Dehydropolymerization of Amine-Boranes using Bis(imino)pyridine Rhodium Pre-Catalysis: σ-Amine-Borane Complexes, Nanoparticles, and Low Residual-Metal BN-Polymers that can be Chemically Repurposed.

The sigma amine-borane complexes [Rh(L1)(η2 :η2 -H3 B⋅NRH2 )][OTf] (L1=2,6-bis-[1-(2,6-diisopropylphenylimino)ethyl]pyridine, R=Me, Et, n Pr) are described, alongside [Rh(L1)(NMeH2 )][OTf]. Using R=Me as a pre-catalyst (1 mol %) the dehydropolymerization of H3 B ⋅ NMeH2 gives [H2 BNMeH]n selectively. Added NMeH2 , or the direct use of [Rh(L1)(NMeH2 )][OTf], is required for initiation of catalysis, which is suggested to operate through the formation of a neutral hydride complex, Rh(L1)H. The formation of small (1-5 nm) nanoparticles is observed at the end of catalysis, but studies are ambiguous as to whether the catalysis is solely nanoparticle promoted or if there is a molecular homogeneous component. [Rh(L1)(NMeH2 )][OTf] is shown to operate at 0.025 mol % loadings on a 2 g scale of H3 B ⋅ NMeH2 to give polyaminoborane [H2 BNMeH]n [Mn =30,900 g/mol, Ð=1.8] that can be purified to a low residual [Rh] (6 µg/g). Addition of Na[N(SiMe3 )2 ] to [H2 BNMeH]n results in selective depolymerization to form the eee-isomer of N,N,N-trimethylcyclotriborazane [H2 BNMeH]3 : the chemical repurposing of a main-group polymer.

A Series of Crystallographically Characterized Linear and Branched σ-Alkane Complexes of Rhodium: From Propane to 3-Methylpentane.

Using solid-state molecular organometallic (SMOM) techniques, in particular solid/gas single-crystal to single-crystal reactivity, a series of σ-alkane complexes of the general formula [Rh(Cy2PCH2CH2PCy2)(ηn:ηm-alkane)][BArF4] have been prepared (alkane = propane, 2-methylbutane, hexane, 3-methylpentane; ArF = 3,5-(CF3)2C6H3). These new complexes have been characterized using single crystal X-ray diffraction, solid-state NMR spectroscopy and DFT computational techniques and present a variety of Rh(I)···H-C binding motifs at the metal coordination site: 1,2-η2:η2 (2-methylbutane), 1,3-η2:η2 (propane), 2,4-η2:η2 (hexane), and 1,4-η1:η2 (3-methylpentane). For the linear alkanes propane and hexane, some additional Rh(I)···H-C interactions with the geminal C-H bonds are also evident. The stability of these complexes with respect to alkane loss in the solid state varies with the identity of the alkane: from propane that decomposes rapidly at 295 K to 2-methylbutane that is stable and instead undergoes an acceptorless dehydrogenation to form a bound alkene complex. In each case the alkane sits in a binding pocket defined by the {Rh(Cy2PCH2CH2PCy2)}+ fragment and the surrounding array of [BArF4]- anions. For the propane complex, a small alkane binding energy, driven in part by a lack of stabilizing short contacts with the surrounding anions, correlates with the fleeting stability of this species. 2-Methylbutane forms more short contacts within the binding pocket, and as a result the complex is considerably more stable. However, the complex of the larger 3-methylpentane ligand shows lower stability. Empirically, there therefore appears to be an optimal fit between the size and shape of the alkane and overall stability. Such observations are related to guest/host interactions in solution supramolecular chemistry and the holistic role of 1°, 2°, and 3° environments in metalloenzymes.

Chalcogen Bonding Ion-Pair Cryptand Host Discrimination of Potassium Halide Salts.

