Heterofunctionalization catalysis with organometallic complexes of calcium, strontium and barium by Anthony G. M. Barrett, Mark R. Crimmin, Michael S. Hill, and Panayiotis A. Procopiou Proceedings A Volume ():rspa January 25, 2010 ©2010 by The Royal Society

(a) Fundamental reactions of trivalent lanthanide organometallics: (i) σ-bond metathesis and (ii) insertion of unsaturated substrates into M–X2 σ-bonds. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

The Schlenk equilibrium of heavier Group II complexes. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

Selected examples of well-defined, kinetically stabilized, heteroleptic heavier Group II complexes. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

Calcium-mediated stereocontrolled polymerization of rac-lactide. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

Reaction scope of calcium and magnesium mediated intramolecular hydroamination of aminoalkenes. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

Diastereoselectivity in the intramolecular hydroamination of pro-chiral aminoalkenes. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

(a) Reaction of pre-catalysts 1 and 2 with primary amines. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

Proposed mechanism of Group II mediated hydroamination of aminoalkenes with (a) non- reversible and (b) reversible pre-catalyst generation. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

Aminotroponate, aminotropiniminate, bis(imidazolin-2-ylidene-1-yl)borate, tris (imi- dazolin-2- ylidene-1-yl)borate and triazenide supported Group II pre-catalysts for intramolecular hydroamination. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

Scope of hydroamination catalysis with complexes 3–9 and 11–12. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

Side-by-side comparison of reaction conditions for the intramolecular cyclization of 1-amino-2,2- diphenyl-4-pentene. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

Intermolecular hydroamination mediated by Group II complexes. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

Proposed transition states to C–N bond formation in the anti-Markovnikov hydroamination of styrenes. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

Free energy profiles for the reaction of ethylene with ammonia catalysed by [{HNC(Me)CHC(Me)NH}M(NH2)]. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

Electron density difference maps for the alkene insertion (a) transition state and (b) intermediate for the Mg-mediated cycle. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

Insertion of 1,3-dialkyl carbodiimides into the Ca–N bonds of derivatives of 1. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

Scope of Group II mediated hydroamination of carbodiimides. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

(a) Proposed mechanism of the Group II mediated hydroamination of carbodiimides and (b) ORTEP representation of 13 thermal ellipsoids at 40% probability; H atoms are omitted for clarity. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

Group II catalysed addition of diphenylamine to isocyanates. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

(a) Proposed mechanism of the Group II catalysed addition of diphenylamine to isocyanates. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

Scope of alkene and alkyne hydrophosphination mediated by 1. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

Explanation for the observed regiochemistry in the Group II mediated hydrophos- phination of styrenes. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

(a) Proposed mechanism of the hydrophosphination of diphenylacetylene catalysed by 1 and (b) ORTEP representation of 15 thermal ellipsoids at 20% probability; H atoms are omitted for clarity. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

Hydrophosphination of diphenylacetylene and 1,4-diphenylbutadiyne catalysed by [Ca{PPh2}2(THF)4]. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

Group II mediated hydrophosphination of carbodiimides. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

(a) Proposed mechanism of Group II mediated hydrophosphination of carbodiimides. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

Scope of Group II mediated hydrosilylation of alkenes and dienes. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

Reaction of 1 with PhSiH3 to yield the molecular hydride 17. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

Proposed mechanisms of the Group II mediated hydrosilylation of alkenes. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

Group II catalysed hydrosilylation of ketones. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

Reaction scope of the calcium-mediated hydrogenation of activated alkenes. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society

(a) Proposed mechanism for the Group II mediated hydrogenation of alkenes. Anthony G. M. Barrett et al. Proc. R. Soc. A doi: /rspa ©2010 by The Royal Society