Michael C. W. Chan

Crowded bis-(M-salphen) [M = Pt(II), Zn(II)] coordination architectures: luminescent properties and ion-selective responses.

For binuclear luminescent host systems, cooperativity between metal-organic moieties becomes feasible with regards to photophysical properties and sensing behavior. A new class of conformationally rigid binuclear platinum(II) and zinc(II) complexes bearing tetradentate aromatic Schiff base (salphen) ligands with limited rotational freedom has been prepared and characterized, and the molecular structure of a (Pt-salphen)2 derivative has been determined by X-ray crystallography. Their UV-vis absorption and emission properties have been investigated and are tentatively ascribed to different excited states depending on the metal and the extent of intramolecular π-stacking interactions. Colorimetric and phosphorescent responses by the bis-Pt(II) complexes in the presence of selected metal ions have been observed. The nature of the host-guest interactions has been examined by quantitative binding studies, mass spectrometry and DFT calculations, and through comparisons with control complexes.

Shape-persistent (Pt-salphen)2 phosphorescent coordination frameworks: structural insights and selective perturbations.

The development of molecular frameworks derived from binuclear platinum(II) aromatic Schiff base (salphen) complexes and their supramolecular chemistry have been undertaken. A series of axially rotating (Pt-salphen)2 luminophores, tethered in a cofacial manner by a rigid linker (xanthene, 1; dibenzofuran, 2; biphenylene, 3), was synthesized in which the O(salphen) groups are potentially amenable for guest-binding. The molecular structures of 1 and 3 have been determined by X-ray crystallography, revealing intra- and intermolecular π-stacking interactions, as well as contrasting syn (1) and anti (3) configurations, for the (Pt-salphen)2 moiety. All complexes are luminescent in solution at room temperature. Their photophysical and solvatochromic properties have been examined, and the emissions are assigned to mixed triplet O(p)/Pt(d)→π*(diimine) excited states. The red-shifted fluid emissions and lower quantum yields of 1 and 3, relative to 2, are ascribed to enhanced intramolecular π-stacking interactions. Photophysical changes and selective responses to metal ions (particularly Pb(2+)) have been investigated by using various spectroscopic methods and DFT calculations, and through comparative studies with control complexes. A plausible binding mechanism is proposed based on occupation of the O(salphen)-binding cavity, which induces perturbation of intramolecular π-π interactions, and hence the self-quenching and emission properties, of the (Pt-salphen)2 unit.

Attractive interactions in olefin polymerization mediated by post-metallocene catalysts with fluorine-containing ancillary ligands

The deployment of fluorinated moieties to engender electronic effects through non-covalent attractive interactions is a new concept for olefin polymerization catalysts, and was proposed to account for the unprecedented living polymerization mediated by certain catalysts bearing fluorine-containing ancillary ligands. This strategy is distinct from conventional approaches based on steric influences to control olefin polymerization processes. In this perspective, the concept, generality and beneficial effects of applying non-covalent interactions to control polymerization reactions are discussed, with particular emphasis given to intramolecular C–H⋯F–C interactions between a fluorinated ligand and growing polymer chain.

Scalar Coupling Across [CH⋅⋅⋅FC] Interactions in (σ‐Aryl)‐Chelating Post‐Metallocenes

The nature and importance of C-H···F-C interactions is a topical yet controversial issue, and the development of spectroscopic methods to probe such contacts is therefore warranted. A series of Group 4 bis(benzyl) complexes supported by (σ-aryl)-2-phenolate-6-pyridyl [O,C,N-R(1)] ligands bearing a fluorinated R(1) group (CF(3) or F) in the vicinity of the metal has been prepared. The X-ray crystal structure of the CF(3)-substituted Hf derivative features intramolecular C-H···F-C and Hf···F-C contacts. All complexes have been characterized by multinuclear NMR spectroscopy. The (1)H and (13)C NMR spectra of [M(O,C,N-CF(3))(CH(2)Ph)(2)] derivatives display coupling (assigned to (1h)J(HF) and (2h)J(CF) for Ti; (3)J(HF) and (2)J(CF) (through M···F) for Hf and Zr) between the benzyl CH(2) and CF(3) moieties. [(1)H,(19)F]-HMBC NMR experiments have been performed for the M-[O,C,N-R(1)] complexes and their [O,N,C] counterparts, revealing significant scalar coupling across the C-H···F-C interactions for Ti-[O,C,N] and [O,N,C] species.