A series of chalcogen, halogen and hydrogen bonding heteroditopic macrobicyclic cryptands are reported and their potassium halide ion-pair recognition properties investigated. Saliently, the co-bound potassium cation was determined to be crucial in switching on the bromide and iodide recognition properties of the respective cryptand receptor. Importantly, the nature of the sigma-hole mediated interaction employed in the anion recognition component is demonstrated to significantly augment the ion-pair binding behaviour, markedly so for the halogen bonding analogue. Most notably the incorporation of a chelating chalcogen bonding donor motif significantly improves the selectivity towards KBr over KI, relative to halogen and hydrogen bonding analogues.

η2-Alkene Complexes of [Rh(PONOP-iPr)(L)]+ Cations (L = COD, NBD, Ethene). Intramolecular Alkene-Assisted Hydrogenation and Dihydrogen Complex [Rh(PONOP-iPr)(η-H2)].

Rhodium-alkene complexes of the pincer ligand κ3-C5H3N-2,6-(OPiPr2)2 (PONOP-iPr) have been prepared and structurally characterized: [Rh(PONOP-iPr)(η2-alkene)][BArF4] [alkene = cyclooctadiene (COD), norbornadiene (NBD), ethene; ArF = 3,5-(CF3)2C6H3]. Only one of these, alkene = COD, undergoes a reaction with H2 (1 bar), to form [Rh(PONOP-iPr)(η2-COE)][BArF4] (COE = cyclooctene), while the others show no significant reactivity. This COE complex does not undergo further hydrogenation. This difference in reactivity between COD and the other alkenes is proposed to be due to intramolecular alkene-assisted reductive elimination in the COD complex, in which the η2-bound diene can engage in bonding with its additional alkene unit. H/D exchange experiments on the ethene complex show that reductive elimination from a reversibly formed alkyl hydride intermediate is likely rate-limiting and with a high barrier. The proposed final product of alkene hydrogenation would be the dihydrogen complex [Rh(PONOP-iPr)(η2-H2)][BArF4], which has been independently synthesized and undergoes exchange with free H2 on the NMR time scale, as well as with D2 to form free HD. When the H2 addition to [Rh(PONOP-iPr)(η2-ethene)][BArF4] is interrogated using pH2 at higher pressure (3 bar), this produces the dihydrogen complex as a transient product, for which enhancements in the 1H NMR signal for the bound H2 ligand, as well as that for free H2, are observed. This is a unique example of the partially negative line-shape effect, with the enhanced signals that are observed for the dihydrogen complex being explained by the exchange processes already noted.

A Structurally Characterized Cobalt(I) σ-Alkane Complex.

A cobalt σ-alkane complex, [Co(Cy2 P(CH2 )4 PCy2 )(norbornane)][BArF 4 ], was synthesized by a single-crystal to single-crystal solid/gas hydrogenation from a norbornadiene precursor, and its structure was determined by X-ray crystallography. Magnetic data show this complex to be a triplet. Periodic DFT and electronic structure analyses revealed weak C-H→Co σ-interactions, augmented by dispersive stabilization between the alkane ligand and the anion microenvironment. The calculations are most consistent with a η1 :η1 -alkane binding mode.

Reversible Encapsulation of Xenon and CH2 Cl2 in a Solid-State Molecular Organometallic Framework (Guest@SMOM).

Reversible encapsulation of CH2 Cl2 or Xe in a non-porous solid-state molecular organometallic framework of [Rh(Cy2 PCH2 PCy2 )(NBD)][BArF4 ] occurs in single-crystal to single-crystal transformations. These processes are probed by solid-state NMR spectroscopy, including 129 Xe SSNMR. Non-covalent interactions with the -CF3 groups, and hydrophobic channels formed, of [BArF4 ]- anions are shown to be important, and thus have similarity to the transport of substrates and products to and from the active site in metalloenzymes.

A Potent Halogen-Bonding Donor Motif for Anion Recognition and Anion Template Mechanical Bond Synthesis.

The covalent attachment of electron deficient perfluoroaryl substituents to a bis-iodotriazole pyridinium group produces a remarkably potent halogen bonding donor motif for anion recognition in aqueous media. Such a motif also establishes halogen bonding anion templation as a highly efficient method for constructing a mechanically interlocked molecule in unprecedented near quantitative yield. The resulting bis-perfluoroaryl substituted iodotriazole pyridinium axle containing halogen bonding [2]rotaxane host exhibits exceptionally strong halide binding affinities in competitive 50 % water containing aqueous media, by a factor of at least three orders of magnitude greater in comparison to a hydrogen bonding rotaxane host analogue. These observations further champion and advance halogen bonding as a powerful tool for recognizing anions in aqueous media.

