Crystal structure of cis-dichloro-1,2-ethylenediamine-bis(1,4- (diphenylphosphino)butane)-ruthenium(II) dichloromethane disolvate, RuCl2(C2H8N2)(C28H28P2) · 2CH2Cl2

Abstract

C 32H40Cl6N2P2Ru, triclinic, P1 (no. 2), a = 10.338(6) Å, b = 13.024(5) Å, c = 14.491(5) Å, a = 81.02(2)°, b = 87.65(3)°, g = 66.95(3)°, V = 1772.9 Å 3 , Z = 2, R gt(F) = 0.028, wRref(F 2 ) = 0.075, T = 173 K. Source of materialAll the reactions were performed using Schlenk-type flask under argon and standard high vacuum-line techniques. [4,11,12], while the opposite was observed in solution and some solid state studies [3,[6][7][8]13]. The ruthenium center is in a distorted octahedral environment with a five-membered diamine ring coordinating in cis form via N1 and N2, a seven-membered bis(phosphine) ring coordinating in cis form via P1 and P2 as well as cis-dichloro coordination. The bis(phosphine) ring allows for PRuP angle to be larger than the ideal value of 94.13°, the smaller 1,2-diamine enforces NRuN angle that is 10.85°less than the ideal value, while the ClRuCl was found to be 89.61°which is very close to the ideal value. The RuN1 distance trans to Cl1 is shorter than the RuN2 distance trans to P2, 2.1213 Å and 2.1825 Å, respectively. The RuP1 distance trans to Cl2 slightly shorter than RuP2 distance trans to N2, 2.266 Å and 2.278 Å, respectively. The RuCl1 distance trans to N1 is slightly shorter than the RuCl2 distance trans to P1 by 0.034 Å, and found to be 2.489 Å and 2.455 Å, respectively. In the crystal structure there are a number of RuCl···H2N contacts smaller than 3.0 Å, indicating the presence of unconventional intra-hydrogen bonds [7,13].

Crystal structure of cis-dichloro(1,2-R,R-diaminocyclohexane)-bis[1,3-(diphenylphosphino)propane]ruthenium(II), RuCl2(C27H26P2)(C6H14N2)

“…Metal complexes containing phosphorus ligands have always been important, due to their possible catalytic activity [2][3][4][5][6]. Recently, a ruthenium(II) complex system containing diphosphine and 1,2-diamine ligands of type RuCl 2/PP/NN was discovered, which in the presence of abase and 2-propanol, proved to be excellent catalysts for the hydrogenation of ketones under mild conditions [5,6].…”

“…Diphosphines such dppp are of the most versatile ligands, since they can stablize metal-phosphorus bonds and at the same time [1][2][3], very different functionalization may be introduced by means of the groups bound to the phosphorus atom [4,5]. Metal complexes containing phosphorus ligands have always been important, due to their possible catalytic activity [2][3][4][5][6].…”

“…The title complex is crystallized as solvent-free in full cis form with lost of the C 2 symmetry. The cis-[RuCl 2 (dppp)NN] thermodynamical isomer is structurally favored over the trans-[RuCl 2 (dppp)NN] kinetic isomer [3], while the opposite was observed in solution and some solid state studies [2,8]. The ruthenium center is in adistorted octahedral environment with afivemembered diamine ring coordinating in cis form via N1 and N2, a six-membered bis(phosphine) ring coordinating in cis form via P1 and P2 as well as cis-dichloro coordination ( figure, top).…”

Trans-dichloro-2,3-naphthalenediamine bis[(2-methoxyethyl)­(diphenyl)phosphine]­ruthenium(II) Complex

“…These ligands are provided with oxygen atoms incorporated in open-chain ether moieties which form a weak metal-oxygen contact while the phosphorus atom is strongly coordinated to the metal [3][4][5][6][7][8][9]. In these "hemilabile" ligands, the ether moiety is regarded as an intramolecular solvent molecule stabilizing the vacant coordination site by chelation.…”

“…In these "hemilabile" ligands, the ether moiety is regarded as an intramolecular solvent molecule stabilizing the vacant coordination site by chelation. Phosphorusoxygen hemilabile ligands like 2-(diphenylphosphino)ethyl methyl ether (P~O), reacts with various metals of catalytic relevance due to their ability to act as both a chelate ligand, stabilizing the metal complex, and a monodentate ligand providing a free coordination site for an incoming substrate (through the labilization of the weakly bonded oxygen atom) [1][2][3][4][5][6][7][8][9][10].…”