Topologically diverse shape-persistent bis-(Zn–salphen) catalysts: efficient cyclic carbonate formation under mild conditions

By adopting a shape-persistent bimetallic design approach, high initial molecular turnover frequencies (up to 14,800 h(-1)) for coupling of CO2 with epoxides in conjunction with (n)Bu4NI, plus excellent yields under mild conditions (1 bar of CO2, 45 °C) have been achieved for catalysts containing cofacial Zn-salphen units.

Chelating σ-Aryl Post-Metallocenes: Probing Intramolecular [C-H···F-C] Interactions and Unusual Reaction Pathways.

Our interest in chelating σ-aryl ancillary ligands was motivated by their potential to impart unusual reactivity, since we envisioned that σ-donors with minimal π-donation would create a catalytic center with enhanced electrophilicity. We developed a family of Group 4 post-metallocene catalysts supported by pyridine-2-phenolate-6-(σ-aryl) [O,N,C] ligands bearing a fluorinated moiety in the vicinity of the metal. Notable features of these meta-substituted tris(hetero)aryl frameworks include their coordination geometry and inherent rigidity. For the first time, the elusive C-H···F-C interaction was manifested as NMR-discernible (1)H-(19)F coupling in solution and characterized by a neutron diffraction study. Their existence carries implications for catalyst design and in the context of weak attractive ligand-polymer interactions (WALPI), since they substantiate the practical viability of the ortho-F···H(β) ligand-polymer interactions proposed for living Group 4 fluorinated bis(phenoxyimine) catalysts. In metal-catalyzed olefin polymerization reactions, the notion of noncovalent interactions between an active ancillary ligand and the growing polymer chain is new. These interactions must be fragile and transient in nature, otherwise the intrinsic chain propagation process would be disrupted, and inherently tunable attractive forces such as hydrogen bonds are ideally suited to this role. The nature, relevance, and usability of extremely weak hydrogen bonds such as C-H···F-C has been a topical yet controversial area of research. We subsequently prepared a series of Group 4 complexes supported by fluorinated (σ-aryl)-2-phenolate-6-pyridyl [O,C,N] ligands. [(1)H,(19)F]-HMBC NMR experiments were conducted to probe the observed (1)H-(19)F coupling, and specifically separate contributions from scalar (J) coupling and cross-correlation (CR) interference. For the first time, a significant scalar component was confirmed for the (1)H-(19)F coupling in Ti-[O,C,N] and [O,N,C] complexes, which occurs with chemical connectivity across intramolecular C-H···F-C interactions. This result is important because the applicability of weak attractive ligand-polymer interactions in catalysis is feasible only if the observed coupling and hence the noncovalent interaction is genuine. The verified intramolecular C-H···F-C contacts in these complexes can therefore be considered as synthetic models for ligand-polymer interactions in olefin polymerization processes. Significantly, reports concerning late transition metal systems have appeared that hint at the generality of the WALPI concept for modulating polymerization reactions. We evaluated the olefin polymerization reactivity of Ti-[O,N,C] catalysts through judicious substitution. DFT calculations, which revealed diverse kinetically competitive reaction pathways and active sites (including unusual ethylene-assimilated species) in addition to normal chain propagation, were also employed to rationalize polymerization efficiencies. Further developments in catalytic applications of multidentate σ-aryl ligand systems and novel reactivity of the corresponding complexes can be envisaged.