Modulation of σ-Alkane Interactions in [Rh(L2)(alkane)]+ Solid-State Molecular Organometallic (SMOM) Systems by Variation of the Chelating Phosphine and Alkane: Access to η2,η2-σ-Alkane Rh(I), η1-σ-Alkane Rh(III) Complexes, and Alkane Encapsulation.

Solid/gas single-crystal to single-crystal (SC-SC) hydrogenation of appropriate diene precursors forms the corresponding σ-alkane complexes [Rh(Cy2P(CH2) nPCy2)(L)][BArF4] ( n = 3, 4) and [ RhH(Cy2P(CH2)2( CH)(CH2)2PCy2)(L)][BArF4] ( n = 5, L = norbornane, NBA; cyclooctane, COA). Their structures, as determined by single-crystal X-ray diffraction, have cations exhibiting Rh···H-C σ-interactions which are modulated by both the chelating ligand and the identity of the alkane, while all sit in an octahedral anion microenvironment. These range from chelating η2,η2 Rh···H-C (e.g., [Rh(Cy2P(CH2) nPCy2)(η2η2-NBA)][BArF4], n = 3 and 4), through to more weakly bound η1 Rh···H-C in which C-H activation of the chelate backbone has also occurred (e.g., [ RhH(Cy2P(CH2)2( CH)(CH2)2PCy2)(η1-COA)][BArF4]) and ultimately to systems where the alkane is not ligated with the metal center, but sits encapsulated in the supporting anion microenvironment, [Rh(Cy2P(CH2)3PCy2)][COA⊂BArF4], in which the metal center instead forms two intramolecular agostic η1 Rh···H-C interactions with the phosphine cyclohexyl groups. CH2Cl2 adducts formed by displacement of the η1-alkanes in solution ( n = 5; L = NBA, COA), [ RhH(Cy2P(CH2)2( CH)(CH2)2PCy2)(κ1-ClCH2Cl)][BArF4], are characterized crystallographically. Analyses via periodic DFT, QTAIM, NBO, and NCI calculations, alongside variable temperature solid-state NMR spectroscopy, provide snapshots marking the onset of Rh···alkane interactions along a C-H activation trajectory. These are negligible in [Rh(Cy2P(CH2)3PCy2)][COA⊂BArF4]; in [ RhH(Cy2P(CH2)2( CH)(CH2)2PCy2)(η1-COA)][BArF4], σC-H → Rh σ-donation is supported by Rh → σ*C-H "pregostic" donation, and in [Rh(Cy2P(CH2) nPCy2)(η2η2-NBA)][BArF4] ( n = 2-4), σ-donation dominates, supported by classical Rh(dπ) → σ*C-H π-back-donation. Dispersive interactions with the [BArF4]- anions and Cy substituents further stabilize the alkanes within the binding pocket.

Structural Studies of Cesium, Lithium/Cesium, and Sodium/Cesium Bis(trimethylsilyl)amide (HMDS) Complexes.

