Solid state and theoretical study of structural properties induced by step-wise chloro functionalization in dicarbonyl-[2-(phenylamino)pent-3-en-4-onato]rhodium(I) complexes

Packing polymorphism of dicarbonyl-[2-(phenylamino)pent-3-en-4-onato]rhodium(I)

“…The geometry of the solid state structure of two [Rh(CH3COCHCN(Ph)CH3)(CO)2] crystals presented in this contribution, compares well with the previously published structure [13] for the same complex, as well as with the DFT calculated optimised single molecular unit QTAIM results further suggested the formation of wire-like rhodium-rhodium chains as the lateral shift between the two molecular units decreases as was found for the -polymorphs of this study.…”

“…These B3LYP optimised gas phase structures were used to further conduct a natural bond orbital (NBO) analysis (using the NBO 3.1 module [25] in Gaussian 09), a fragment analysis, as well as an electronic density analysis (using Bader's quantum theory of atoms in molecules (QTAIM) [26,27,28], as implemented in ADF2013 [29,30,31]), at the same level of theory. These experimental results were then compared to a previously published structure [13] and packing of the same complex (-polymorph with space group I2/a, data collected at 100 K); see n/a n/a n/a n/a n/a Largest diff. peak and hole 0.348 and -0.470 e.Å -3 0.499 and -0.183 e.Å -3 0.260 and -0.494 e.Å -3 0.472 and -0.463 e.Å -3 0.410 and -0.439 e.Å -3…”

“…The extended metal-metal interactions along the linear chains in the latter case, have been described as resulting from the overlap of the filled orbitals and the empty pz orbitals that lie along the direction of the metal-metal axis [12]. Similarly to the latter, it has been shown recently that crystals of the complex [Rh(CH3COCHCN(Ph)CH3)(CO)2] (dicarbonyl- [2-(phenylamino)pent-3-en-4-onato]rhodium(I)) [13] (see Figure 1), in the solid state also pack in linear chains of consecutive unit cells along the intermolecular rhodium-metal axis in a wire-like structure (called the -polymorph), while a related molecule of dicarbonyl-(4-((2,6dichlorophenyl)imino)pent-2-en-2-olato)-rhodium did not show any inter-molecular rhodiumrhodium interaction in the solid state at all [13].…”

Crystal structure of (Z)-4,4,4-trifluoro-3-((2-hydroxyphenyl)amino)-1- (thiophen-2-yl)but-2-en-1-one, C14H10F3NO2S

“…The phenol-imine type b-keto-imine ligands are structurally and electronically analogous to the Schiff-base type ligands derived from salicylaldehyde [2][3][4][5][6]. The b-ketoiminate complexes have drawn interest because of their higher thermalstability [7]than the b-diketonate analogues and their versatility, by changing the imine substituents,f or tailoring their reactivity and volatility [7][8][9][10][11].The condensation of equimolar amounts of the 1,3-diketone and 2-aminophenol in ethanol afforded the phenolimino-ketone ligand.…”

Crystal structure of dichlorido bis(2-methylbenzothiazole-κ 1N)palladium( II) chloride, C16H14Cl2N2PdS2

“…Research interest in phenol-imine type b-keto-imine ligands due to their structural and electronical similarityt ot he Schiff-base type ligands derived from salicylaldehyde [3][4][5][6].Itisofimportance to exchange the coordinating atoms, e.g. the oxygen atom with sulphur atom to study the effect on coordination behaviour of these ligands [7][8][9][10].…”