Synthesis and Oligonuclear Structures of Strontium and Barium Complexes with Protonated and Deprotonated N-Mesityl-P,P-diphenylphosphinic Amide Ligands.

Metalation of N-mesityl-P,P-diphenylphosphinic amide Ph2P(O)-NHMes (HL, I) with MgBu2 and Ae{N(SiMe3)2}2 (Ae = Ca, Sr, and Ba) yields alkaline-earth metal complexes with the compositions of [(thf)nAe(L·HL)2] [Ae/n = Mg/0 (II), Ca/2 (III)] as well as of [Sr2L3(L·HL)(HL)] (1), [Ba2L3(L·HL)(HL)] (2), [Ba3L6] (3), and [(thf)2Ba3L6] (4). In III, 1, 2, and 3, the alkaline-earth metal atoms are in severely distorted octahedral environments, and the structural distortions are partially caused by the small O-Ae-N bite angles of the chelating Ph2P(O)-NMes anions. The substructures (L·HL) contain N-H···N hydrogen bridges, stabilizing the arrangement of the ligands in complexes II, III, 1, and 2. In the trinuclear barium complex [Ba(μ-L)3Ba(μ-L)3Ba] (3), a rigid adjustment of the anionic L bases leads to a C3-symmetric molecule in the crystalline state with bridging oxygen atoms. Due to the small O-Ba-N bite angles of the chelating anions, vacant coordination sites are available at the outer barium centers. Coordination of thf bases in these gaps yields the complex [(thf)Ba(μ-L)3Ba(μ-L)3Ba(thf)] (4). However, THF is unable to deaggregate the trinuclear complexes into smaller barium-containing moieties. Increasing the radius of the alkaline-earth metals and increasing the nuclearity of these compounds lead to decreasing solubility in common organic solvents. NMR studies verify that the molecular structures of these alkaline-earth metal complexes are maintained in ethereal solvents and toluene.