Reacting cesium fluoride with an equimolar n-hexane solution of lithium bis(trimethylsilyl)amide (LiHMDS) allows the isolation of CsHMDS (1) in 80% yield (after sublimation). This preparative route to 1 negates the need for pyrophoric Cs metal or organocesium reagents in its synthesis. If a 2:1 LiHMDS:CsF ratio is employed, the heterobimetallic polymer [LiCs(HMDS)2]∞ 2 was isolated (57% yield). By combining equimolar quantities of NaHMDS and CsHMDS in hexane/toluene [toluene·NaCs(HMDS)]∞ 3 was isolated (62% yield). Attempts to prepare the corresponding potassium-cesium amide failed and instead yielded the known monometallic polymer [toluene·Cs(HMDS)]∞ 4. With the aim of expanding the structural diversity of Cs(HMDS) species, 1 was reacted with several different Lewis basic donor molecules of varying denticity, namely, (R,R)-N,N,N',N'-tetramethylcyclohexane-1,2-diamine [(R,R)-TMCDA] and N,N,N',N'-tetramethylethylenediamine (TMEDA), N,N,N',N″,N″-pentamethyldiethylenetriamine (PMDETA), tris[2-(dimethylamino)ethyl]amine (Me6-TREN) and tris[2-(2-methoxyethoxy)ethyl]amine (TMEEA). These reactions yielded dimeric [donor·NaCs(HMDS)2]2 5-7 [where donor is (R,R)-TMCDA, TMEDA and PMDETA respectively], the tetranuclear "open"-dimer [{Me6-TREN·Cs(HMDS)}2{Cs(HMDS)}2] 8 and the monomeric [TMEEA·Cs(HMDS)] 9. Complexes 2, 3, and 5-9 were characterized by X-ray crystallography and in solution by multinuclear NMR spectroscopy.

Synthetic and Structural Studies of Mixed Sodium Bis(trimethylsilyl)amide/Sodium Halide Aggregates in the Presence of η(2)-N,N-, η(3)-N,N,N/N,O,N-, and η(4)-N,N,N,N-Donor Ligands.

When n-hexane solutions of an excess of sodium bis(trimethylsilyl)amide (NaHMDS) are combined with cesium halide (halide = Cl, Br, or I) in the presence of the tetradentate donor molecule [tris[2-(dimethylamino)ethyl]amine] (Me6TREN), the isolation and characterization of a series of sodium amide/sodium halide mixed aggregates was forthcoming. Cesium halide was employed because it efficiently reacted with NaHMDS to produce a molecular, soluble source of sodium halide salt (which was subsequently captured by an excess of NaHMDS) via a methathetical reaction. These mixed sodium amide/sodium halide complexes are formally sodium sodiates, are deficient in halide with respect to the amide, and have the general formula [{Na5(µ-HMDS)5(µ5-X)}{Na(Me6TREN)}] [where X = Cl (1), Br (2), or I (3)]. The influence of the donor ligand was studied for the NaI/NaHMDS system, and when n-hexane solutions of this composition were treated with tridentate donors such as N,N,N',N″,N″-pentamethyldiethylenetriamine (PMDETA) or N,N,N',N'-tetramethyldiaminoethyl ether (TMDAE), solvent-separated ion-pair cocomplexes [Na5(µ-HMDS)5(µ5-I)](-)[Na3(µ-HMDS)2(PMDETA)2](+) (4) and [Na5(µ-HMDS)5(µ5-I)](-)[Na(TMDAE)2](+) (5) were isolated. However, upon reaction with bidentate proligands such as the chiral diamine (R,R)-N,N,N',N'-tetramethylcyclohexane-1,2-diamine [(R,R)-TMCDA] or N,N,N',N'-tetramethylethylenediamine (TMEDA), neutral complexes [Na4(µ-HMDS)3(µ4-I)(donor)2] [donor = (R,R)-TMCDA (6) and TMEDA (7)] were produced. To illustrate the generality of the latter reaction with other halides, [Na4(µ-HMDS)3(µ4-Br)(TMEDA)2] (8) was also prepared by employing NaBr in the synthesis instead of NaI.

Alkali-Metal-Mediated Magnesiations of an N-Heterocyclic Carbene: Normal, Abnormal, and "Paranormal" Reactivity in a Single Tritopic Molecule.

Herein the sodium alkylmagnesium amide [Na4Mg2(TMP)6(nBu)2] (TMP=2,2,6,6-tetramethylpiperidide), a template base as its deprotonating action is dictated primarily by its 12 atom ring structure, is studied with the common N-heterocyclic carbene (NHC) IPr [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]. Remarkably, magnesiation of IPr occurs at the para-position of an aryl substituent, sodiation occurs at the abnormal C4 position, and a dative bond occurs between normal C2 and sodium, all within a 20 atom ring structure accommodating two IPr(2-). Studies with different K/Mg and Na/Mg bimetallic bases led to two other magnesiated NHC structures containing two or three IPr(-) monoanions bound to Mg through abnormal C4 sites. Synergistic in that magnesiation can only work through alkali-metal mediation, these reactions add magnesium to the small cartel of metals capable of directly metalating a NHC.

