Octacarbonyl Anion Complexes of Group Three Transition Metals [TM(CO)8]− (TM=Sc,Y, La) and the 18‐Electron Rule

We report the gas‐phase synthesis of stable 20‐electron carbonyl anion complexes of group 3 transition metals, TM(CO)₈^? (TM=Sc, Y, La), which are studied by mass‐selected infrared (IR) photodissociation spectroscopy. The experimentally observed species, which are the first octacarbonyl anionic complexes of a TM, are identified by comparison of the measured and calculated IR spectra. Quantum chemical calculations show that the molecules have a cubic (O_h) equilibrium geometry and a singlet (¹A_1g) electronic ground state. The 20‐electron systems TM(CO)₈^? are energetically stable toward loss of one CO ligand, yielding the 18‐electron complexes TM(CO)₇^? in the ¹A₁ electronic ground state; these exhibit a capped octahedral structure with C_3v symmetry. Analysis of the electronic structure of TM(CO)₈^? reveals that there is one occupied valence molecular orbital with a_2u symmetry, which is formed only by ligand orbitals without a contribution from the metal atomic orbitals. The adducts of TM(CO)₈^? fulfill the 18‐electron rule when only those valence electrons that occupy metal–ligand bonding orbitals are considered.     

Formation and Characterization of the Boron Dicarbonyl Complex [B(CO)2]−

We report the synthesis and spectroscopic characterization of the boron dicarbonyl complex [B(CO)₂]^?. The bonding situation is analyzed and compared with the aluminum homologue [Al(CO)₂]^? using state‐of‐the‐art quantum chemical methods.     

Transition‐Metal Chemistry of Alkaline‐Earth Elements: The Trisbenzene Complexes M(Bz)3 (M=Sr,Ba)

We report the synthesis and spectroscopic identification of the trisbenzene complexes of strontium and barium M(Bz)₃ (M=Sr, Ba) in low‐temperature Ne matrix. Both complexes are characterized by a D₃ symmetric structure involving three equivalent η⁶‐bound benzene ligands and a closed‐shell singlet electronic ground state. The analysis of the electronic structure shows that the complexes exhibit metal–ligand bonds that are typical for transition metal compounds. The chemical bonds can be explained in terms of weak donation from the π MOs of benzene ligands into the vacant (n?1)d AOs of M and strong backdonation from the occupied (n?1)d AO of M into vacant π* MOs of benzene ligands. The metals in these 20‐electron complexes have 18 effective valence electrons, and, thus, fulfill the 18‐electron rule if only the metal–ligand bonding electrons are counted. The results suggest that the heavier alkaline earth atoms exhibit the full bonding scenario of transition metals.     

Redox Non‐Innocent Behavior of a Terminal Iridium Hydrazido(2−) Triple Bond

The synthesis of the first terminal Group 9 hydrazido(2‐) complex, Cp*IrN(TMP) ( 6 ) (TMP=2,2,6,6‐tetramethylpiperidine) is reported. Electronic structure and X‐ray diffraction analysis indicate that this complex contains an Ir?N triple bond, similar to Bergman's seminal Cp*Ir(N^tBu) imido complex. However, in sharp contrast to Bergman's imido, 6 displays remarkable redox non‐innocent reactivity owing to the presence of the N_β lone pair. Treatment of 6 with MeI results in electron transfer from N_β to Ir prior to oxidative addition of MeI to the iridium center. This behavior opens the possibility of carrying out facile oxidative reactions at a formally Ir^III metal center through a hydrazido(2?)/isodiazene valence tautomerization.     

Structure and Magnetization Dynamics of Dy−Fe and Dy−Ru Bonded Complexes

We present an investigation of isostructural complexes that feature unsupported direct bonds between a formally trivalent lanthanide ion (Dy³⁺) and either a first‐row (Fe) or a second‐row (Ru) transition metal (TM) ion. The sterically rigid, yet not too bulky ligand PyCp₂^2? (PyCp₂^2?=[2,6‐(CH₂C₅H₃)₂C₅H₃N]^2?) facilitates the isolation and characterization of PyCp₂Dy?FeCp(CO)₂ ( 1 ; d(Dy–Fe)=2.884(2) Å) and PyCp₂Dy?RuCp(CO)₂ ( 2 ; d(Dy–Ru)=2.9508(5) Å). Computational and spectroscopic studies suggest strong TM→Dy bonding interactions. Both complexes exhibit field‐induced slow magnetic relaxation with effectively identical energy barriers to magnetization reversal. However, in going from Dy?Fe to Dy?Ru bonding, we observed faster magnetic relaxation at a given temperature and larger direct and Raman coefficients, which could be due to differences in the bonding and/or spin–phonon coupling contributions to magnetic relaxation.     

