Stereoselective Ring Expansion Metathesis Polymerization with Cationic Molybdenum Alkylidyne N-Heterocyclic Carbene Complexes.

Molybdenum alkylidyne N-heterocyclic carbene (NHC) complexes of the type [Mo(C-p-C6H4Y)(OC(R)(CF3)2)2 (L)(NHC)][B(ArF)4] (Y = OMe, NO2; R = CH3, CF3; L = none, pivalonitrile, tetrahydrofuran; NHC = 1,3-dimesitylimidazol-2-ylidene (IMes), 1,3-dimesityl-3,4-dihydroimidazol-2-ylidene (IMesH2), 1,3-dimesityl-3,4-dichloroimidazol-2-ylidene (IMesCl2), 1,3-diisopropylimidazol-2-ylidene (IiPr); B(ArF)4- = tetrakis(3,5-bis(trifluoromethyl)phen-1-yl)borate) were used in the ring expansion metathesis polymerization (REMP) of cyclic olefins. With cis-cyclooctene (cCOE) cyclic, low molecular weight oligomers were obtained at low monomer concentrations and the cyclic nature of the polymer was confirmed by MALDI-TOF measurements. High-molecular weight cyclic poly(cCOE) became available at high monomer concentrations. Also, post-REMP allowed for converting low-molecular-weight cyclic poly(cCOE) into high-molecular-weight cyclic poly(cCOE). Tailored catalysts together with suitable additives offered access to the stereoselective REMP of functional norbornenes providing functional cis-isotactic (cis-it), cis-syndiotactic (cis-st) and trans-it poly(norbornene)s with up to 99% stereoselectivity. Mechanistic details supported by density functional theory (DFT) calculations are outlined.

Neutral and Cationic Molybdenum Imido Alkylidene Cyclic Alkyl Amino Carbene (CAAC) Complexes for Olefin Metathesis.

The first neutral and cationic Mo imido alkylidene cyclic alkyl amino carbene (CAAC) complexes of the general formulae [Mo(N-Ar)(CHCMe2 Ph)(X)2 (CAAC)] and [Mo(N-Ar)(CHCMe2 Ph)(X)(CAAC)][B(ArF )4 ] (X=Br, Cl, OTf, OC6 F5 ; CAAC=1-(2,6-iPr2 -C6 H3 )-3,3,5,5-tetramethyltetrahydropyrrol-2-ylidene) have been synthesized from molybdenum imido bishalide alkylidene DME precursors. Different combinations of the imido and "X" ligands have been employed to understand synthetic peculiarities. Selected complexes have been characterized by single-crystal X-ray analysis. Due to the pronounced σ-donor/π-acceptor characteristics of CAACs, the corresponding neutral and cationic molybdenum imido alkylidene CAAC complexes do not require the presence of stabilizing donor ligands such as nitriles. Calculations on the PBE0-D3BJ/def2-TZVP level for PBE0-D3BJ/def2-SVP optimized geometries revealed partial charges at molybdenum similar to the corresponding molybdenum imido alkylidene N-heterocyclic carbene (NHC) complexes with a slightly higher polarization of the molybdenum alkylidene bond in the CAAC complexes. All cationic complexes have been tested in olefin metathesis reactions and showed improved activity compared to the analogous NHC complexes for hydrocarbon-based substrates, allowing for turnover numbers (TONs) up to 9500 even at room temperature. Some Mo imido alkylidene CAAC complexes are tolerant towards functional groups like thioethers and sulfonamides.

Quantitative Distinction between Noble Metals Located in Mesopores from Those on the External Surface.

We compare three methods for quantitatively distinguishing the location of noble metal (NM) particles in mesopores from those found on the external support surface. MCM-41 and SBA-15 with NM located in mesopores or on the external surface were prepared and characterized by TEM. 31 P MAS NMR spectroscopy was used to quantify arylphosphines in complexes with NM. Phosphine/NM ratios drop from 2.0 to 0.2 when increasing the probe diameter from 1.08 to 1.54 nm. The reaction between NM and triphenylphosphine (TPP) within 3.0 nm MCM-41 pores takes due to confinement effects multiple weeks. In contrast, external NM react with TPP instantly. A promising method is filling the pores by using the pore volume impregnation technique with tetraethylorthosilicate (TEOS). TPP loading revealed that 66 % of NMs are located on the external surface of MCM-41. The pore filling method can be used in association with any probe molecule, also for the quantification of acid sites.

Interplay of Polarity and Confinement in Asymmetric Catalysis with Chiral Rh Diene Complexes in Microemulsions.

Microemulsions provide a unique opportunity to tailor the polarity and liquid confinement in asymmetric catalysis via nanoscale polar and nonpolar domains separated by a surfactant film. For chiral diene Rh complexes, the influence of counterion and surfactant film on the catalytic activity and enantioselectivity remained elusive. To explore this issue chiral norbornadiene Rh(X) complexes (X=OTf, OTs, OAc, PO2 F2 ) were synthesized and characterized by X-ray crystallography and theoretical calculations. These complexes were used in Rh-catalyzed 1,2-additions of phenylboroxine to N-tosylimine in microemulsions stabilized either exclusively by n-octyl-ß-D-glucopyranoside (C8 G1 ) or a C8 G1 -film doped with anionic or cationic surfactants (AOT, SDS and DTAB). The Rh(OAc) complex showed the largest dependence on the composition of the microemulsion, yielding up to 59 % (90 %ee) for the surfactant film doped with 5 wt% of AOT as compared to 52 % (58 %ee) for neat C8 G1 at constant surfactant concentration. Larger domains, determined by SAXS analysis, enabled further increase in yield and selectivity while the reaction rate almost remained constant according to kinetic studies.