Synthesis and Structural Characterization of p-Carboranylamidine Derivatives.

In this contribution, the first amidinate and amidine derivatives of p-carborane are described. Double lithiation of p-carborane (1) with n-butyllithium followed by treatment with 1,3-diorganocarbodiimides, R-N=C=N-R (R = iPr, Cy (= cyclohexyl)), in DME or THF afforded the new p-carboranylamidinate salts p-C2H10B10[C(NiPr)2Li(DME)]2 (2) and p-C2H10B10[C(NCy)2Li(THF)2]2 (3). Subsequent treatment of 2 and 3 with 2 equiv. of chlorotrimethylsilane (Me3SiCl) provided the silylated neutral bis(amidine) derivatives p-C2H10B10[C{iPrN(SiMe3)}(=NiPr)]2 (4) and p-C2H10B10[C{CyN(SiMe3)}(=NCy)]2 (5). The new compounds 3 and 4 have been structurally characterized by single-crystal X-ray diffraction. The lithium carboranylamidinate 3 comprises a rare trigonal planar coordination geometry around the lithium ions.

Small compound - big colors: synthesis and structural investigation of brightly colored alkaline earth metal 1,3-dimethylviolurates.

A series of brightly colored alkaline earth metal 1,3-dimethylviolurates M(Me2Vio)2 have been prepared and fully characterized. The title compounds AE(Me2Vio)2·nH2O (AE = Mg, n = 6 (3); AE = Ca, n = 8 (4), AE = Sr, n = 6 (5); AE = Ba, n = 4 (6)) were obtained by neutralizing 1,3-dimethylvioluric acid monohydrate (=H(Me2Vio)·H2O; 2) with 0.5 equiv. of the corresponding metal dihydroxides AE(OH)2. The hair-like appearance of the Sr derivative 5 prevented the growth of single-crystals. This problem could be solved by crystallizing the crown ether derivative Sr(Me2Vio)2(18-crown-6) (5a). The isolated salts exhibit intense colors ranging from red to purple. Various attempts to prepare the beryllium derivative Be(Me2Vio)2 failed. Instead, work-up of the reaction mixtures provided pink crystals of a new modification of 2 formulated as [H3O][Me2Vio] (2b) as shown by an X-ray diffraction study. An unexpected oxidation reaction of the barium salt Ba(Me2Vio)2 led to formation of the novel mixed-anion salt Ba(Me2Vio)(Me2NO2Barb)·2H2O (8, Me2NO2Barb- = 1,3-dimethyl-5-nitrobarbiturate anion). Compound 8 could also be synthesized deliberately by treatment of Ba(OH)2 with a 1 : 1 mixture of 2 and 1,3-dimethyl-5-nitrobarbituric acid (7, =H(Me2NO2Barb)·H2O). All new compounds were fully characterized by their IR, Raman, NMR (1H, 13C{1H}) and UV-vis spectra as well as elemental analyses. Single-crystal X-ray diffraction studies revealed that the solid-state structures of compounds 3, 4, 5a and 6 are governed by the typical coordination behavior of the alkaline-earth metals, i.e. increasing coordination numbers and a decreasing degree of hydration when going from Mg to Ba. The dimensions of the structures range from hydrogen-bonded ions (3) over monomeric, neutral complex molecules (4, 5a), to polymeric networks (6). The successful isolation of the mixed-anion barium salt 8 adds a new facet to the coordination chemistry of violurate and related ligands.

Synthesis and Structure of Alkaline Earth Bis{hydrido-tris(3,5-diisopropyl-pyrazol-1-yl)borate} Complexes: Ae(TpiPr2)2 (Ae = Mg, Ca, Sr, Ba).

