Highly Efficient Rh(I) Homo- and Heterogeneous Catalysts for C-N Couplings via Hydrogen Borrowing.

Rhodium(I) complexes were explored as catalysts for the hydrogen borrowing reactions of amines and alcohols. Bidentate carbene-triazole ligands were readily synthesized via "click" reactions which allowed a diversity of ligand backbones to be accessed. The catalytic transformations are highly efficient, able to reach completion in under 6 h, and promote C-N bond formation across a range of primary alcohol and amine substrates. Moreover, site-selective catalysis can be achieved using substrates with more than one reactive site. A rhodium(I) complex covalently attached to a carbon black surface was also deployed in the hydrogen borrowing coupling reaction of aniline with benzyl alcohol. This represents the first report of a heterogeneous rhodium catalyst used for hydrogen borrowing.

Bi- and tri-metallic Rh and Ir complexes containing click derived bis- and tris-(pyrazolyl-1,2,3-triazolyl) N-N' donor ligands and their application as catalysts for the dihydroalkoxylation of alkynes.

A series of bi-topic and tri-topic pyrazolyl-1,2,3-triazolyl donor ligands (; = 1,X-bis((4-((1H-pyrazol-1-yl)methyl)-1H-1,2,3-triazol-1-yl)methyl)benzene (X = 2, 3 and 4; o-C6H4(PyT)2, m-C6H4(PyT)2 and p-C6H4(PyT)2) and = 1,3,5-tris((4-((1H-pyrazol-1-yl)methyl)-1H-1,2,3-triazol-1-yl)methyl)benzene, 1,3,5-C6H3(PyT)3) were conveniently synthesised in 'one pot' reactions using the Cu(i) catalysed 'click' reaction. Rh(i), Ir(i), Rh(iii) and Ir(iii) complexes with ligands of the general formulae C6H6-n[(PyT)M(CO)2]n[BAr]n (M = Rh, Ir; n = 2, 3; ; ) and C6H6-n[(PyT)MCp*Cl]n[BAr]n (M = Rh, Ir; n = 2, 3; ; ) were synthesised and fully characterised. In solution each of the bi- or tri-metallic complexes and exists as a mixture of two (, ) or three ( and ) diastereomers due to the presence of a chiral centre at each metal centre in these complexes. The solid state structures of complexes and were determined by single crystal X-ray crystallography and showed that each bidentate arm of these multitopic ligands coordinates to the Rh or Ir centre in a bidentate fashion via the pyrazolyl-N2 and 1,2,3-triazolyl N3' donors. The intermetallic distances in these solid state structures vary from 8.66 Å to 15.17 Å. These complexes were assessed as catalysts for the dihydroalkoxylation of alkynes using the cyclisation of 2-(5-hydroxypent-1-ynyl)benzyl alcohol, , to a mixture of two spiroketals, 2,3,4,5-tetrahydro-spirol[furan-2,3'-isochroman], , and 3',4',5',6'-tetrahydro-spiro[isobenzofuran-1(3H),2'(2H)pyran], , as the model reaction. The Rh(i) complexes (), with the highest TOF of 2052 h(-1) for complex , were the most active catalysts when compared with the other complexes under investigation here. The Ir(i) complexes () were moderately active as catalysts for the same transformation. No significant enhancement in catalytic reactivity was observed with the Rh(i) series bi- and trimetallic complexes () when compared with their monometallic analogues. The bi- and trimetallic Ir(i) complexes () were much more efficient as catalysts for this transformation than their monometallic analogues, suggesting some intermetallic cooperativity. Rh(iii), , and Ir(iii), , complexes were not active as catalysts for this transformation.

Comparison of three methods for cyclosporine area under the curve monitoring calculations.

A method of therapeutic monitoring of cyclosporine by using area under the curve (AUC) has been previously proposed. However, different mathematical methods of calculating AUC may produce different results. We compared three methods of calculating whole blood 12-h AUC of cyclosporine A (CsA) at steady state in 16 pediatric renal allograft recipients. The linear trapezoidal method tended to significantly overestimate AUC when compared with a method combining linear and log trapezoidal methods, or the Lagrange technique combined with the logarithmic trapezoidal method, producing mean differences of 13.8 ng*h/ml [95% confidence interval (CI), 7.3-20.3] and 12.8 ng*h/ml [95% CI, 7.3-18.3], respectively. However, these differences appear to be of little clinical significance because they comprised < 1% of the calculated AUC value. The calculated AUCs by the three methods produced values with similar means and overlapping 95% CI. These data suggest that use of any of these three mathematical methods, when used to calculate CsA AUC for the determination of average steady-state concentrations and dose rate calculations, will produce similar results.