Revealing unbound ß-diketiminate anions: structural dynamics from caesium complexes.

This study reports the first structural elucidation of ß-diketiminate anions (BDI-), known for strong coordination, in their unbound form within caesium complexes. ß-Diketiminate caesium salts (BDICs) were synthesised, and upon the addition of Lewis donor ligands, free BDI- anions and donor-solvated Cs+ cations were observed. Notably, the liberated BDI- anions exhibited an unprecedented dynamic cisoid-transoid exchange in solution.

The Iron and Calcium Availability and the Satiating Effect of Different Biscuits.

Biscuits are bakery products made with wheat flour. Wheat is a good source of minerals and dietary fibre, although the presence of phytate or other components could modify mineral availability. In addition, cereal-based products are usually characterised by high fibre content that can influence satiety. The objectives of this study were to evaluate both the iron and calcium availability and the satiety effect of different types of biscuits (traditional recipe vs. "Digestive") sold in the Spanish market, identifying whether the biscuit type could have effects on these parameters. Nutritional composition and the use of the generic descriptor "Digestive" of biscuits were collected from labels. Phytate and mineral contents were also measured. All samples were previously digested by a simulated process of the gastrointestinal conditions. The satiating effect of biscuits was evaluated according to VAS questionnaires. Results indicated that the mineral content and availability were different between types of biscuits (the traditional recipe showed the highest calcium concentration, while iron was higher in the "Digestive" type). However, mineral availability showed the highest percentages for both minerals, calcium and iron, in the Maria-type samples. Regardless of the different fibre content of both types of biscuits, and despite being higher in the Digestive type than in the Maria type, the satiety measures indicated that the Maria type had more effect on the food intake control. Thus, the descriptor "Digestive¨ in biscuits does not seem to be a marker of better nutritional quality, including parameters of effects on health such as mineral availability or satiety.

Photofunctional Scope of Fluorescent Dithienylethene Conjugates with Aza-Heteroaromatic Cations.

A series of dithienylethene (DTE) photoswitches with aza-heteroaromatic cationic moieties is synthesized. The switches are characterized regarding their photochemical and photophysical properties in acetonitrile and in water. The efficiency of the switching and the photostationary state composition depend on the degree of π-conjugation of the heteroaromatic systems. Thus, DTEs with acridinium-derived moieties have very low quantum yields for the ring-closing process, which is in contrast to switches with pyridinium and quinolinium moieties. All switches emit fluorescence in their open forms. The involved electronic transitions are traced back to an integrative picture including the DTE core and the cationic arms. The emission can be fine-tuned by the π-conjugation of the heteroaromatic cations, reaching the red spectral region for DTEs with acridinium moieties. On ring-closing of the DTEs the fluorescence is not observable anymore. Theoretical calculations point to rather low-lying energy levels of the highly conjugated ring-closed DTEs, which would originate near-infrared emission (> 1200 nm). The latter is predicted to be very weak due to the concurrent non-radiative deactivation, according to the energy-gap law. In essence, an ON-OFF fluorescence switching as the result of the electrocyclic ring-closing reaction is observed.

Organotelluroxane molecular clusters assembled via Te⋯X- (X = Cl-, Br-) chalcogen bonding anion template interactions.

The synthesis and characterisation of two novel molecular organotelluroxane clusters, comprising of an inorganic Te8O6X4 (X = Cl, Br) core structure are described. The integration of highly electron withdrawing 3,5-bis-trifluoromethylphenyl groups to the constituent Te(IV) centres is determined to be crucial in the chalcogen bonding (ChB) halide template directed assembly. Characterised by multi-nuclear 1H, 125Te, 19F NMR, UV-Vis, IR spectroscopies and X-ray crystal structure analysis, the discrete molecular clusters exhibit excellent organic solvent solubility and remarkable chemical stability. Furthermore, preliminary fluorescence investigations reveal the telluroxanes exhibit aggregation induced emission (AIE) behaviour in organic aqueous solvent mixtures.

