Structure-Solubility Relationship of 1,4-Dioxane Complexes of Di(hydrocarbyl)magnesium.

Systematic variation of the 1,4-dioxane (dx) concentration during the precipitation of sparingly soluble [MgBr2 (dx)2 ] from ethereal Grignard solutions of RMgBr has allowed the structural investigation of crystallized [R2 Mg(dx)n ] (n=1, 1.5, 2, and 3), which form during this dioxane method, depending on the bulkiness of R. The numbering of the complexes explored in this study is based on the number n of dioxane molecules per magnesium atom, followed by the substituent R; an apostrophe denotes coordination polymers. The following derivatives were studied by X-ray crystal-structure determination and NMR spectroscopy: n=1: [Me2 Mg(µ-dx)]∞ (1'-Me) and [nPr2 Mg(µ-dx)]∞ (1'-nPr); n=1.5: [{iPr2 Mg(dx)}2 (µ-dx)] (1.5-iPr), [{oTol2 Mg(dx)}2 (µ-dx)] (1.5-oTol), and [(Me3 Si-C≡C)2 Mg(dx)1.5 ]∞ (1.5'-C2 SiMe3 ); n=2: [tBu2 Mg(dx)2 ] (2-tBu) and [oTol2 Mg(dx)2 ] (2-oTol); n=3: [Ph2 Mg(dx)3 ] (3-Ph). In the structure types 1', 1.5, and 2, the magnesium atom exhibits the coordination number 4, whereas pentacoordinate metal atoms are observed in types 3 and 1.5'. The structure type 2' is realized for [(Ph-C≡C)2 Mg(dx)2 ]∞ (2'-C2 Ph), [MgCl2 (dx)2 ]∞ (2'-Cl), and [MgBr2 (dx)2 ]∞ (2'-Br) with hexacoordinate metal atoms. The solubility of the dioxane adducts in common organic solvents strongly depends on the degree of aggregation with the solubility decreasing from molecular to strand to layer structures.

Aryl calcium compounds: syntheses, structures, physical properties, and chemical behavior.

Organocalcium chemistry is still in its infancy. The direct synthesis of activated calcium and (substituted) iodobenzenes allows for the large-scale and high-yield synthesis of aryl calcium iodides. The influence of the substitution patterns of the phenyl group, halogen atom, and solvent is discussed. Aryl calcium iodides show a Schlenk equilibrium that enables the isolation of diaryl calcium derivatives. Owing to the high reactivity of aryl calcium halides, low temperatures have to be maintained throughout the preparative procedures in order to avoid side reactions. A decrease of reactivity and, hence, an enhanced stability at higher temperatures can be achieved by shielding of the calcium atom by increasing the coordination number of the metal center or by substitution of the iodide anion by bulky groups.

A key step in the formation of acrylic acid from CO2 and ethylene: the transformation of a nickelalactone into a nickel-acrylate complex.

The reaction of a nickelalactone with dppm, resulting in the formation of a stable binuclear Ni(I) complex with an acrylate, a Ph2P- and a dppm bridge, models a key step in the formation of acrylic acid from CO2 and ethylene.

Selective Intermolecular Coupling of Alkynes with Nitriles and Ketones via beta,beta' Carbon-Carbon Bond Cleavage of Zirconacyclopentenes.

Selective intermolecular coupling of alkynes with nitriles and ketones was performed by the reaction of a mixture of alkynes and Cp(2)ZrEt(2) with nitriles and ketones, respectively. Hydrolysis of the mixture gave alpha,beta-unsaturated ketones and allylic alcohols in good to excellent yields, respectively. These reactions proceeded via zirconacyclopentenes which were prepared by the reaction of alkynes with Cp(2)ZrEt(2). The structure of zirconacyclopentene, which was prepared from diphenylacetylene and Cp(2)ZrEt(2), was determined by X-ray analysis. It clearly indicated that there is a single bond between the beta- and beta'-carbons of the zirconacyclopentene. The reaction of zirconacyclopentenes with nitriles or ketones proceeded via the beta,beta' carbon-carbon bond cleavage of the zirconacyclopentenes. In a similar way, addition of PMe(3) to the zirconacyclopentene afforded a zirconocene-alkyne complex in 87% yield.

Heavy Grignard reagents: challenges and possibilities of aryl alkaline earth metal compounds.

