TY - JOUR
T1 - Ru(0) and Ru(II) nitrosyl pincer complexes
T2 - Structure, reactivity, and catalytic activity
AU - Fogler, Eran
AU - Iron, Mark A.
AU - Zhang, Jing
AU - Ben-David, Yehoshoa
AU - Diskin-Posner, Yael
AU - Leitus, Gregory
AU - Shimon, Linda J.W.
AU - Milstein, David
PY - 2013/10/7
Y1 - 2013/10/7
N2 - Despite considerable interest in ruthenium carbonyl pincer complexes and their substantial catalytic activity, there has been relatively little study of the isoelectronic ruthenium nitrosyl complexes. Here we describe the synthesis and reactivity of several complexes of this type as well as the catalytic activity of complex 6. Reaction of the PNP ligand (PNP = 2,6-bis( tBu2PCH2)pyridine) with RuCl 3(NO)(PPh3)2 yielded the Ru(II) complex 3. Chloride displacement by BArF- (BArF- = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) gave the crystallographicaly characterized, linear NO Ru(II) complex 4, which upon treatment with NaBEt 3H yielded the Ru(0) complexes 5. The crystallographically characterized Ru(0) square planar complex 5·BF4 bears a linear NO ligand located trans to the pyridilic nitrogen. Further treatment of 5·BF4 with excess LiOH gave the crystallographicaly characterized Ru(0) square planar, linear NO complex 6. Complex 6 catalyzes the dehydrogenative coupling of alcohols to esters, reaching full conversion under air or under argon. Reaction of the PNN ligand (PNN = 2-(tBu 2PCH2)-6-(Et2NCH2)pyridine) with RuCl3(NO)(H2O)2 in ethanol gave an equilibrium mixture of isomers 7a and 7b. Further treatment of 7a + 7b with 2 equivalent of sodium isopropoxide gave the crystallographicaly characterized, bent-nitrosyl, square pyramidal Ru(II) complex 8. Complex 8 was also synthesized by reaction of PNN with RuCl3(NO)(H2O)2 and Et3N in ethanol. Reaction of the "long arm" PN2N ligand (PN 2N = 2-(tBu2PCH2-)-6-(Et 2NCH2CH2)pyridine) with RuCl 3(NO)(H2O)2 in ethanol gave complex 9, which upon treatment with 2 equiv of sodium isopropoxide gave complex 10. Complex 10 was also synthesized directly by reaction of PN2N with RuCl 3(NO)(H2O)2 and a base in ethanol. A noteworthy aspect of these nitrosyl complexes is their preference for the Ru(0) oxidization state over Ru(II). This preference is observed with both aromatized and dearomatized pincer ligands, in contrast to the Ru(II) oxidation state which is preferred by the analogous carbonyl complexes.
AB - Despite considerable interest in ruthenium carbonyl pincer complexes and their substantial catalytic activity, there has been relatively little study of the isoelectronic ruthenium nitrosyl complexes. Here we describe the synthesis and reactivity of several complexes of this type as well as the catalytic activity of complex 6. Reaction of the PNP ligand (PNP = 2,6-bis( tBu2PCH2)pyridine) with RuCl 3(NO)(PPh3)2 yielded the Ru(II) complex 3. Chloride displacement by BArF- (BArF- = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) gave the crystallographicaly characterized, linear NO Ru(II) complex 4, which upon treatment with NaBEt 3H yielded the Ru(0) complexes 5. The crystallographically characterized Ru(0) square planar complex 5·BF4 bears a linear NO ligand located trans to the pyridilic nitrogen. Further treatment of 5·BF4 with excess LiOH gave the crystallographicaly characterized Ru(0) square planar, linear NO complex 6. Complex 6 catalyzes the dehydrogenative coupling of alcohols to esters, reaching full conversion under air or under argon. Reaction of the PNN ligand (PNN = 2-(tBu 2PCH2)-6-(Et2NCH2)pyridine) with RuCl3(NO)(H2O)2 in ethanol gave an equilibrium mixture of isomers 7a and 7b. Further treatment of 7a + 7b with 2 equivalent of sodium isopropoxide gave the crystallographicaly characterized, bent-nitrosyl, square pyramidal Ru(II) complex 8. Complex 8 was also synthesized by reaction of PNN with RuCl3(NO)(H2O)2 and Et3N in ethanol. Reaction of the "long arm" PN2N ligand (PN 2N = 2-(tBu2PCH2-)-6-(Et 2NCH2CH2)pyridine) with RuCl 3(NO)(H2O)2 in ethanol gave complex 9, which upon treatment with 2 equiv of sodium isopropoxide gave complex 10. Complex 10 was also synthesized directly by reaction of PN2N with RuCl 3(NO)(H2O)2 and a base in ethanol. A noteworthy aspect of these nitrosyl complexes is their preference for the Ru(0) oxidization state over Ru(II). This preference is observed with both aromatized and dearomatized pincer ligands, in contrast to the Ru(II) oxidation state which is preferred by the analogous carbonyl complexes.
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U2 - 10.1021/ic401780p
DO - 10.1021/ic401780p
M3 - Article
C2 - 24047217
AN - SCOPUS:84885095227
VL - 52
SP - 11469
EP - 11479
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 19
ER -