Characterization of Five-Coordinate Ruthenium(II) Phosphine Complexes by X-ray Diffraction and Solid-State³¹P CP/MAS NMR Studies and Their Reactivity with Sulfoxides and Thioethers

Abstract

31P CP/MAS NMR spectroscopy is examined as a method of characterization for ruthenium(II) phosphine complexes in the solid state, and the results are compared with X-ray crystallographic data determined for RuCl(2)(dppb)(PPh(3)) (dppb = Ph(2)P(CH(2))(4)PPh(2)), RuBr(2)(PPh(3))(3), and the previously determined RuCl(2)(PPh(3))(3). Crystals of RuBr(2)(PPh(3))(3) (C(54)H(45)Br(2)P(3)Ru) are monoclinic, space group P2(1)/a, with a = 12.482(4) Å, b = 20.206(6) Å, c = 17.956(3) Å, beta = 90.40(2) degrees, and Z = 4, and those of RuCl(2)(dppb)(PPh(3)) (C(46)H(43)Cl(2)P(3)Ru) are also monoclinic, space group P2(1)/n, with a = 10.885(2) Å, b = 20.477(1) Å, c = 18.292(2) Å, beta = 99.979(9) degrees, and Z = 4. The structure of RuBr(2)(PPh(3))(3) was solved by direct methods, and that of RuCl(2)(dppb)(PPh(3)) was solved by the Patterson method. The structures were refined by full-matrix least-squares procedures to R = 0.048 and 0.031 (R(w) = 0.046 and 0.032) for 5069 and 5925 reflections with I >/= 3sigma(I), respectively. Synthetic routes to RuBr(2)(dppb)(PPh(3)) and [RuBr(dppb)](2)(&mgr;(2)-dppb) are reported. The reactivity of RuCl(2)(dppb)(PPh(3)) with the neutral two-electron donor ligands (L) dimethyl sulfoxide, tetramethylene sulfoxide, tetrahydrothiophene, and dimethyl sulfide to give [(L)(dppb)Ru(&mgr;-Cl)(3)RuCl(dppb)] is discussed.

Synthesis, characterization, X-ray structure and in vitro antimycobacterial and antitumoral activities of Ru(II) phosphine/diimine complexes containing the “SpymMe2” ligand, SpymMe2=4,6-dimethyl-2-mercaptopyrimidine

“…The Ru-P bonds of 2.3092(8) and 2.3326(8) Å are within the normal range found for Ru(II) tertiary phosphine complexes [43][44][45][46][47][48]. The P-Ru-P angle in the seven-membered ring of dppb is 94.02(3)°, comparable with the values previously observed for 3 [33].…”

“…In the precursors, the high-field doublet corresponds to the P trans N, as previously described [33]. These assignments are based on an empirical linear correlation established between the crystallographically determined Ru-P distances in a series of Ru-dppb complexes and the corresponding 31 P chemical shifts observed in solution, with the chemical shifts becoming more high-field with increasing Ru-P bond lengths [33,46]. Based on this previous information, we suggest that in the new complexes the high-field doublet belongs to the P trans (N-N) (N-H), which appears at 3200-3100 cm À1 in free thiones, is absent in 1 and 2, indicating that the SpymMe 2 is coordinated in the deprotonated form [56].…”

Ruthenium(II) phosphine/diimine/picolinate complexes: Inorganic compounds as agents against tuberculosis

“…In the precursors, the high-field doublet corresponds to the P trans N, as previously described [15]. These assignments are based on an empirical linear correlation established between the crystallographically determined RueP distances in a series of Ru-dppb complexes and the corresponding 31 P chemical shifts observed in solution, in which the chemical shifts become more high-field with increasing RueP bond length [15,16,19]. In light of this information, we suggest that in the new complexes the high-field doublet belongs to the P trans to nitrogen from bipy (N-N), because the Ru-P1 distance of 2.347(3) Å (trans N-N) is longer than that observed for the Ru-P2 trans O of the pic ligand (2.324(2) Å) (see Table 1).…”

Mesoporous Silica with Multiple Catalytic Functionalities

“…Two peaks at 36 ppm and 71 ppm are attributed to the phosphor ligands with different positions in the five-coordinated Ru(II) complex. [27] The peak around 18 ppm is ascribed to the phosphor ligands in the four-coordinated Pd(II) complex. [28] These results are quite similar to those of RuCl 2 (PPh 3 ) 3 and PdCl 2 (PPh 3 ) 3 , which indicates that the assembled MOC catalyst could perfectly retain the instinctive chemical environment of an organometallic catalyst.…”