Five-coordinate rhenium(I) hydride complexes of the type [Re(Br)(H)(NO)(PR3)2] (R = Cy 1a, iPr 1b) were reacted with terminal alkynes R1C�CH (R1 = Ph, SiEt3, H), yielding 18-electron �2alkyne adducts [Re(Br)(H)(NO)(PR3)2(�2-HC�CR1)] (R1 = Ph (R = Cy 2a, iPr 2b), SiEt3 (R = Cy 4a, iPr 4b), H (R = Cy 6a, iPr 6b)). Alkyne insertion into the Re−H bond led to the formation of rhenium(I) �1-vinyl der...

The interaction between (PNP)PdH (1); PNP = bis(2-diisopropylphosphino-4-methylphenyl)amide and different acids (CF3SO3H, HBF4∙Et2O, fluorinated alcohols formic acid) was studied in benzene or toluene as well neat by IR NMR spectroscopies. structures of hydrogen-bonded complexes were also optimized at the DFT/ωB97-XD/def2-TZVP level. nitrogen atom amidophosphine pincer ligand readily accepts pr...

In the present study the Mo(0) and W(0) complexes [M(PNP)(CO)3] as well as seven-coordinate cationic hydridocarbonyl Mo(II) and W(II) complexes of the type [M(PNP)(CO)3H]+, featuring PNP pincer ligands based on 2,6-diaminopyridine, have been prepared and fully characterized. The synthesis of Mo(0) complexes [Mo(PNP)(CO)3] was accomplished by treatment of [Mo(CO)3(CH3CN)3] with the respective PN...

The new [{Co5C(CO)12}Au{Co(CO)4}](-), , cluster has been obtained from the reaction of [Co6C(CO)15](2-) with two equivalents of [AuCl4](-). reacts with an excess of HBF4 resulting in the formation of [{Co5C(CO)12}2Au](-), . The new derivatives [Co5C(CO)12(AuPPh3)], , and [Co5C(CO)11(AuPPh3)3], , have been obtained by reacting with two and four equivalents of [Au(PPh3)Cl], respectively. All the ...

A new iron complex with a thioamide SNS pincer type ligand, [FeBr2(κ(3)-H2L(DPM))] (κ(3)-H2L(DPM) = 2,6-bis(N-2,6-bis(diphenylmethyl)-4-isopropylphenylthioamide)pyridine), was synthesized. This complex reacts with NaH in THF to yield a unique Fe(ii) complex with two THF molecules, [Fe(THF)2(κ(3)-L(DPM))] (κ(3)-L(DPM) = 2,6-bis(N-2,6-bis(diphenylmethyl)-4-isopropylphenyliminothiolate)pyridine). ...

Bis(η(5)-2,4-dimethylpentadienyl)ruthenium(II), [(η(5)-C7H11)2Ru] (1, “open ruthenocene”), which has become accessible in high yield and large quantities via an isoprene-derived diallyl ruthenium(IV) complex, can be converted into the protonated open ruthenocene 2 by treatment with HBF4 and subsequently into the protonated half-open ruthenocene 3 by reaction with cyclopentadiene. The electronic...

The one-pot condensation of glyoxal, two equivalents of cyclohexylamine, and paraformaldehyde in the presence of aqueous HBF4 provided a straightforward access to 1,3-dicyclohexylimidazolium tetrafluoroborate (ICy·HBF4). 1,3-Dibenzylimidazolium tetrafluoroborate (IBn·HBF4) was obtained along the same lines. To synthesize 1,3-diarylmidazolium salts, it was necessary to isolate the intermediate N...

Dicationic tetranuclear ruthenium octahydride [(Cp*Ru)4H8]2+ (5) with tetrahedral geometry was obtained by reaction of dinuclear ruthenium tetrahydride (Cp*Ru)2(μ-H)4 (1) with an excess of Brønsted acids, such as HBF4·OEt2, in toluene. Monocationic tetraruthenium heptahydride [(Cp*Ru)4H7]+ (7) was obtained by dropwise addition of a diluted acid to a rigorously stirred solution of 1 at ambient t...