REACTIONS OF [RU(BPY)(CO)(2)CL-2] IN ACIDIC MEDIA - FORMATION AND STRUCTURAL CHARACTERIZATION OF [RU(BPY)CL-3(NO)], [RU2N(BPY)(2)CL-5(H2O)], AND (H5O(2))[RU2N(BPY)(2)CL-6]
M. Haukka et al., REACTIONS OF [RU(BPY)(CO)(2)CL-2] IN ACIDIC MEDIA - FORMATION AND STRUCTURAL CHARACTERIZATION OF [RU(BPY)CL-3(NO)], [RU2N(BPY)(2)CL-5(H2O)], AND (H5O(2))[RU2N(BPY)(2)CL-6], Inorganic chemistry, 34(11), 1995, pp. 2931-2936
Reactions of [Ru(bpy)(CO)(2)Cl-2] in concentrated HCl/HNO3 solutions a
t high temperatures were studied. In acidic solutions carbonyl groups
are lost and replaced by chlorine and nitrosyl, nitrido or water ligan
ds. Formation of [Ru(bpy)Cl-3(NO)] and [Ru2N(bpy)(2)Cl-5(H2O)] was tim
e-dependent; with shorter reaction times (<6 h, 240 degrees C) solid c
rystalline fac(Cl)-[Ru(bpy)Cl-3(NO)] (1a) and mer(Cl)- [Ru(bpy)Cl-3(NO
)] (1b) were formed, and with longer reaction times a new crystalline
nitrido-bridged complex [Ru2N(bpy)(2)Cl-5(H2O)] (2) was produced, most
probably via a nitrosyl intermediate. Both 1 and 2 are practically in
soluble and highly stable. However, the reaction of [Ru(bpy)(CO)(2)Cl-
2] in HCl/HNO3 solution with small amounts of [Ru(bpy)Cl-3(NO)] added
gave in low yield another nitrido-bridged product, (H5O2)[Ru2N(bpy)(2)
Cl-6] (3). The role of added [Ru(bpy)Cl-3(NO)] in this reaction is unc
lear, and it is possible that (3) may also form directly from pure [Ru
(bpy)(CO)(2)Cl-2]. Crystal structures of fac(Cl)-[Ru(bpy)Cl-3(NO)], me
r(Cl)- [Ru(bpy)Cl-3(NO)], [Ru2N(bpy)(2)Cl-5(H2O)], and (H5O2)[Ru2N(bpy
)(2)Cl-6] showed that the ruthenium atoms are octahedrally coordinated
in all complexes. Crystal data: 1a, monoclinic, space 6.798(3) Angstr
om, b = 11.993(4) Angstrom, c = 16.760(8) Angstrom, beta = 98.89(3)deg
rees, Z = 4; 1b, monoclinic, space group Pn, a = 8.175(2) Angstrom, b
= 6.733(2) Angstrom, c = 12.594(5) Angstrom, beta = 105.06(3)degrees,
Z = 2; 2, monoclinic, space group P2(1)/n, a = 10.133(5) Angstrom, b =
15.042(6) Angstrom, c = 16.506(8) Angstrom, beta = 104.86(4)degrees,
Z = 4; 3, triclinic, space group P ($) over bar 1, a = 10.281(3) Angst
rom, b = 10.776(3) Angstrom, c = 12.527(5) Angstrom, alpha = 90.78(3)d
egrees, beta = 98.31(3)degrees, gamma = 100.91(2)degrees, Z = 2.