Inverse Isotope Effects in Single-Crystal to Single-Crystal Reactivity and the Isolation of a Rhodium Cyclooctane σ-Alkane Complex.

The sequential solid/gas single-crystal to single-crystal reaction of [Rh(Cy2P(CH2)3PCy2)(COD)][BArF 4] (COD = cyclooctadiene) with H2 or D2 was followed in situ by solid-state 31P{1H} NMR spectroscopy (SSNMR) and ex situ by solution quenching and GC-MS. This was quantified using a two-step Johnson-Mehl-Avrami-Kologoromov (JMAK) model that revealed an inverse isotope effect for the second addition of H2, that forms a σ-alkane complex [Rh(Cy2P(CH2)3PCy2)(COA)][BArF 4]. Using D2, a temporal window is determined in which a structural solution for this σ-alkane complex is possible, which reveals an η2,η2-binding mode to the Rh(I) center, as supported by periodic density functional theory (DFT) calculations. Extensive H/D exchange occurs during the addition of D2, as promoted by the solid-state microenvironment.

Synthesis of a family of 3-alkyl- or 3-aryl-substituted 1,2-dihydroquinazolinium salts and their isomerization to 4-iminium-1,2,3,4-tetrahydroquinolines.

A straightforward synthesis of substituted 1,2-dihydroquinazolinium triflates (3) is reported by reaction of 2-imino-substituted anilines with a range of carbonyl compounds in the presence of triflic acid via intermediate iminium salts. Similar reactions with di- or trialdehydes and triflic acid give bis- or tris-(1,2-dihydroquinazolinium) salts. Some 4-methyl substituted 1,2-dihydroquinazolinium salts rearrange, under various conditions, to their corresponding 4-iminium-1,2,3,4-tetrahydroquinolinium isomers (7). Most of salts 3 derived from ketones are rather unstable, which prevents their isolation or full characterization. The crystal structures of various 3 and 7 salts have been determined.

Ortho-aryl substituted DPEphos ligands: rhodium complexes featuring C-H anagostic interactions and B-H agostic bonds.

The synthesis of new Schrock-Osborn Rh(i) pre-catalysts with ortho-substituted DPEphos ligands, [Rh(DPEphos-R)(NBD)][BArF 4] [R = Me, OMe, iPr; ArF = 3,5-(CF3)2C6H3], is described. Along with the previously reported R = H variant, variable temperature 1H NMR spectroscopic and single-crystal X-ray diffraction studies show that these all have axial (C-H)⋯Rh anagostic interactions relative to the d8 pseudo square planar metal centres, that also result in corresponding downfield chemical shifts. Analysis by NBO, QTAIM and NCI methods shows these to be only very weak C-H⋯Rh bonding interactions, the magnitudes of which do not correlate with the observed chemical shifts. Instead, as informed by Scherer's approach, it is the topological positioning of the C-H bond with regard to the metal centre that is important. For [Rh(DPEphos-iPr)(NBD)][BArF 4] addition of H2 results in a Rh(iii) iPr-C-H activated product, [Rh(κ3,σ-P,O,P-DPEphos-iPr')(H)][BArF 4]. This undergoes H/D exchange with D2 at the iPr groups, reacts with CO or NBD to return Rh(i) products, and reaction with H3B·NMe3/tert-butylethene results in a dehydrogenative borylation to form a complex that shows both a non-classical B-H⋯Rh 3c-2e agostic bond and a C-H⋯Rh anagostic interaction at the same metal centre.

2-(Aminomethyl)phenyl complexes of Au(III), mixed Au(III)/Ag(I), and Pd(II) with the 2,2-diacetyl-1,1-ethylenedithiolato ligand: dancing of palladacycles around a juggler ligand.