Spectroscopic Evidence for Aminomethylene (H−C̈−NH2)—The Simplest Amino Carbene

Although N‐heterocyclic carbenes have been well‐studied, the simplest aminocarbene, aminomethylene H?C??NH₂, has not been spectroscopically identified to date. Herein we report the gas‐phase preparation of aminomethylene by high‐vacuum flash pyrolysis of cyclopropylamine and subsequent trapping of the pyrolysate in an inert argon matrix at 12 K. Aminomethylene was characterized by matching matrix IR and UV/Vis spectroscopic data with ab initio coupled cluster computations. After UV irradiation of the matrix aminomethylene rearranges to its isomer methanimine (formaldimine) H₂C=NH. Based on our experimental results and computations aminomethylene has a singlet ground state with a reaction barrier of almost 46 kcal mol^?1 to methanimine so that H‐tunneling is excluded.     

Carbon Monoxide Bonding With BeO and BeCO3: Surprisingly High CO Stretching Frequency of OCBeCO3

The complexes OCBeCO₃ and COBeCO₃ have been isolated in a low‐temperature neon matrix. The more stable isomer OCBeCO₃ has a very high C? O stretching mode of 2263 cm^?1, which is blue‐shifted by 122 cm^?1 with respect to free CO and 79 cm^?1 higher than in OCBeO. Bonding analysis of the complexes shows that OCBeO has a stronger OC? BeY bond than OCBeCO₃ because it encounters stronger π backdonation. The isomers COBeCO₃ and COBeO exhibit red‐shifted C? O stretching modes with respect to free CO. The inverse change of C? O stretching frequency in OC? BeY and CO? BeY is explained with the reversed polarization of the σ and π bonds in CO.     

Maximum carbonyl‐coordination number of scandium Computational study of Sc(CO)n (n = 1–7), Sc(CO)7− and Sc(CO)63−

Understanding the maximum bonding ability is very important with the potential both to design new compounds and to broaden chemists' imagination. While the coordination ability of the late transition metals has been richly understood, that of scandium is very poor. In this work, a detailed computational study on the equilibrium geometries, stability and vibrational frequencies of a series of Sc(CO)_n (n = 1–7), Sc(CO) and Sc(CO) is reported using density functional theory functionals and the coupled cluster (single‐point) method with 6‐311+G(3df) basis set. It was shown that the obtained sequential and average CO binding energies of Sc(CO)_n (n = 4–7), Sc(CO) and Sc(CO) are comparable to those of the experimentally known species, i.e., smaller Sc‐carbonyls (n ≤3) and the analog Ti(CO)₇⁺. Thus, the studied high scandium carbonyls could all be experimentally accessible. In addition, the studied Sc(CO)_n generally favor the low‐spin ground state (doublet) structures except ScCO and Sc(CO)₃ that are in the quartet states. The previously uncertain spectrum bands were assigned to Sc(CO)₄ and Sc(CO)₅ in this work. In all, the appreciable stability suggested that the last 18‐electron first‐row transition metal carbonyls, that is, Sc(CO) and Sc(CO), could be accessible in experiment. © 2013 Wiley Periodicals, Inc.     

2,2‐Bis(5‐tetrazolyl)propane as Ligand in Energetic 3d Transition Metal Complexes

This contribution covers the preparation and characterization of 2,2‐bis(5‐tetrazolyl)propane (5‐DTP) ( 1 ). The bridged bitetrazole is used as a neutral nitrogen‐rich ligand in 3d transition metal(II) based complexes for the first time and can be synthesized via [2+3] cycloaddition from sodium azide and dimethylmalononitrile. The combination with different anions (e.g., perchlorate, nitrate, sulfate, and chloride) yields materials with widely varying physicochemical properties. The obtained coordination compounds were characterized using low‐temperature single‐crystal X‐ray diffraction (except 14 ), IR spectroscopy, elemental analysis, and DTA (except 16 ). The sensitivities toward external stimuli (impact and friction) were determined according to the Bundesamt für Materialforschung und ‐prüfung (BAM) standard methods together with its sensitivities against electrostatic discharge (except 16 ). Complexes 10 and 14 were characterized in laser ignition experiments. For determination of the compounds' deflagration to detonation transition (DDT) capability, hot plate and hot needle tests were performed for the zinc(II) and copper(II) perchlorate complexes.     