The synthesis and structural characterization of Ae(TpiPr2)2 (Ae = Mg, Ca, Sr, Ba; TpiPr2 = hydrido-tris(3,5-diisopropyl-pyrazol-1-yl)borate) are reported. In the crystalline state, the alkaline earth metal centers are six-coordinate, even the small Mg2+ ion, with two κ3-N,N',N''-TpiPr2 ligands, disposed in a bent arrangement (B···Ae···B < 180°). However, contrary to the analogous Ln(TpiPr2)2 (Ln = Sm, Eu, Tm, Yb) compounds, which all exhibit a bent-metallocene structure close to Cs symmetry, the Ae(TpiPr2)2 compounds exhibit a greater structural variation. The smallest Mg(TpiPr2)2 has crystallographically imposed C2 symmetry, requiring both bending and twisting of the two TpiPr2 ligands, while with the similarly sized Ca2+ and Sr2+, the structures are back toward the bent-metallocene Cs symmetry. Despite the structural variations, the B···M···B bending angle follows a linear size-dependence for all divalent metal ions going from Mg2+ to Sm2+, decreasing with increasing metal ion size. The complex of the largest metal ion, Ba2+, forms an almost linear structure, B···Ba···B 167.5°. However, the "linearity" is not due to the compound approaching the linear metallocene-like geometry, but is the result of the pyrazolyl groups significantly tipping toward the metal center, approaching "side-on" coordination. An attempt to rationalize the observed structural variations is made.

Rubidium and Cesium Enediamide Complexes Derived from Bulky 1,4-Diazadienes.

The first rubidium and cesium enediamide complexes based on bulky 1,4-diaza-1,3-diene ligands (DADs) have been prepared by metalation of either 1,4-bis(2,6-diisopropylphenyl)-1,4-diaza-1,3-butadiene (1, = H2DADDipp) or 1,4-bis(2,6-diisopropylphenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene (2, = Me2DADDipp) with an excess of Rb or Cs metals in coordinating solvents such as tetrahydrofuran (THF) or 1,2-dimethoxyethane (DME). All new complexes were fully characterized by spectroscopic and analytical methods as well as single-crystal X-ray diffraction studies.

Catenated and spirocyclic polychalcogenides from potassium carbonate and elemental chalcogens.

The reaction of potassium carbonate with elemental sulfur or selenium in acetone in the presence of [PPN]Cl (PPN = (Ph3P)2N) produces catena-[S12]2-, the longest structurally characterised polysulfide dianion, or spiro-[Se11]2- as ion-separated [PPN]+ salts.

An unsymmetrical dinuclear scandium complex comprising salophen ligands [H2salophen = N,N'-bis-(salicyl-idene)-1,2-phenyl-enedi-amine].

Treatment of scandium nitrate tetra-hydrate with the tetra-dentate ligand H2salophen [N,N'-bis-(salicyl-idene)-1,2-phenyl-enedi-amine] afforded the yellow dinuclear complex Sc(NO3)2(µ-salophen)Sc(salophen)(EtOH) or [Sc2(C20H14N2O2)2(NO3)2(C2H6O)] (systematic name: (ethanol-κO)bis-(nitrato-κ2 O,O'){µ-2,2'-[1,2-phenyl-enebis(nitrilo-methanylyl-idene)]diphenolato-κ4 N,N',O,O':κ2 O,O'}{2,2'-[1,2-phenyl-enebis(nitrilo-methanylyl-idene)]diphenolato-κ4 O,N,N',O'}discandium). In this compound, one salophen ligand displays a bridging coordination via the two oxygen atoms, while the other salophen ligand is attached to only one Sc center. This arrangement is stabilized by a hydrogen-bonded EtOH co-ligand, and by π-π stacking inter-actions between the two salophen ligands.

Formation and structural characterization of a potassium amidino-guanidinate.

The first potassium amidino-guanidinate complex, catena-poly[[bis-(µ-1-amidinato-N,N',N'',N'''-tetra-iso-propyl-guanidinato-κ5 N 1:N 1,N 2:N 2,N 4)dipotassium]-µ-1,2-di-meth-oxy-ethane-κ2 O:O'], [K2(C14H32N4)2(C4H10O2)] n or [{ i PrN= CHN( i Pr)N(N i Pr)2K}2(µ-DME)] n where DME is 1,2-di-meth-oxy-ethane, has been synthesized and structurally characterized. The title compound was isolated in 76% yield from a reaction of N,N'-diiso-propyl-carbodi-imide with potassium hydride in DME. The single-crystal X-ray structure determination of the title compound revealed a polymeric chain structure comprising cage-like dimeric units, with the amidino-guanidinate ligand displaying a mixed σ-/π-coordination mode.

