A series of enantiopure MOP-phosphonite ligands, with tailored steric profiles, have been synthesised and are proven to be very successful in high-yielding, regio- and enantioselective catalytic hydrosilylation reactions of substituted styrenes, affording important chiral secondary alcohols.

A fluorescent tridentate phosphine, BodP3 (2), forms rhenium complexes which effectively image cancer cells. Related technetium analogues are also readily prepared and have potential as dual SPECT/fluorescent biological probes.

The syntheses of highly fluorescent analogues of PPh3 and PhPCy2 based on the Bodipy chromophore are described. The ligands have been incorporated into two- to four-coordinate group 11 metal complexes. The synthesis, characterisation and photophysical properties of the novel ligands and their metal complexes are reported; many of these compounds have also been characterised by single-crystal X-ray diffraction. Incorporation of the phosphino group and complexation to the group 11 metal centre has little effect on the absorption and emission profiles; high molar extinction coefficients and fluorescence quantum yields were still obtained. In particular, incorporation of the dicyclohexylphosphino substituent significantly increases the quantum yields relative to the parent dyes.

The air-stable chiral primary phosphines 1a,b facilitate the synthesis of previously inaccessible or hard-to-access chiral MOP-type ligands 2a,b–5a,b, which can be prepared in one-pot reactions. These derivatives have been prepared to allow for a unique comparison of their differing structural and electronic profiles, determined here by a number of experimental and theoretical studies. Phosphiranes 2a,b and phosphonites 5a,b are electron-poor compounds, with the former possessing exceptional thermal stability. Conversely, the dimethylarylphosphines 3a,b and bis(dimethylamino)arylphosphines 4a,b are good electron donors, and, in contrast to earlier reports, the dialkylarylphosphines were found to be remarkably air-stable. The ligands were coordinated to platinum(II), and the weak trans-influence of the highly strained phosphiranes 2a,b was revealed both in solution and in the solid state. The steric parameters of the ligands were investigated by the allyl rotation of their methallylpalladium(II) complexes, which showed subtle differences in exchange rates. Aryl side-on coordination of the MOP-backbone to palladium(II) was observed for complexes with a non-coordinating counterion and structurally analyzed in the case of ligand 4b. The asymmetric induction and catalytic activity of 2a,b–5a,b were tested in the hydrosilylation of styrene as well as the allylic alkylation of (rac)-(E)-1,3-diphenylallyl acetate. Major differences in reactivity were related back to the electronic parameters of the ligands.

The synthesis of rhodium(I) and iridium(I) complexes of chiral MOP-phosphonite ligands is reported. The full characterisation of η1,η6-(σ-P, π-arene) chelated 18VE rhodium(I) complexes reveals hemilabile binding on the arene which has been quantitatively analysed.

Chiral phosphonite ligands (S,Rb)-5a, (S,Sb)-5b, (R,Rb)-6a and (R,Sb)-6b are introduced, comprising a MOP-type backbone with a binol-based binaphthyl group bound to the phosphorus. Their reaction with [Pd(η3-C4H7)Cl]2 affords η3-methallylpalladium chloride complexes 7a/b and 8a/b which have been isolated and structurally characterised. Solid-state and solution studies indicate subtle differences in their coordination behaviour, which ultimately affects their efficacy in the asymmetric hydrosilylation of styrene.

Enantiopure chiral phosphiranes possessing a binaphthyl backbone demonstrate remarkable thermal stability, are highly resistant to air-oxidation and are effective ligands in catalytic asymmetric hydrosilylations.

DFT calculations form the basis of a model capable of predicting the air stability of phosphines. The sensitivity of 18 primary phosphines is accounted for; the model also predicts the trend of increasing stability from phenylphosphine to triphenylphosphine. There is evidence that the radical cation SOMO energy for each corresponding phosphine may be key to its air stability/sensitivity.

The synthesis of rhodium(I) and iridium(I) complexes of chiral MOP-phosphonite ligands is reported. The full characterisation of η1,η6-(σ-P, π-arene) chelated 18VE rhodium(I) complexes reveals hemilabile binding on the arene which has been quantitatively analysed.

Enantiopure chiral phosphiranes possessing a binaphthyl backbone demonstrate remarkable thermal stability, are highly resistant to air-oxidation and are effective ligands in catalytic asymmetric hydrosilylations.

Six chiral MOP-phosphonites have been synthesised and compared via experimental and computational methods in an effort to quantify their differing structural and electronic profiles. They were found to be electron-poor ligands in comparison to their arylphosphine analogues and have a larger trans influence in square planar Pt(II) complexes. Four [Rh(LP)(η2:η2-cod)Cl] complexes were synthesised and characterised by NMR, HRMS and X-ray crystallography. Two [Rh(LP)2]BF4 complexes were prepared where one ligand acts as a chelating P,C-π-donor; detailed NMR studies demonstrated a hemilabile η6-coordination mode, which in one case was confirmed by X-ray crystallography. Rh(I) complexes were used as catalysts in asymmetric hydrogenation and hydroformylation reactions and in the addition of phenyl boronic acid to an isatin. Pd(II) complexes were successfully employed in asymmetric Suzuki–Miyaura cross-coupling reactions yielding binaphthyl products. Two [Pd(LP)2Cl2] complexes were synthesised and characterised by X-ray crystallography, both adopting cis orientations, with one of the complexes crystallising as two pseudo-polymorphs.

A series of enantiopure MOP-phosphonite ligands, with tailored steric profiles, have been synthesised and are proven to be very successful in high-yielding, regio- and enantioselective catalytic hydrosilylation reactions of substituted styrenes, affording important chiral secondary alcohols.

Chiral phosphonite ligands (S,Rb)-5a, (S,Sb)-5b, (R,Rb)-6a and (R,Sb)-6b are introduced, comprising a MOP-type backbone with a binol-based binaphthyl group bound to the phosphorus. Their reaction with [Pd(η3-C4H7)Cl]2 affords η3-methallylpalladium chloride complexes 7a/b and 8a/b which have been isolated and structurally characterised. Solid-state and solution studies indicate subtle differences in their coordination behaviour, which ultimately affects their efficacy in the asymmetric hydrosilylation of styrene.

The syntheses of highly fluorescent analogues of PPh3 and PhPCy2 based on the Bodipy chromophore are described. The ligands have been incorporated into two- to four-coordinate group 11 metal complexes. The synthesis, characterisation and photophysical properties of the novel ligands and their metal complexes are reported; many of these compounds have also been characterised by single-crystal X-ray diffraction. Incorporation of the phosphino group and complexation to the group 11 metal centre has little effect on the absorption and emission profiles; high molar extinction coefficients and fluorescence quantum yields were still obtained. In particular, incorporation of the dicyclohexylphosphino substituent significantly increases the quantum yields relative to the parent dyes.

A fluorescent tridentate phosphine, BodP3 (2), forms rhenium complexes which effectively image cancer cells. Related technetium analogues are also readily prepared and have potential as dual SPECT/fluorescent biological probes.