Ruthenium Complexes of a Simple Tridentate Ligand Bearing Two "Distal" Pyridine Bases.
Treatment of N,N'-bis(6-methyl-2-pyridinyl)-2,6-pyridinedicarboxamide (1) (H(2)LMe(2)) with RuCl(2)(PPh(3))(3) in toluene yields the complex RuCl(2)(PPh(3))(LMe(2){H}(2)) (2) in which the ruthenium atom is coordinated to the nitrogen atoms of the two deprotonated amides and the central pyridine of 1. The two pendant pyridines in 2 are both protonated, and hydrogen bonds are formed to the coordinated chloride positioned in the molecular cleft between these two groups. Both of the chlorides in 2 can be replaced by other anions in simple metathesis reactions, and treatment of 2 with excess SCN(-) or CH(3)CO(2)(-) yields the corresponding complexes RuX(2)(PPh(3))(LMe(2){H}(2)) (X: SCN(-), 3; CH(3)CO(2)(-), 4). Treatment of 2 with NO(2)(-) also results in displacement of the chlorides, but in this case, the protons on the pendant pyridines are lost and the nitrosyl-containing complex Ru(NO(2))(NO)(PPh(3))(LMe(2)) (5) is formed. Single-crystal X-ray structure determinations have been carried out for the following compounds: 1, space group C2/c, a = 13.588(6) Å, b = 11.518(2) Å, c = 12.731(3) Å, Z = 4, V = 1826.7 Å(3); 2, space group P&onemacr;, a = 10.482(5) Å, b = 11.349(8) Å, c = 15.710(4) Å, Z= 2, V = 1689(2) Å(3); 5, space group P&onemacr;, a = 12.204(2) Å, b = 13.065(3) Å, c = 14.722(6) Å, Z = 2, V = 1973.9(10) Å(3).
Redmore
Seth M.
SM
Department of Chemistry, University of Auckland, Private Bag 92019, Auckland, New Zealand.
Rickard
Clifton E. F.
CE
Webb
Simon J.
SJ
Wright
L. James
LJ