Synthesis and structural characterization of four di-chlorido-bis-(cyclo-propyl-alkynyl-amidine)-metal complexes.

Deliberate hydrolysis of lithium cyclo-propyl-alkynylamidinates, Li[c-C3H5-C≡C(NR')2] [R' = i Pr, Cy = cyclo-hex-yl)], afforded the hitherto unknown neutral cyclo-propyl-alkynyl-amidine derivatives c-C3H5-C≡C-C(NR')(NHR') [R' = i Pr (1), Cy (2)]. Subsequent reactions of 1 or 2 with metal(II) chlorides, MCl2 (M = Mn, Fe, Co), provided the title complexes di-chlorido-bis-(3-cyclo-propyl-N,N'-diisopropyl-prop-2-ynamidine)-manganese(II), [MnCl2(C12H20N2)2], (3), di-chlorido-bis-(3-cyclo-propyl-N,N'-diisopropyl-prop-2-ynamidine)-iron(II), [FeCl2(C12H20N2)2], (4), di-chlorido-bis-(N,N'-di-cyclo-hexyl-3-cyclo-propyl-prop-2-ynamidine)-iron(II), [FeCl2(C18H28N2)2], (5), and di-chlorido-bis-(N,N'-di-cyclo-hexyl-3-cyclo-propyl-prop-2-ynamidine)-cobalt(II), [CoCl2(C18H28N2)2], (6), or more generally MCl2[c-C3H5-C≡C-C(NR')(NHR')]2 [R' = i Pr, M = Mn (3), Fe (4); R' = Cy, M = Fe (5), Co (6)] in moderate yields (30-39%). Besides their spectroscopic data (IR and MS) and elemental analyses, all complexes 3-6 were structurally characterized. The two isopropyl-substituted complexes 3 and 4 are isotypic, and so are the cyclo-hexyl-substituted complexes 5 and 6. In all cases, the central metal atom is coordinated by two Cl atoms and two N atoms in a distorted-tetra-hedral fashion, and the structure is supported by intra-molecular N-H⋯Cl hydrogen bonds.

Electronic and Geometric Structures of Paramagnetic Diazadiene Complexes of Lithium and Sodium.

The electronic and molecular structures of the lithium and sodium complexes of 1,4-bis(2,6-diisopropylphenyl)-2,3-dimethyl-1,4-diazabutadiene (Me2DADDipp) were fully characterized by using a multi-frequency electron paramagnetic resonance (EPR) spectroscopy approach and crystallography, together with density functional theory (DFT) calculations. EPR measurements, using T1 relaxation-time-filtered pulse EPR spectroscopy, revealed the diagonal elements of the A and g tensors for the metal and ligand sites. It was found that the central metals in the lithium complexes had sizable contributions to the SOMO, whereas this contribution was less strongly observed for the sodium complex. Such strong contributions were attributed to structural specifications (e.g. geometrical data and atomic size) rather than electronic effects.

The "Wanderlust" of Me3Si groups in rare-earth triple-decker complexes: a combined experimental and computational study.

The migration of Me3Si groups ("Wanderlust") in rare-earth triple-decker sandwich complexes of the type Ln2(COT'')3 (COT'' = bis(trimethylsilyl)cyclooctatetraenyl) has been elucidated by a combined experimental and computational study. For the first time, two isomers of a Ln2(COT'')3 triple-decker have been isolated and characterized in the case of Y2(COT'')3.

Three new types of transition metal carboranylamidinate complexes.

