Nathan D. Jones

Homo- and Heterobimetallic Precursor Catalysts for the Heck Reaction, and a Proposal for a General Catalytic Cooperativity Index

Homo- (Pd2) and heterobimetallic (PtPd) complexes supported by a P,P-bridging, bis(P,N-chelating) coordination mode of the potentially hexadentate ligand 1,1-bis[di(o-N,N-dimethylanilinyl)phosphino]methane (dmapm) are effective catalyst precursors for the aerobic Heck coupling of iodobenzene and styrene at 100 °C in DMF/H2O solution containing K2CO3. This medium allows for trivial separation of the trans-stilbene product which precipitates after the reaction mixture is cooled. The bimetallic precursors are more active than predicted from the sum of the activities of complexes chosen to mimic their mono-metallic “half units,” suggesting some degree of intermetallic cooperativity during the reaction. A non-linear dependence of initial rate on catalyst concentration implies, however, that the complexes do not remain intact, and may be involved in dissociative equilibria with non-dmapm containing monometallic components that are more active species for the Heck coupling. The complexes are slowly degraded by oxidation at a phosphorus centre. A general index for quantifying the degree of intermetallic cooperativity during a catalytic cycle is proposed and its utility and limitations are discussed.

Synthesis, reactivity, and computational analysis of halophosphines supported by dianionic guanidinate ligands.

The reported chemistry and reactivity of guanidinate supported group 15 elements in the +3 oxidation state, particularly phosphorus, is limited when compared to their ubiquity in supporting metallic elements across the periodic table. We have synthesized a series of chlorophosphines utilizing homo- and heteroleptic (dianionic)guanidinates and have completed a comprehensive study of their reactivity. Most notable is the reluctancy of these four-membered rings to form the corresponding N-heterocyclic phosphenium cations, the tendency to chemically and thermally eliminate carbodiimide, and the scarcely observed ring expansion by insertion of a chloro(imino)phosphine into a P-N bond of the P-N-C-N framework. Computational analysis has provided corroborating evidence for the unwillingness of the halide abstraction reaction by demonstrating the exceptional electron acceptor properties of the target phosphenium cations and the underscoring strength of the P-X bond.

Synthesis, Structure, Electrochemistry, and Electrochemiluminescence of Thienyltriazoles

Four blue-emitting thienyltriazoles with desired N and O coordination atoms were prepared in high yield via click chemistry for potential incorporation into metal complexes. Three of their crystal structures were determined by X-ray crystallography. The electrochemical properties, electronic structures of these thienyltriazoles, 1-4, and their correlations were studied using cyclic voltammetry and differential pulse voltammetry techniques along with density function theory (DFT) calculations. All of the compounds underwent irreversible redox reactions, leading to unstable electrogenerated radical cations and anions. Electrochemical gaps determined from the differences between first formal reduction and oxidation reactions were correlated to HOMO-LUMO energy gaps obtained from UV-vis spectroscopy and the DFT calculations as well as energies of excited states measured from photoluminescence spectroscopy. We observed weak electrochemiluminescence (ECL) from annihilation of these thienyltriazole radicals in acetonitrile containing 0.1 M tetra-n-butylammonium perchlorate as electrolyte. An enhancement in ECL efficiency ranging from 0.16 to 0.50% was observed upon addition of benzoyl peroxide as a coreactant in the above electrolyte solutions. The generation of excimers in solutions of 1-4 was observed as seen by the red-shift in ECL maxima relative to their corresponding photoluminescence peak wavelengths. Our work is of importance for the development of efficient blue-emitting fluorophores via click chemistry that could be potential luminophores in metal complexes.

An N-Heterocyclic Carbene Containing a Bithiophene Backbone: Synthesis and Coordination Chemistry

A new N-heterocyclic carbene (NHC) containing a fused bithiophene backbone has been synthesized along with its silver(I) and BPh(3) complexes. The donor strength of this unique NHC has been determined from the IR stretching frequencies of the isolated NHC-Rh(CO)(2)Cl complex. The photophysical properties of all of the novel compounds have been investigated and are presented.

Group 15 pnictenium cations supported by a conjugated bithiophene backbone.

Thiophene based polymers and oligomers have attracted considerable attention because they can be functionalized to alter the gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), which enables the design of tunable light emitting materials. One area, which has been less explored, is the incorporation of low coordinate, low oxidation state main group elements into these systems. We have currently developed a novel π-conjugated ligand containing two contiguous thiophene rings in which we have demonstrated its ability to support both pnictogen cations and their metal complexes.

Platinum(II)-Silver(I) Polymers Bearing Platinum(II) Clusters Containing Chelated P,P- and Bridged P, N-2-Pyridylphosphine Ligands

Reactions PtI2L (L = P,P-bonded 1,2-bis ((2-pyridyl)phosphino(ethane, d(py)pe, or 1,2-bis ((2-pyridyl)phosphino)cyclopentane, d(py)pcp) with excess AgNO3 in acetic acid/ethanol afford the polymers [Pt2(d(py)pe)2Ag4(NO3)8(H2O)2]n(1 ) and [Pt2(d(py)pcp)2Ag6(NO3)10]n (2), respectively, which contain Pt2L24+ cores with each L ligand nowP,N-bridging two Pt-atoms; these Pt2 cores are connected via bridging AgNO3 clusters, the Ag being bound to the pyridyl-N or nitrate-O atoms. X-ray crystallographic data reveal Pt–Pt contacts of ∼2.76 Å indicative of bonding.

Potassium tetracyanoplatinate (II) trihydrate (K2Pt(CN)4·3H2O) studied by high resolution solid state 13C MAS NMR

Prudent analysis of the solid state 13C MAS NMR spectra of polycrystalline K2Pt(CN)4 x 3H2O (KTCP)- reveals that in crystals of this compound there are two types of carbon nuclei with slightly different 13C chemical shift tensors, contrary to what is found for the solution NMR spectrum and previous static powder NMR studies on this compound and the high resolution solid state NMR studies on other similar compounds. The 13C MAS spectra measured at different rotor spinning speeds are satisfactorily simulated though the use of a newly developed computer program based on a novel density matrix formulation. The present method is eminently successful even though the spectra are rather complicated because of (1) the relatively large anisotropies of the chemical shift tensors; (2) the high-order dipolar interactions between 13C and 14N nuclei because of the strong quadrupolar coupling constants of 14N nuclei; and (3) the indirect J-coupling between the 13C and 195Pt. The principal elements as well as their orientations of the two 13C chemical shift tensors are evaluated from the spectral simulations.

Diastereoselective formation of a dipalladium(I) complex supported by a bridging tetradentate ligand, and oxidative addition of RS–H across a phosphine-bridged PdI–PdI bond

The ligand CH2(P(o-C6H4NMe2)2)2 (dmapm) gives access to the first example of a dipalladium(I) complex supported by a tetradentate ligand, Pd2Cl2(mu-N,P,P,N-dmapm), which, unlike the well-known Pd2X2(mu-dppm)2 complexes (X = halide, dppm = bis(diphenylphosphino)methane), reacts with thiols to give addition of RS-H across a phosphine-bridged Pd-Pd bond.