Small molecule binding and activation on a cationic ruthenium center of a pincer complex

Ramaraj, A. ; Jagirdar, Balaji R. ; Nethaji, Munirathinam (2016) Small molecule binding and activation on a cationic ruthenium center of a pincer complex Journal of Organometallic Chemistry, 825-26 . pp. 114-124. ISSN 0022-328X

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Official URL: http://www.sciencedirect.com/science/article/pii/S...

Related URL: http://dx.doi.org/10.1016/j.jorganchem.2016.10.030

Abstract

Ruthenium pincer complex [RuHCl(PPh3)(PNP)] (PNP = Me−N(CH2CH2PPh2)2) (1) was synthesized by reaction of RuHCl(PPh3)3 with Me-N(CH2CH2PPh2)2 and characterized. Abstraction of chloride ligand in complex 1 using NaBAr4f in the presence of small molecules such as N2, H2, O2, and CO resulted in the formation of trans-[RuH(L)(PPh3)(PNP)]BAr4f {L = N2 (2), H2 (4), O2 (5), CO (6)} complexes. Complexes 2, 4, 5, and 6 have been characterized by various techniques. The reaction of [RuHCl(PPh3)(PNP)] complex with NaBH4 gave a borohydrido complex [RuH(η1−BH4)(PPh3)(PNP)] (7) which upon reaction with NEt3 generates a mixture of cis and trans dihydrides [RuH2 (PPh3)(PNP)] (8). The reaction of dihydride complexes with CO2 leads to the formation of formate complex [RuH(η1−HCO2)(PPh3)(PNP)] (9). In addition, dihydrogen complexes [Ru(η2-H2)(L)(PPh3)(PNP)]n+ (L = Cl (10), CO (11)) having different trans donor ligands were synthesized by protonation of trans-[RuH(L)(PPh3)(PNP)]n+ {n = 0, L = Cl; n = 1, L = CO} complexes with HOTf at low temperature. Complexes 1 and 6 have been characterized by X-ray crystallography.

Item Type:Article
Source:Copyright of this article belongs to Elsevier Science.
Keywords:Small Molecules; Catalysis; NMR Spectroscopy; Ruthenium Complex; Binding; Activation
ID Code:102312
Deposited On:12 Feb 2018 12:19
Last Modified:12 Feb 2018 12:19

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