Three new types of transition metal carboranylamidinate complexes are reported. The tetranuclear Mn(ii) complex Mn4Cl6[(o-C2B10H10)C(NiPr)(NHiPr)]2(THF)4·THF (2) was prepared by treatment of anhydrous MnCl2 with Li[(o-C2B10H10)C(NiPr)(NHiPr)] ([double bond, length as m-dash]Li[HLiPr]) in THF, while the analogous reaction with FeCl2 afforded ionic [Li(DME)3][FeCl2{(o-C2B10H10)C(NiPr)(NHiPr)}] (3). The dinuclear Mo(ii) complex Mo2[(o-C2B10H10)C(NiPr)(NHiPr)]2(OAc)2·2THF (4), obtained from Mo2(OAc)4 and 2 equiv. of Li[HLiPr], represents the first example of a M-M multiple bond stabilized by carboranylamidinate ligands. All title compounds were structurally characterized by single-crystal X-ray diffraction. The M-M bonding in compound 4 has been further elucidated through Complete Active Space Self Consistent Field (CASSCF) calculations.

Bright Photoluminescence of [{(CptBu2 )2 Ce(µ-Cl)}2 ]: A Valuable Technique for the Determination of the Oxidation State of Cerium.

The synthesis and photoluminescence properties of the bright-yellow organocerium complex [{(CptBu2 )2 Ce(µ-Cl)}2 ] (CptBu2 =1,3-di(tert-butyl)cyclopentadienyl) are presented. This coordination compound exhibits highly efficient photoluminescence within the yellow-light wavelength range, with a high internal quantum yield of 61(±2) % at room temperature. The large red shift is attributed to the delocalizing ability of the aromatic ligands, whilst its quantum yield even makes this compound competitive with Ce3+ -activated LED phosphors in terms of its photoluminescence efficiency (disregarding its thermal stability). A bridging connection between two crystallographically independent Ce3+ ions is anticipated to be the reason for the highly efficient photoluminescence, even up to room temperature. The emission spectrum is characterized by two bands in the orange-light range at both 10 K and room temperature, which are attributed to the parity-allowed transitions 5d1 (2 D3/2 )→4f1 (2 F7/2 ) and 5d1 (2 D3/2 )→4f1 (2 F5/2 ) of Ce3+ , respectively. The photoluminescence spectra were interpreted in relation to the structure and vibrational modes of the coordination compound. The spectra and optical properties indicate that trivalent cerium ions are the dominant species in the ground state, which also resolves an often-encountered ambiguity in organocerium compounds. This result shows that photoluminescence spectroscopy is a versatile tool that can help elucidate the oxidation state of Ce in such compounds.

High-yield synthesis of a unique Mn(iii) siloxide complex through KMnO4 oxidation of a Mn(ii) precursor.

A unique trivalent manganese siloxide complex, blue-violet MnIIILi2Cl[(Ph2SiO)2O]2(THF)4·2THF (3) has been prepared by a straightforward two-step synthetic protocol. Lithiation of (Ph2SiOH)2O (1) followed by reaction with MnCl2(THF)2 gave the structurally remarkable Mn(ii) precursor MnIILi4Cl2[(Ph2SiO)2O]2(THF)5·2THF (2). Surprisingly, the final oxidation step could be achieved using KMnO4 in THF to provide the Mn(iii) species 3 in high yield (91%). Both title compounds were structurally characterized by single-crystal X-ray diffraction.

Synthesis and crystal structures of two new tin bis-(carboranylamidinate) complexes.

Reaction of 2 equiv. of the lithium carboranylamidinate Li[o-(C2H10B10)C(NCy)(NHCy)] with SnCl2 in THF afforded the stannylene compound bis(N,N'-dicyclohexylamidinatocarboranate)tin(II), SnII[o-(C2H10B10)C(NCy)(NHCy)]2 (1). A similar reaction of SnCl4 with 2 equiv. of Li[o-(C2H10B10)C(N i Pr)(NH i Pr)] unexpectedly afforded the known solvated penta-chlorido-stannate(IV) salt [Li(THF)4][SnCl5(THF)] as the main reaction product. Small amounts of the new chlorido-tin(IV) bis-(carboranylamidinate) bis(N,N'-diiso-propylamidinatocarboranate)chloridotin(IV), SnIVCl[o-(C2H10B10)C(N i Pr)(NH i Pr)][o-(C2H10B10)C(N i Pr)2] (2), were isolated as a by-product. Single-crystal X-ray structure analysis revealed a κC,κN-chelating coordination of the carboranylamidinate ligands in both 1 and 2. The Sn atom in 1 adopts a pseudo-trigonal-bipyramidal coordination under participation of a stereoactive lone pair. In 2, a trigonal-bipyramidal coordination of Sn is completed by a chlorido ligand.