OsII-Phthalocyaninate(2−): Darstellung und Eigenschaften von (Halogeno)-(carbonyl)phthalocyaninato(2−)osmat(II)

Os^II Phthalocyaninates(2?): Synthesis and Properties of (Halo)(carbonyl)phthalocyaninato-(2?)osmate(II) Soluble, blue tetra(n-butyl)ammonium (halo)(carbonyl)phthalocyaninato(2?)osmate(II), (ⁿBu₄N)[Os(X)(CO)Pc^2?] (X = Cl, Br, I) is obtained by the reaction of [Os(THF)(CO)Pc^2?] (THF: tetrahydrofurane) with (ⁿBu₄N)X in THF. In the cyclovoltammograms there are three reversible electrode processes at ?1.21 ± 0.01, 0.18 ± 0.04 and 0.65 ± 0.01 V assigned to the three redox pairs Pc^2?/Pc^3?, Os^II/Os^III and Pc^2?/Pc^3?. In the electronic absorption spectra only the intense B and Q regions are observed at ～ 15800 resp. 27500, 33000 cm^?1. The infrared and resonance Raman spectra closely resemble those of other phthalocyaninates(2?) of low valent osmium. In the infrared spectrum v(C? O) is detected at 1896 ± 4 cm^?1 and v(Os? X) at 260 (X = Cl), 175 (X = Br) or 143 cm^?1 (X = I).     

A Copper(I)–Arene Complex With an Unsupported η6 Interaction

Addition of PR₃ (R=Ph or OPh) to [Cu(η²‐Me₆C₆)₂][PF₆] results in the formation of [(η⁶‐Me₆C₆)Cu(PR₃)][PF₆], the first copper–arene complexes to feature an unsupported η⁶ arene interaction. A DFT analysis reveals that the preference for the η⁶ binding mode is enforced by the steric clash between the methyl groups of the arene ligand and the phenyl rings of the phosphine co‐ligand.     

N‐Heterocyclic Phosphenium,Arsenium, and Stibenium Ions as Ligands in Transition Metal Complexes: A Comparative Experimental and Computational Study

Reaction of 2‐chloro‐1,3,2‐diazaarsolenes and ‐diazaphospholenes with Tl[Co(CO)₄] gives instable complexes of type [Co(ER₂)(CO)₄] which decarbonylated to yield [Co(ER₂)(CO)₃]. Spectroscopic and X‐ray diffraction studies revealed that the tetracarbonyl complexes can be formulated as ion pair for E = P and as covalent metalla‐arsine for E = As, and the tricarbonyl complexes as carbene‐like species with a formal E=Co double bond. A similar reactivity towards Tl[Co(CO)₄] was also inferred for 1,3,2‐diazastibolenes although the products were not isolable and their constitution remained uncertain. Evaluation of structural and computational data suggests that the weak and polarized Co–As bond in [Co(AsR₂)(CO)₄] can be characterized as an “inverse” M→L donor‐acceptor bond. The computational studies disclosed further η²(EN)‐coordination of the EN₂C₂ heterocycle as an alternative to the formation of a carbene‐like structure for [Co(ER₂)(CO)₃]. The η²‐complex is less stable for E = P but close in energy for E = As and more stable than the carbene‐like complex for E = Sb.     

Chemical Bonding in Homoleptic Carbonyl Cations [M{Fe(CO)5}2]+ (M=Cu,Ag, Au)

