Novel Layered Ruthenium Diphosphonate Containing a Mixed Valent Diruthenium Paddlewheel Core

Abstract

This paper reports the synthesis and crystal structure of a novel mixed valence ruthenium(II,III) compound, (NH(4))(3)Ru(2)(hedp)(2).2H(2)O (1), where hedp represents 1-hydroxyethylidenediphosphonate. It has a two-dimensional structure in which the paddlewheel diruthenium(II,III) units of Ru(2)(hedp)(2) are cross-linked through the phosphonate groups. The layers are stacked along the [100] direction with strong intra- and interlayer hydrogen bonds. Primary magnetic results are presented.

Ruthenium Compounds

“…85 It exhibits a two-dimensional layer structure similar to those of K 3 [Ru 2 (O 2 CO) 4 ]·4H 2 O and Na 3 [Ru 2 (O 2 CO) 4 ]·6H 2 O, with a Ru-Ru bond length of 2.347(1) Å (Table 9.1). This distance is much longer than the distances for most Ru 2 5+ compounds, due to the larger "bite" of the phosphonate ligands.…”

Metal phosphonates incorporating metalloligands: assembly, structures and properties

“…19 The Ru 2 -diphosphonate system has superiority over carbonate because the organic groups of the phosphonate ligand can be modified with additional functions. In 2003, we reported the first example of metal phosphonates with extended structures which contain a diruthenium diphosphonate paddlewheel core, (NH 4 ) 3 Ru 2 (hedp) 2 Á2H 2 O (1), 20 and Ln III ions, the significant structural difference between 3-4 and 5-15 originates from the slight difference in the geometry of {LnOp 4 Ow 4 } polyhedra. In particular, the geometry of {LnOp 4 } is essential in determining the topology of the final products, which is a distorted square plane in 3-4, but closer to a distorted tetrahedron in 5-15.…”

Structural study of metal complexes of bisphosphonate amide ester: copper, magnesium, zinc and cadmium complexes of (dichloromethylene)bisphosphonic acid P-piperidinium-P′-methyl ester

“…[14][15][16][17] One paddle-wheel structure of a bisphosphonate has been reported. 18 Clodronate, (dichloromethylene)bisphosphonate, Cl 2 MBP, is one of the best-documented bisphosphonates since it is widely used in therapeutics. 19 Recently, several metal complexes of clodronate and its symmetrical dialkyl ester derivatives have been prepared to permit an evaluation of the properties of these solid materials.…”