectra. Despite the ~11.5 Å distance between the isocyanoferrocene iron centers, the second and third oxidation potentials for (FcNC)2FePc are separated by ∼80 mV, which is indicative of a weak long-range metal-metal coupling in this system. Spectroscopic signatures of the mixed-valence [(FcNC)2FePc](2+) dication were obtained using spectroelectrochemical and chemical oxidation approaches. These experimentally assessed characteristics were also correlated with the electronic structure, redox properties, and spectroscopic signatures predicted by density functional theory (DFT) and time-dependent DFT analyses.

Efficient syntheses of all five possible isocyanoazulenes, the four isomeric archetypal compounds CN1Az, CN2Az, CN4Az, and CN6Az, as well as the 1,3-di-tert-butyl derivative of CN5Az (Az = azulenyl), are described. Compounds CN1Az and CN2Az show unexpected shifts of the S0 → S1 transition in their electronic spectra relative to azulene. The origins of these “anomalous” shifts have been addressed by DFT calculations, cyclic voltammetry, and comparison of the electronic spectra of isocyanoazulenes with those of the corresponding isomeric cyanoazulenes. Despite the high propensity of the azulenic nucleus to undergo multihapto coordination and C−C coupling in the presence of low-valent metals, the isocyanoazulenes react with 1/6 equiv of Cr(η6-naphthalene)2 to afford thermally stable Cr(CN x Az)6 (x = 1, 2, 4, 6), which contain six discrete azulenyl groups separated from the Cr center by isocyanide linkers. All Cr(CN x Az)6 species undergo oxidation to form the corresponding paramagnetic cations [Cr(CN x Az)6]+, which have been crystallographically characterized. Changing the atom of attachment of the azulenyl groups to the “Cr(CN)6” core substantially alters the donor/acceptor properties of the isocyanoazulene ligands. The half-wave Cr0/+ and Cr+/2+ redox potentials for [Cr(CN x Az)6] z form the “electrochemical series” that constitutes a quantitative measure of electronic inhomogeneity of the azulenic framework. Unpaired spin delocalization within the azulenic moieties of [Cr(CN x Az)6]+ has been observed by multinuclear NMR. The CrI(dπ)→CN x Az(pπ*) interaction has been shown to be an important contributor to the mechanism of unpaired electron delocalization in [Cr(CN x Az)6]+.

Treatment of [M(CO)(6)](-), M = Nb, Ta, with Ag(+), I(2) or NO(+) in the presence of CNXyl provided [M(CNXyl)(7)](+), M(CNXyl)(6)I, or cis-[M(CNXyl)(4)(NO)(2)](+), which are isocyanide analogues of the unknown carbonyl complexes [M(CO)(7)](+), M(CO)(6)I, or cis-[M(CO)(4)(NO)(2)](+), respectively. Reduction of M(CNXyl)(6)I by cesium graphite gave the respective Cs[M(CNXyl)(6)], which have been structurally characterized and represent the first isolable homoleptic isocyanidemetalates for second or third row transition metals. Nitrosylation of [Ta(CNXyl)(6)](-) affords a rare example of a mononitrosyl tantalum complex, Ta(CNXyl)(5)NO, which is an isocyanide analogue of the unknown Ta(CO)(5)NO. This study emphasizes, inter alia, the remarkable versatility of the CNXyl ligand compared to CO in stabilizing various electronic environments at heavier group 5 metal centers.

Reactions of alkali-metal naphthalenides with VCl3(THF)3, CrCl3(THF)3, MoCl3(THF)3, and MoCl4(THF)2 in THF provided up to 29%, 24%, 20%, and 17% yields of the respective bis(naphthalene)metal(0) complexes. These highly reactive “naked” early-transition-metal atom reagents were accessible previously as pure substances only from metal atom reactions carried out in specialized apparatus available to few chemists. The nature of bis(naphthalene)vanadium(0) has been confirmed by a single-crystal X-ray structural characterization. These results provide another indication that the arene radical anion route is an important general strategy for the synthesis of homoleptic transition-metal arene complexes.

The preparation of 2,6-azulenedicarboxylic acid (I) from its diester, 2-CO(2)(t)Bu-6-CO(2)-C(10)H(6) (II), is reported together with the crystal and molecular structure of the ester, II. From the reactions between the dicarboxylic acid I and the MM quadruply bonded complexes M(2)(O(2)C(t)Bu)(4), where M = Mo or W, the azulenedicarboxylate bridged complexes [M(2)(O(2)C(t)Bu)(3)](2)(mu-2,6-(CO(2))(2)-C(10)H(6)) have been isolated, III (M = Mo) and IV (M = W). The latter compounds provide examples of electronically coupled M(2) centers via a polar bridge. The compounds show intense electronic absorptions due to metal-to-bridge charge transfer. This occurs in the visible region of the spectrum for III (M = Mo) but in the near-IR for IV (M = W). One electron oxidation with Ag(+)PF(6)(-) in THF generates the radical cations III(+) and IV(+). By both UV-vis-NIR and EPR spectroscopy the molybdenum ion III(+) is shown to be valence trapped or Class II on the Robin and Day classification scheme. Electrochemical, UV-vis-NIR, and EPR spectroscopic data indicate that, in the tungsten complex ion IV(+), the single electron is delocalized over the two W(2) centers that are separated by a distance of ca. 13.6 A. Furthermore, from the hyperfine coupling to (183)W (I = (1)/(2)), the singly occupied highest molecular orbital is seen to be polarized toward one W(2) center in relationship to the other. Electronic structure calculations employing density functional theory indicate that the HOMO in compounds III and IV is an admixture of the two M(2) delta orbitals that is largely centered on the M(2) unit having proximity to the C(5) ring of the azulenedicarboxylate bridge. The energy of the highest occupied orbital of the bridge lies very close in energy to the M(2) delta orbitals. However, this orbital does not participate in electronic coupling by a hole transfer superexchange mechanism, and the electronic coupling in the radical cations of III and IV occurs by electron transfer through the bridge pi system.