Syntheses of the copper and gold complexes [Cu{Fe(CO)₅}₂][SbF₆] and [Au{Fe(CO)₅}₂][HOB{3,5-(CF₃)₂C₆H₃}₃] containing the homoleptic carbonyl cations [M{Fe(CO)₅}₂]⁺ (M=Cu, Au) are reported. Structural data of the rare, trimetallic Cu₂Fe, Ag₂Fe and Au₂Fe complexes [Cu{Fe(CO)₅}₂][SbF₆], [Ag{Fe(CO)₅}₂][SbF₆] and [Au{Fe(CO)₅}₂][HOB{3,5-(CF₃)₂C₆H₃}₃] are also given. The silver and gold cations [M{Fe(CO)₅}₂]⁺ (M=Ag, Au) possess a nearly linear Fe-M-Fe’ moiety but the Fe-Cu-Fe’ in [Cu{Fe(CO)₅}₂][SbF₆] exhibits a significant bending angle of 147° due to the strong interaction with the [SbF₆]⁻ anion. The Fe(CO)₅ ligands adopt a distorted square-pyramidal geometry in the cations [M{Fe(CO)₅}₂]⁺, with the basal CO groups inclined towards M. The geometry optimization with DFT methods of the cations [M{Fe(CO)₅}₂]⁺ (M=Cu, Ag, Au) gives equilibrium structures with linear Fe-M-Fe’ fragments and D₂ symmetry for the copper and silver cations and D_4d symmetry for the gold cation. There is nearly free rotation of the Fe(CO)₅ ligands around the Fe-M-Fe’ axis. The calculated bond dissociation energies for the loss of both Fe(CO)₅ ligands from the cations [M{Fe(CO)₅}₂]⁺ show the order M=Au (D_e=137.2 kcal mol⁻¹)>Cu (D_e=109.0 kcal mol⁻¹)>Ag (D_e=92.4 kcal mol⁻¹). The QTAIM analysis shows bond paths and bond critical points for the M−Fe linkage but not between M and the CO ligands. The EDA-NOCV calculations suggest that the [Fe(CO)₅]→M⁺←[Fe(CO)₅] donation is significantly stronger than the [Fe(CO)₅]←M⁺→[Fe(CO)₅] backdonation. Inspection of the pairwise orbital interactions identifies four contributions for the charge donation of the Fe(CO)₅ ligands into the vacant (n)s and (n)p AOs of M⁺ and five components for the backdonation from the occupied (n-1)d AOs of M⁺ into vacant ligand orbitals.     

Studies on the Reactivity of [Ge9]4− towards [Fe(cot)(CO)3]: Synthesis and Characterization of [Ge8Fe(CO)3]3− and of the Anionic Organometallic Species [Fe(cot)(CO)3]−

Reaction of cyclooctatetraene (COT) iron(II) tricarbonyl, [Fe(cot)(CO)₃], with one equivalent of K₄Ge₉ in ethylenediamine (en) yielded the cluster anion [Ge₈Fe(CO)₃]^3? which was crystallographically‐characterized as a [K(2,2,2‐crypt)]⁺ salt in [K(2,2,2‐crypt)]₃[Ge₈Fe(CO)₃]. The chemically‐reduced organometallic species [Fe(η³‐C₈H₈)(CO)₃]^? was also isolated as a side‐product from this reaction as [K(2,2,2‐crypt)][Fe(η³‐C₈H₈)(CO)₃]. Both species were further characterized by EPR and IR spectroscopy and electrospray mass spectrometry. The [Ge₈Fe(CO)₃]^3? cluster anion represents an unprecedented functionalized germanium Zintl anion in which the nine‐atom precursor cluster has lost a vertex, which has been replaced by a transition‐metal moiety.     

The Forgotten Nitroaromatic Phosphines as Weakly Donating P‐ligands: An N‐Aryl‐benzimidazolyl Series in RhCl(CO) Complexes

The coordination chemistry of a priori weakly σ ‐donating nitroaromatic phosphines is addressed through a series of nitro‐substituted (N ‐phenyl‐benzimidazol‐1‐yl)diphenylphosphines in Rh^I complexes. From a set of seven such phosphines L=L_xyz^(′) (x , y , z =0 or 1=number of NO₂ substituents at the 5, 6 and N‐Ph para positions, respectively), including the non‐nitrated parent L₀₀₀ and its dicationic N‐methyl counterpart L₀₀₀′, three LRhCl(COD) and seven L₂RhCl(CO) complexes have been obtained in 72–95 % yield. Despite of a cis orientation of the L and CO ligands, the C=O IR stretching frequency ν _CO varies in the expected sense, from 1967±1 cm⁻¹ for L_xy0 to 1978±1 cm⁻¹ for L_xy1, and 2005 cm⁻¹ for L₀₀₀′. The ¹⁰³Rh NMR chemical shift δ _Rh varies from −288 ppm for L₀₀₀ to −316±1 ppm for L_10z or L_01z, and −436 ppm for L₀₀₀′. The ν _CO and δ _Rh probes thus reveal moderate but systematic variations, and act as “orthogonal” spectroscopic indicators of the presence of nitro groups on the N‐Ph group and the benzimidazole core, respectively. For the dicationic ligand L₀₀₀′, a tight electrostatic sandwiching of the Rh‐Cl bond by the benzimidazole moities is evidenced by X‐ray crystallography (RhCl^{δ −}⋅⋅⋅CN₂⁺ ≈3.01 Å). Along with the LRhCl(CO) complexes, dinuclear side‐products (μ‐CO)(RhClL)₂ were also obtained in low spectroscopic yield: for the dinitro ligand L=L₀₁₁, a unique 1:6.7 clathrate structure, with dichloromethane as solvate, is also revealed by X‐ray crystallography.