Compounds of the type aryl--M--X, with M=Ca, Sr, Ba and X as any kind of ligand (such as halide, phosphanide, amide, aryl), are presented. The low reactivity of the heavy alkaline earth metals calcium, strontium, and barium enforces an activation prior to use for the direct synthesis. The insertion of these metals into C--I bonds of aryl iodides (direct synthesis) yields aryl metal iodides and has to be performed at low temperatures and in THF. Aryl alkaline-earth-metal compounds show some characteristics: 1) the ease of ether cleavage enforces low reaction temperatures, 2) for Sr and Ba the Schlenk equilibrium is shifted towards homoleptic MI2 and MPh2, 3) high solubility of diaryl alkaline-earth-metal derivatives in THF even at low temperatures initiated quantum chemical investigations on the aggregation behavior, and 4) a strong low field shift of the 13C resonances of the ipso carbon atoms in NMR spectra was observed. First results from quantum chemical calculations on diaryl dicalcium(I) suggest a long Ca--Ca bond with a considerable Ca--Ca bond dissociation energy. Initial results on a selection of applications such as metallation, metathesis, and addition reactions of aryl calcium compounds are presented as well.

Syntheses and structures of alkaline earth metal bis(diphenylamides).

Various preparative procedures are employed in order to synthesize alkaline earth metal bis(diphenylamides) such as (i) metalation of HNPh2 with the alkaline earth metal M, (ii) metalation of HNPh2 with MPh2, (iii) metathesis reaction of MI2 with KNPh2, (iv) metalation of HNPh2 with PhMI in THF, and (v) metathesis reaction of PhMI with KNPh2 followed by a dismutation reaction yielding MPh2 and M(NPh2)2. The magnesium compounds [(diox)MgPh2]infinity (1) and (thf)2Mg(NPh2)2 (2) show tetracoordinate metal atoms, whereas in (dme)2Ca(NPh2)2 (3), (thf)4Sr(NPh2)2 (4), and (thf)4Ba(NPh2)2 (5) the metals are 6-fold coordinated. Additional agostic interactions between an ipso-carbon of one of the phenyl groups of the amide ligand and the alkaline earth metal atom lead to unsymmetric coordination of the NPh2 anions with two strongly different M-N-C angles in 3-5.

Metal complexes with 2,3-bis(diphenylphosphino)-1,4-diazadiene ligands: synthesis, structures, and an intramolecular metal-mediated [4 + 2] cycloaddition employing a benzene ring as a dienophile.

2,3-Bis(diphenylphosphino)-1,4-diazadienes RN=C(PPh2)-C(PPh2)=NR (1a, R = 4-tolyl; 1b, R = 4-tert-butylphenyl; 1c, R = mesityl) were used as novel ligands for transition metals. The metal complexes [(1c)Mo(CO)4] (2a), [(1c)[Mo(CO)4]2] (2b), [(1a)Cu(Cl)(PPh3)] (3), and [(1b)[(NiBr2(THF))]2] (4) were characterized by elemental analysis, MS, and 31P[1H], 1H, and 13C NMR spectra (except the paramagnetic complex 4). Additionally, the molecular structure of the complexes in the solid state was determined by single-crystal X-ray diffraction. In 2a and 2b the chelating ligand coordinates via the N,P donor set, whereas in 3 the chelating ligand coordinates via the two P atoms. 4 contains a square-planar (P,P)NiBr2 moiety on the one side of the bridging ligand 1b. On the opposite side the 1,2-dimine unit bonds to another Ni center having octahedral geometry. The bulkier ligand 1c reacts to form the mononuclear compound 5. X-ray diffraction analysis of single crystals shows that 5 contains a quinoxaline derivative with a cyclohexa-1,3-diene ring in the peripheral position. Furthermore, it contains a bis(diphenylphosphino)-ethylene unit coordinating the NiBr2. This arrangement is the result of an intramolecular [4 + 2] cycloaddition between the 1,2-diimine unit (as diheterodiene) and the benzene ring of the 4-tolyl-N substituent (as dieneophile). The same type of ring-closing reaction followed by a tautomerization reaction to form the mononuclear compound 6 occurred by dissolution of the binuclear complex 4 in methanol. This reaction can be used as a simple method for the synthesis of novel 1,2-bis(diarylphosphanyl)ethylenes containing a quinoxaline backbone.