Preparation of Neutral trans - cis [Ru(O₂CR)₂P₂(NN)], Cationic [Ru(O₂CR)P₂(NN)](O₂CR) and Pincer [Ru(O₂CR)(CNN)P₂] (P = PPh₃, P₂ = diphosphine) Carboxylate Complexes and their Application in the Catalytic Carbonyl Compounds Reduction.

Content Provider	Europe PMC
Author	Baldino, Salvatore Giboulot, Steven Lovison, Denise Nedden, Hans Günter Pöthig, Alexander Zanotti-Gerosa, Antonio Zuccaccia, Daniele Ballico, Maurizio Baratta, Walter
Copyright Year	2021
Abstract	The diacetate complexes trans-[Ru(κ1-OAc)2(PPh3)2(NN)] (NN =ethylenediamine (en) (1), 2-(aminomethyl)pyridine (ampy)(2), 2-(aminomethyl)pyrimidine (ampyrim) (3)) have been isolated in 76–88% yield by reaction of [Ru(κ2-OAc)2(PPh3)2] with the correspondingnitrogen ligands. The ampy-type derivatives 2 and 3 undergo isomerization to the thermodynamically most stablecationic complexes [Ru(κ1-OAc)(PPh3)2(NN)]OAc (2a and 3a) and cis-[Ru(κ1-OAc)2(PPh3)2(NN)] (2b and 3b) in methanolat RT. The trans-[Ru(κ1-OAc)2(P2)2] (P2 = dppm (4), dppe (5)) compounds have been synthesizedfrom [Ru(κ2-OAc)2(PPh3)2] by reaction with the suitable diphosphine in toluene at95 °C. The complex cis-[Ru(κ1-OAc)2(dppm)(ampy)](6) has been obtainedfrom [Ru(κ2-OAc)2(PPh3)2] and dppm in toluene at reflux and reaction with ampy. Thederivatives trans-[Ru(κ1-OAc)2P2(NN)] (7–16;NN = en, ampy, ampyrim, 8-aminoquinoline; P2 = dppp, dppb,dppf, (R)-BINAP) can be easily synthesized from [Ru(κ2-OAc)2(PPh3)2] with a diphosphineand treatment with the NN ligands at RT. Alternatively these compoundshave been prepared from trans-[Ru(OAc)2(PPh3)2(NN)] by reaction with the diphosphinein MEK at 50 °C. The use of (R)-BINAP affords trans-[Ru(κ1-OAc)2((R)-BINAP)(NN)] (NN = ampy (11), ampyrim (15)) isolated as single stereoisomers. Treatment of the ampy-typecomplexes 8–15 with methanol at RTleads to isomerization to the cationic derivatives [Ru(κ2-OAc)P2(NN)]OAc (8a–15a; NN = ampy, ampyrim; P2 = dppp, dppb, dppf, (R)-BINAP). Similarly to 2, the dipivalate trans-[Ru(κ1-OPiv)2(PPh3)2(ampy)] (18) is prepared from [Ru(κ2-OPiv)2(PPh3)2] (17) and ampy in CHCl3. The pincer acetate [Ru(κ1-OAc)(CNNOMe)(PPh3)2] (19) has been synthesized from [Ru(κ2-OAc)2(PPh3)2] and HCNNOMe ligandin 2-propanol with NEt3 at reflux. In addition, the dppbpincer complexes [Ru(κ1-OAc)(CNN)(dppb)] (CNN = AMTP(20), AMBQPh (21)) have beenobtained from [Ru(κ2-OAc)2(PPh3)2], dppb, and HAMTP or HAMBQPh with NEt3, respectively. The acetate NN and pincer complexes are activein transfer hydrogenation with 2-propanol and hydrogenation with H2 of carbonyl compounds at S/C values of up to 10000 and withTOF values of up to 160000 h–1.
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ISSN	02767333
Journal	Organometallics
Volume Number	40
DOI	10.1021/acs.organomet.1c00059
PubMed Central reference number	PMC8155570
Issue Number	8
PubMed reference number	34054183
e-ISSN	15206041
Language	English
Publisher	American Chemical Society
Publisher Date	2021-04-14
Access Restriction	Open
Rights License	Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). © 2021 The Authors. Publishedby AmericanChemical Society
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Physical and Theoretical Chemistry Inorganic Chemistry