Crystal Structure of (2,2'-Bipyridine-N,N')(diphenyl-2-phosphinopyridine-P)-chloro(dicarbonyl)ruthenium(II) Hexafluorophosphate

Abstract

The chemistry of polynuclear metal complexes including various bridging ligands has been widely developed for many years. 1 In particular, the diphenyl-2-phosphinopyridine (dppy) ligand has been used to construct hetero-binuclear metal complexes due to its possessing both the soft (P) and hard (N) donor atoms. 2In this work, an X-ray structural analysis of [Ru(bpy)(dppy)(CO)2Cl] + (bpy = 2,2′-bipyridine), which is a precursor for constructing new hetero-binuclear metal complex systems based on polypyridyl ruthenium complexes, was carried out.The title compound was prepared by the following procedure: [Ru(bpy)(CO)2Cl2] (0.1 g) 3 was added to H2O (10 cm 3 ), and an ethanolic solution (10 cm 3 ) of dppy (0.09 g) was added to the suspension. The mixture was refluxed with stirring for 2 h. The addition of a saturated aqueous solution of KPF6 to the solution resulted in a colorless precipitate. The recrystallized compound from ethanol-acetone was identified as a dppy coordination complex, [Ru(bpy)(dppy)(CO)2Cl]PF6. 4 A colorless crystal of the title compound, having approximate dimensions of 0.33 × 0.28 × 0.05 mm, was mounted on a glass fiber. Data collections were performed at 173 K with graphitemonochromated Mo Kα radiation (λ = 0.71070 Å) on a Rigaku/MSC Mercury CCD diffractometer. The data were corrected for Lorentz and polarization effects. The structure was solved by the Patterson method using DIRDIF94 PATTY.All of the non-hydrogen atoms were refined anisotoropically by full-matrix least-squares methods. All hydrogen atoms were located by a geometrical calculation, and were not refined. All calculations were performed using the teXsan crystallographic software package. The crystal and experimental data are given in Table 1. The atomic positional and thermal parameters are given in Table 2.The molecular structure of the cation is shown in Fig. 2 and selected bond distances and angles are listed in Table 3. Although both the P-mono and P,N-bidentate coordination manners have been known for mononuclear systems, 5 the dppy ligand coordinates to the ruthenium center through only the phosphorus atom, as shown in Fig. 2. The coordination sphere of the ruthenium atom consists of one dppy ligand, two mutually cis carbonyl ligands, a chelating bipyridine ligand, and one chloride ligand. The Ru-P bond is not significantly x39 ANALYTICAL SCIENCES 2003, VOL. 19 X-ray Structure Analysis Online Crystal Structure of (2,2′-Bipyridine-N,N′)(diphenyl-2-phosphinopyridine-P)-chloro(dicarbonyl)ruthenium(II) HexafluorophosphateDai OOYAMA † and Masahito SATO Faculty of Education, Fukushima University, Kanayagawa, Fukushima 960-1296, Japan The crystal structure of (2,2′-bipyridine-N,N′)(diphenyl-2-phosphinopyridine-P)-chloro(dicarbonyl)ruthenium(II) hexafluorophosphate ([Ru(bpy)(dppy)(CO)2Cl]PF6; bpy = 2,2′-bipyridine, dppy = diphenyl-2-phosphinopyridine) has been determined by X-ray diffraction. This compound crystallizes in a monoclinic system, space group P21/n, with the following unit cell parameters: a = 10.237 (1)

Facile and Selective Synthetic Approach for Ruthenium Complexes Utilizing a Molecular Sieve Effect in the Supporting Ligand

“…The Ru-P bond distances of bis-phosphine complexes (2.4306(7) Å for 2, 2.430(2) and 2.436(2) Å for 3) are longer than that of the 2.3272(7) Å distance in 8, which has a trans chlorido ligand. However, these distances are in the range previously observed in Ru(II)-phosphine complexes [15][16][17][18]. The nitrile units (N≡CR) are essentially linear and the Ru-N, N-C, and C-C bond distances are similar to typical values in other Ru(II)-N≡CR complexes [15].…”

Crystallographic report: A synthetic precursor for hetero‐binuclear metal complexes, [Ru(bpy)(dppy)2(CO)2](PF6)2 (bpy = 2,2′‐bipyridine, dppy = 2‐(diphenylphosphino)pyridine)

“…8,9 The Ru-P distance of 2.407(1)Å is longer than that of the 2.327(6)Å Ru-P distance with trans chloride in [Ru(bpy)(dppy)(CO) 2 Cl] + . 5 The Ru-C-O angle (176.8(4) • ) is approximately linear, and the Ru-C and C-O distances (1.901(5)Å and 1.142(5)Å respectively) are normal. Thus, there are no significant differences in the RuCO moiety compared with other ruthenium(II) carbonyl complexes containing polypyridyl ligands.…”

“…[Ru(CO) 2 Cl 2 ] n , cis(CO),trans(Cl)-[Ru(bpy)(CO) 2 Cl 2 ], and [Ru(bpy)(dppy)(CO) 2 Cl]PF 6 (dppy = 2-(diphenylphosphino)pyridine) were prepared by the reported methods. 4,5…”

Role of X-Ray Crystallography in Structural Studies of Pyridyl-Ruthenium Complexes

“…Although both the P-mono and P,N-bidentate coordination modes have been known for mononuclear systems (Fig. 21) (Moldes et al, 1998), 13 coordinates to the ruthenium center through only the P atom in [Ru(bpy)(13)(CO) 2 Cl] + (Ooyama & Sato, 2003). A prominent feature of the structure is that the pyridyl nitrogen atom of 13 directs toward the plane that includes two carbonyl ligands (Fig.…”