Formation and structural characterization of a europium(II) mono(scorpionate) complex and a sterically crowded pyraza-bole.

The reaction of EuI2(THF)2 with potassium hydro-tris-(3,5-diiso-propyl-pyrazol-yl)borate (K[HB(3,5- iPr2pz)3] (= KTp iPr2, pz = pyrazol-yl) in a molar ratio of 1:1.5 resulted in extensive ligand fragmentation and formation of the europium(II) mono(scorpionate) complex bis-(3,5-diisopropyl-1H-pyrazole)[hydro-tris-(3,5-diiso-propyl-pyrazol-yl)borato]iodido-europium(II), [Eu(C27H46BN6)I(C9H16N2)2] or (Tp iPr2)(3,5- iPr2pzH)2EuIII, 1, in high yield (78%). As a typical by-product, small amounts of the sterically crowded pyraza-bole derivative trans-4,8-bis-(3,5-diiso-propyl-pyrazol-1-yl)-1,3,5,7-tetra-iso-propyl-pyraza-bole, C36H62B2H8 or trans-{(3,5- iPr2pz)HB(µ-3,5- iPr2pz)}2, 2, were formed. Both title compounds have been structurally characterized through single-crystal X-ray diffraction. In 1, two isopropyl groups are each disordered over two orientations with occupancy ratios of 0.574 (10):0.426 (10) and 0.719 (16):0.281 (16). In 2, one isopropyl group is similarly disordered, occupancy ratio 0.649 (9):0.351 (9).

The difficult search for organocerium(iv) compounds.

This Tutorial Review provides an overview of the historic and current development of the organometallic chemistry of cerium in its oxidation state 4+. Among the tetravalent lanthanide ions, only Ce4+ forms stable coordination compounds (e.g. (NH4)2[Ce(NO3)6]). Important fields of applications for cerium(iv) compounds include organic synthesis, bioinorganic chemistry, materials science, and industrial catalysis. In sharp contrast, organometallic cerium(iv) compounds are still exceedingly rare. The history of organocerium(iv) compounds is an exciting story of ups and downs. The so-called cerocene (= bis(η8-cyclooctatetraenyl) cerium) has been known since 1976. Other early reports e.g. about Cp4Ce (Cp = η5-cyclopentadienyl), were later disproven. However, significant progress in this field has been made in recent years through the use of carefully designed ligands and more sophisticated synthesis protocols. Taking the case of organocerium(iv) chemistry, this Tutorial Review also tries to exemplarily show how difficult synthetic and theoretical problems can eventually be solved through newly designed synthesis strategies (e.g. as accomplished for cyclopentadienyl and carbene derivatives) and a rewarding collaboration between synthetic and theoretical chemists (cf. the cerocene problem).

Synthesis and crystal structures of three new benzotriazolylpropanamides.

The base-catalyzed Michael addition of 2-methyl-acryl-amide to benzotriazole afforded 3-(1H-benzotriazol-1-yl)-2-methyl-propanamide, C10H12N4O (1), in 32% yield in addition to small amounts of isomeric 3-(2H-benzotriazol-2-yl)-2-methyl-propanamide, C10H12N4O (2). In a similar manner, 3-(1H-benzotriazol-1-yl)-N,N-di-methyl-propanamide, C11H14N4O (3), was prepared from benzotriazole and N,N-di-methyl-acryl-amide. All three products have been structurally characterized by single-crystal X-ray diffraction. The crystal structures of 1 and 2 comprise infinite arrays formed by N-H⋯O and N-H⋯N bridges, as well as π-π inter-actions, while the mol-ecules of 3 are aggregated to simple π-dimers in the crystal.

