Di-μ-iodido-bis[acetyl(4-methyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane)(N-nitroso-N-oxidoaniline-κ²O,O′)rhodium(III)]

Abstract

The title compound, [Rh2(C6H5N2O2)2(C2H3O)2I2(C5H9O3P)2], contains a binuclear centrosymmetric RhIII dimer bridged by iodide anions, with respective Rh⋯Rh and I⋯I distances of 4.1437 (5) and 3.9144 (5) Å. The RhIII atom is in a distorted octa­hedral RhCI2O2P coordination with considerably different Rh—I distances to the bridging iodide anions. There are no classical hydrogen-bonding inter­actions observed for this complex.

Crystal structure of 4-methyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane

“…3) in the metal-coordinated phosphites, M-{P(OCH 2 ) 3 CR} (e.g. Aroney et al, 1994;Venter et al, 2009;Davis & Verkade, 1990;Predvoditelev et al, 2009;Basson et al, 1992;Erasmus et al, 1998;Joslin et al, 2012;Albright et al, 1977) are ca 1.59 Å , and 4) in our results, correlate with those of other unsubstituted phosphites, (e.g. Wojczykowski & Jutzi, 2006;Milbrath et al, 1976;Predvoditelev et al, 2009) with P-O bond lengths of ca 1.62 Å .…”

“…The average of O-P-O bond angle (a, Scheme 1) in our study is 100.7 o , whereas the average O-P-O bond angle in coordinated phosphites (a 0 , Scheme 1) is larger, e.g. in Ru{P(OCH 2 ) 3 CEt}Cl 2 , it is 102.5 o (Joslin et al, 2012), the same as in (Venter et al, 2009); this suggests a slightly larger Tolman angle (Tolman et al, 1977) after metal ligation. In another study, the enhanced -accepting ability of the bicyclic phosphite ligand compared to the PPh 3 and other phosphine ligands was demonstrated clearly in the shorter M-P bond distances in the bicyclic phosphite complexes (Erasmus et al, 1998).…”

Orientation of trimethylolethane cyclic phosphite in rhodium complexes: Structure of [Rh(CH3COCHCOCH3)(CO)(P(OCH2)3CCH3)]

“…The cyclic (P(OCH 2 ) 3 CCH 3 ) group thus adopts orientation 2 (Scheme 2) in both the DFT lowest energy optimized geometry, as well as in the experimental crystal structure of the square pyramidal complex (4). The experimental three dihedral angles O cupf trans to I -Rh-P-O of 34.7°, 81.5° and 153.8° [27], are thus near perpendicular to the plane through the four atoms coordinated to Rh. These dihedral angles should be 45°, 90° and 135°, respectively, to be exactly perpendicular.…”

“…Table 2 gives selected geometrical parameters of [Rh(acac)(CO)(P(OCH 2 ) 3 CCH 3 )], (1), and related Rh-(P(OCH 2 ) 3 CCH 3 ) complexes (2) [25], (3) [26] and (4) [27]. A summary of some of the important crystal data is as follows: Empirical .…”

Crystal structure of tris(N-nitroso-N-oxyanilino-κ2 O, O′) oxidoniobium(V), C18H15N6O7Nb

“…The chelate-forming derivatives of this ligand is known to form stable complexes with various metals, but only few of them have been structurally characterized [3][4][5][6][7][8][9][10][11][12]. Also some cupferrates were investigated in our group [13][14][15][16][17][18]. This study forms part of ongoing research to investigate the mechanism of the reactions of O,O′-and N,O-bidentate ligands with transition metals used in nuclear industry, such as Hf, Zr, Nb, Ta [19][20][21][22][23][24][25][26].…”