Organocalcium compounds have been reported as efficient catalysts for various alkene transformations. In contrast to transition metal catalysis, the alkenes are not activated by metal-alkene orbital interactions. Instead it is proposed that alkene activation proceeds through an electrostatic interaction with a Lewis acidic Ca(2+) . The role of the metal was evaluated by a study using the metal-free catalysts: [Ph2 N(-) ][Me4 N(+) ] and [Ph3 C(-) ][Me4 N(+) ]. These "naked" amides and carbanions can act as catalysts in the conversion of activated double bonds (CO and CN) in the hydroamination of ArNCO and RNCNR (R=alkyl) by Ph2 NH. For the intramolecular hydroamination of unactivated CC bonds in H2 CCHCH2 CPh2 CH2 NH2 the presence of a metal cation is crucial. A new type of hybrid catalyst consisting of a strong organic Schwesinger base and a simple metal salt can act as catalyst for the intramolecular alkene hydroamination. The influence of the cation in catalysis is further evaluated by a DFT study.

The reaction of PhP(DIPP)NH with AlMe cleanly gives an aluminum amide complex that crystallizes as a centrosymmetric dimer with a six-membered Al-N-P-Al-N-P ring. In aromatic solvents the dimer remains intact but the Al-P bond is readily broken upon addition of THF to form PhP(DIPP)NAlMe·THF. Efforts to use [PhP(DIPP)NAlMe] as a "masked" Lewis acidic activator for olefin polymerization catalysts were unsuccessful but the complex showed a Frustrated Lewis pair reactivity instead. The P/Al complex reacts with isocyanates to give the C[double bond, length as m-dash]O inserted product that crystallizes as a five-membered ring system Al-O-C(NR)-P-N. The reaction of [PhP(DIPP)NAlMe] with CO, however, gave an insertion in the N-Al bond and the dimeric product [PhP(DIPP)NCOAlMe] was isolated. The dimer [PhP(DIPP)NAlMe] is one of the few Al/P FLPs that can activate C[double bond, length as m-dash]C double bonds irreversibly. A reaction with allyl methyl sulfide and 1-hexene led to the clean formation of the structurally similar activated alkene products [(DIPP)N-PhP-CH(CHSMe)CH]AlMe and [(DIPP)N-PhP-CH(CH)CH]AlMe.

Syntheses and crystal structures of the monomeric bora-amidinate (bam) complexes NBN-Mg·(THF) and NBN-Ca·(THF) are presented; NBN = HB[N(2,6-iPr-CH)]. The simplicity of their H NMR spectra in THF-d suggest that their monomeric solid state structures are retained in solution. NBN-Mg·(THF) in CD, however, is in equilibrium with a dimeric species. Calculations (B3PW91/6-311++G**) reveal a very high localized negative charge (NPA: -1.103) on the N atoms in NBN-Mg. The strongly basic properties of the bam ligand are in agreement with catalytic activity of these complexes in the intramolecular alkene hydroamination. A mechanism is proposed in which the bam ligand is non-innocent and cooperative, playing an active role in substrate deprotonation and product protonation.

Electron ionization (EI) is a reliable mass spectrometric method for the analysis of the vast majority of thermally stable and volatile compounds. In direct EI-MS, the sample is placed into the probe and introduced to the source. For air-and moisture-sensitive organometallic complexes, the sample introduction step is critical. A small quantity must be briefly exposed to the atmosphere, during which time decomposition can occur. Here we present a simple tool that allows convenient analysis of air-and moisture-sensitive organometallic species by direct probe methods: a small purge-able glove chamber affixed to the front end of the mass spectrometer.Using the upgraded mass spectrometer, we successfully characterized of a series of air-and moisture-sensitive organometallic complexes, ranging from mildly to very air-sensitive.

Reduction of red CpTiCl (Cp = cyclopentadienyl) with zinc dust in acetonitrile produces a blue solution of [CpTi(NCMe)], which when exposed to air rapidly discolors to bright yellow. This behavior makes the blue solution a handy visual indicator for the presence of oxygen, but the chemistry is considerably more complicated than the primary colors suggest at first glance. Real-time mass spectrometric and colorimetric analysis reveals that oxidation from Ti(III) to Ti(IV) produces a host of oxygen-containing complexes, whose appearance parallels the observed color changes.

Hybrid catalysts consisting of alkaline earth iodides (AeI2) and the Schwesinger base tBuP4 catalyse the intramolecular alkene hydroamination of H2C=CHCH2CR2CH2NH2 [CR2=CPh2, C(CH2)5, CMe2]. Activities decrease along the row: Ca > Sr >> Mg > Ba. Hybrid catalysts consisting of tBuP4 and ZnI2, AlI3, FeCI3 or NaI were found to be fully inactive. Also, the hybrid catalyst tBuP3/CaI2 was not active which means that the base strength of the non‐nucleophilic organic base must be higher than that of tBuP3 (pKa BH+ = 38.6). Combinations of tBuP4 with CaX2 (X = Cl, Br, OiPr, OTf, NTf2) were found to be fully inactive which may in part be explained by poor solubility. The hybrid catalysis method is therefore limited to the combination tBuP4/CaI2 but the iodide ligands may be partially or fully replaced by chiral ligands. Chiral modifications of the hybrid catalysts gave in intramolecular alkene hydroamination ee values up to 33 %.

Organocalcium compounds have been reported as efficient catalysts for various alkene transformations. In contrast to transition metal catalysis, the alkenes are not activated by metal–alkene orbital interactions. Instead it is proposed that alkene activation proceeds through an electrostatic interaction with a Lewis acidic Ca2+. The role of the metal was evaluated by a study using the metal‐free catalysts: [Ph2N−][Me4N+] and [Ph3C−][Me4N+]. These “naked” amides and carbanions can act as catalysts in the conversion of activated double bonds (CO and CN) in the hydroamination of ArNCO and RNCNR (R=alkyl) by Ph2NH. For the intramolecular hydroamination of unactivated CC bonds in H2CCHCH2CPh2CH2NH2 the presence of a metal cation is crucial. A new type of hybrid catalyst consisting of a strong organic Schwesinger base and a simple metal salt can act as catalyst for the intramolecular alkene hydroamination. The influence of the cation in catalysis is further evaluated by a DFT study.

Organotrifluoroborates serve as coupling partners during transmetalation in the Suzuki–Miyaura reaction but require hydrolysis prior to the coupling reaction. Their anionic nature allows study of their hydrolysis by electrospray ionization mass spectrometry (ESI‐MS) through real‐time monitoring, complemented by pH analysis. The induction period varied according to the borates employed, and a dynamic series of equilibria for numerous ions was observed during hydrolysis. We found that the induction periods and reaction rates were sensitive to the R group of the borates, the shape of the reaction vessel, and stir rate.