Scandium-Mediated Formation of a Bis(tetrahydropentalene).

The reactivity of Li[Sc(COT'')2 ] (1; COT''=1,4-bis(trimethylsilyl)cyclooctatetraenyl) towards CoCl2 is considerably different from that of related lanthanide triple-decker sandwich complexes. In addition to the expected triple-decker complex Sc2 (COT'')3 (2), the complex Sc2 {µ-BTHP}(COT'')2 (3) is formed, which comprises the novel BTHP2- ligand (BTHP2- =bis(3,5-bis(trimethylsilyl)-1,3a,6,6a-tetrahydropentalene-1-yl)diide or bis(2,7-bis(trimethylsilyl)bicyclo[3.3.0]octa-2,7-dien-4-yl)diide, C16 H10 (SiMe3 )42- ). The formation of 3 is likely facilitated by the fact that scandium prefers η8 ,η3  coordination rather than highly symmetric η8 ,η8  coordination, and the η3 -coordinated COT'' ligand in 1 is activated owing to a loss of aromaticity. Acid hydrolysis of 3 leads to air-stable H2 BTHP (4).

A Structurally Characterized Organometallic Plutonium(IV) Complex.

The blood-red plutonocene complex Pu(1,3-COT'')(1,4-COT'') (4; COT''=η8 -bis(trimethylsilyl)cyclooctatetraenyl) has been synthesized by oxidation of the anionic sandwich complex Li[Pu(1,4-COT'')2 ] (3) with anhydrous cobalt(II) chloride. The first crystal structure determination of an organoplutonium(IV) complex revealed an asymmetric sandwich structure for 4 where one COT'' ring is 1,3-substituted while the other retains the original 1,4-substitution pattern. The electronic structure of 4 has been elucidated by a computational study, revealing a probable cause for the unexpected silyl group migration.

Ceric Cyclopentadienides Bearing Alkoxy, Aryloxy, Chlorido, or Iodido Co-Ligands.

A series of heteroleptic tris(cyclopentadienyl) CeIV complexes has been isolated and crystallographically characterized, revealing the broad accessibility of such organocerium(IV) compounds. The oxidation of complexes CpMe3 Ce(thf) and Cp'3 Ce(thf) (CpMe =C5 H4 Me, Cp'=C5 H4 SiMe3 ), bearing monosubstituted electron-poor cyclopentadienyl ligands, with 0.5 equivalents of 1,4-benzoquinone or C2 Cl6 gave the cerium(IV) hydroquinolate complexes CpMe3 Ce(OC6 H4 O)CeCpMe3 and Cp'3 Ce(OC6 H4 O)CeCp'3 , or the chloride complexes CpMe3 CeCl and Cp'3 CeCl, respectively; the iodide complex Cp'3 CeI was obtained from the reaction of Cp'3 Ce(thf) with elemental iodine. The behavior of Cp'3 CeCl in salt metathesis protocols employing alkali metal amides or alkyl, alkoxide, and aryloxide reagents was investigated, which gave rise to the robust and isolable cerium(IV) alkoxide Cp'3 Ce(OtBu). Trivalent [Cp'2 CeCl]2 was synthesized by AlMe4 →Cl exchange utilizing Cp'2 Ce(AlMe4 ) and AlMe2 Cl. The reactivity of [Cp'2 CeCl]2 towards the oxidants Ph3 CCl, C2 Cl6 , 1,4-benzoquinone, and I2 has been assessed, and has provided useful information on CeIII /CeIV redox deactivation pathways. In addition to X-ray structure analysis, all the complexes were characterized by NMR, DRIFT (diffuse reflectance IR Fourier transform), and UV/Vis spectroscopy as well as elemental analysis. The tetravalent compounds were further analyzed for their magnetic susceptibility by using Evans' method.