2D copper(II) complex built from N-methyl-1,3-diamino-2-propanolate and azide ligands: structure, magnetic, and DFT studies.

The synthesis, structural characterization, and magnetic behavior of a new 2D copper(II) compound with formula {[Cu2(mu-O2CMe)(mu-MedapO)(mu1,1-N3)2]n (CH3OH)n} 1, in which MedapOH is N-methyl-1,3-diamino-2-propanol is reported herein. 1 crystallizes in the triclinic system, space group P1, with unit cell parameters a = 6.688(5) A, b = 10.591(6) A, c = 12.100(7) A, alpha = 113.01(3) degrees, beta = 105.08(4) degrees, gamma = 93.93(3) degrees, Z = 2. The structure of 1 consists of neutral alternate 1D chains formed by the sequence of [Cu(1)-(mu1,1-N3)2-Cu(1)-(MedapO/acetate)-Cu(2)-(mu1,1-N3)2-Cu2)]. Each dinuclear [Cu(1)-Cu(2)] unit interacts with similar dinuclear units of neighbor chains in basis to large Cu-N(azido) distances to give a 2D arrangement. The magnetic behavior of 1 has been checked giving a net ferromagnetic coupling. The fit of the chiM versus T data as dinuclear compound affords a J value of 53.0 cm(-1) as a consequence of the orbital countercomplementarity phenomenon. The exchange pathways have been justified by density functional calculations.

A modular design of ruthenium catalysts with diamine and BINOL-derived phosphinite ligands that are enantiomerically-matched for the effective asymmetric transfer hydrogenation of simple ketones.

A method is reported for making a potentially very wide series of ruthenium hydrido chloro complexes with diamine and readily-prepared diphosphinite ligand modules as precatalysts for the asymmetric transfer hydrogenation of simple ketones to give chiral alcohols in good yield and enantioselectivity.

Applications of ruthenium hydride borohydride complexes containing phosphinite and diamine ligands to asymmetric catalytic reactions.

[reaction: see text] A series of novel trans-ruthenium hydride borohydride complexes with chiral phosphinite and diamine ligands were synthesized. They can be used in the asymmetric transfer hydrogenation of aryl ketones, including base-sensitive ones, to give chiral alcohols in moderate to good enantioselectivities (up to 94% ee). They are also efficient catalysts for the Michael addition of malonates to enones with enantioselectivities of up to 90%. This kind of catalyst allows a one-pot tandem Michael addition/H(2) hydrogenation protocol to build structures with multiple chiral centers.