The reaction of [Tl(2){mu-S,S-S(2)C=C{C(O)Me}(2)}] with [Au(C,N-C(6)H(4)CH(2)NMe(2)-2)Cl(2)] (1:1) gives [{Au(C,N-C(6)H(4)CH(2)NMe(2)-2)}{S,S-S(2)C=C{C(O)Me}(2)}] (1) which, in turn, reacts with AgClO(4) (1:1) to give [{Au(C,N-C(6)H(4)CH(2)NMe(2)-2)}{Ag(OClO(3))}{S(2)C=C{C(O)Me}(2)}] (2). Complexes [{Au(C,N-C(6)H(4)CH(2)NMe(2)-2)}{Ag(X)(PPh(3))}{S(2)C=C{C(O)Me}(2)}] [X = OClO(3) (3), ONO(2) (4)] have been obtained by reaction of 1 with PPh(3) and AgClO(4) or AgNO(3), respectively (1:1:1). Complex 3 can also be obtained by reacting 2 with PPh(3) (1:1). Complexes [Pd(C,N-C(6)H(4)CH(2)NR(2)-2)(mu-Cl)](2) (R = Me, H) react (i) with [Tl(2){S(2)C=C{C(O)Me}(2)}] and [PPN]Cl (0.5:1:1, PPN = Ph(3)P=N=PPh(3)) to form PPN[Pd(C,N-C(6)H(4)CH(2)NR(2)-2){S,S-S(2)C=C{C(O)Me}(2)}] [R = H (5a), Me (5b)], or (ii) with [Tl(2){S(2)C=C{C(O)Me}(2)}] (1:1) to form [{Pd(C,N-C(6)H(4)CH(2)NR(2)-2)}(2){mu-S,S,O-S(2)C=C{C(O)Me}(2)}] [R = H (6a), Me (6b)]. The trinuclear complexes [{Pd(C,N-C(6)H(4)CH(2)NR(2)-2)}(3){mu(3)-O,S,S,O-S(2)C=C{C(O)Me}(2)}]ClO(4) [R = H (7a), Me (7b)] can be prepared by reacting the corresponding dinuclear complex 6a or 6b with [Pd(C,N-C(6)H(4)CH(2)NR(2)-2)(NCMe)(2)]ClO(4) (1:1). The crystal structures of 1, 6b x CH(2)Cl(2), and 7b x CH(2)Cl(2) have been determined. NMR studies have been carried out to explain the solution behavior of these complexes. VT-NMR and line shape analysis for the species where R = Me (5b, 6b, 7b) have allowed the estimation of the activation parameters for these exchange processes.

Solid-State Molecular Organometallic Catalysis in Gas/Solid Flow (Flow-SMOM) as Demonstrated by Efficient Room Temperature and Pressure 1-Butene Isomerization.

The use of solid-state molecular organometallic chemistry (SMOM-chem) to promote the efficient double bond isomerization of 1-butene to 2-butenes under flow-reactor conditions is reported. Single crystalline catalysts based upon the σ-alkane complexes [Rh(R2PCH2CH2PR2)(η2η2-NBA)][BArF 4] (R = Cy, tBu; NBA = norbornane; ArF = 3,5-(CF3)2C6H3) are prepared by hydrogenation of a norbornadiene precursor. For the tBu-substituted system this results in the loss of long-range order, which can be re-established by addition of 1-butene to the material to form a mixture of [Rh(tBu2PCH2CH2PtBu2)(cis-2-butene)][BArF 4] and [Rh(tBu2PCH2CH2PtBu2)(1-butene)][BArF 4], in an order/disorder/order phase change. Deployment under flow-reactor conditions results in very different on-stream stabilities. With R = Cy rapid deactivation (3 h) to the butadiene complex occurs, [Rh(Cy2PCH2CH2PCy2)(butadiene)][BArF 4], which can be reactivated by simple addition of H2. While the equivalent butadiene complex does not form with R = tBu at 298 K and on-stream conversion is retained up to 90 h, deactivation is suggested to occur via loss of crystallinity of the SMOM catalyst. Both systems operate under the industrially relevant conditions of an isobutene co-feed. cis:trans selectivites for 2-butene are biased in favor of cis for the tBu system and are more leveled for Cy.