Luminescent oligo(ethylene glycol)-functionalized cyclometalated platinum(II) complexes: cellular characterization and mitochondria-specific localization

A readily tunable series of non-planar oligo(ethylene glycol)-substituted phosphorescent Pt(II) complexes has been investigated as live cell imaging agents; suitable structural modifications can give good cellular uptake, traceable mitochondria-specific localization and potent cytotoxic characteristics towards HeLa cells.

Polystyrene supports for vanadium ethylene polymerisation catalysts

Amino-functionalised polystyrene resins have been synthesised and used as well-defined supports for imidovanadium ethylene polymerisation catalysts; a dramatic enhancement in the lifetime and productivity of the supported catalysts compared to their unsupported (homogeneous) analogues is found.

Novel µ-methyl complexes of vanadium and their relevance to bimolecular deactivation of homogeneous imidovanadium polymerisation catalysts

Attempted dimethylation of [CpV(NC6H3Pri2-2,6)]Cl2 using Grignard reagents affords novel µ-methyl complexes arising by reductive dimerisation; the structure of one of these products, [CpV(NC6H3Pri2-2,6)(µ-Me)2]2(µ-Mg) 2, reveals V–(µ-Me)–Mg, V–Mg, N–Mg and C–H···Mg interactions.

Effects of the [OC6F5] moiety upon structural geometry: crystal structures of half-sandwich tantalum(V) aryloxide complexes from reaction of Cp*Ta(NtBu)(CH2R)2 with pentafluorophenol

The synthesis, chemical and structural characterization of a series of pentamethylcyclopentadienyl (Cp*) tantalum imido complexes and aryloxide derivatives are presented. Specifically, the imido complexes Cp*Ta(N(t)Bu)(CH(2)R)(2), where R = Ph [dibenzyl(tert-butylamido) (η(5)-pentamethylcyclopentadienyl)tantalum(IV) (1)], Me(2)Ph [tert-butylamido)bis(2-methyl-2-phenylpropyl) (η(5)-pentamethylcyclopentadienyl)tantalum(IV) (2)], CMe(3) [(tert-butylamido)bis(2,2-dimethylpropyl) (η(5)-pentamethylcyclopentadienyl)tantalum(IV) (3)], are reported. The crystal structure of (3) reveals α-agostic interactions with the Ta atom. The resulting increase in the tantalum core coordination improves electronic stability. As such it does not react with pentafluorophenol, in contrast to the other two reported imido complexes [(1) and (2)]. Addition of C(6)F(5)OH to (1) yields a dimeric aryl-oxide derivative, [Cp*Ta(CH(2)Ph)(OC(6)H(5))(μ-O)](2) [di-μ-oxido-bis[benzyl(pentafluorophenolato) (η(5)-pentamethylcyclopentadienyl)tantalum(V)] (4)]. Its crystal structure reveals long Ta-O(C(6)H(5)) bonds but short oxo-bridging Ta-O bonds. This is explained by accounting for the fierce electronic competition for the vacant d(π) orbitals of the electrophilic Ta(V) centre. Steric congestion around each metal is alleviated by a large twist angle (77.1°) between the benzyl and pentafluorophenyl ligands and the ordering of each of these groups into stacked pairs. The imido complex (2) reacts with C(6)F(5)OH to produce a mixture of Cp*Ta(OC(6)F(5))(4) [tetrakis(pentafluorophenolato)(η(5)-pentamethylcyclopentadienyl)tantalum(V) (5)] and [Cp*Ta(OC(6)F(5))(2)(μ-O)](2) [di-μ-oxido-bis[bis(pentafluorophenolato)(η(5)-pentamethylcyclopentadienyl)tantalum(V)] (6)]. Steric congestion is offset in both cases by the twisting of its pentafluorophenyl ligands. Particularly strong electronic competition for the empty d(π) metal orbitals in (6) is reflected in its bond geometry, and owes itself to the more numerous electron-withdrawing pentafluorophenyl ligands. The balance of steric and electronic factors affecting the reactivity of Cp* tantalum imido based complexes with pentafluorophenol is therefore addressed.