TY - JOUR
T1 - C-P Bond Cleavage Through Hydrogenation in Ruthenium Complexes Supported by P,N Ligands
AU - Cacho, Vanessa R.G.
AU - Veiros, Luís F.
AU - Gomes, Clara S.B.
AU - Sardo, Mariana
AU - Figueira, Cláudia A.
AU - Martins, Ana M.
AU - Ferreira, Maria João
N1 - Funding Information:
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDB%2F00100%2F2020/PT#
info:eu-repo/grantAgreement/FCT/Concurso de avaliação no âmbito do Programa Plurianual de Financiamento de Unidades de I&D (2017%2F2018) - Financiamento Programático/UIDP%2F00100%2F2020/PT#
info:eu-repo/grantAgreement/FCT/Concurso para Atribuição do Estatuto e Financiamento de Laboratórios Associados (LA)/LA%2FP%2F0056%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDB%2F50006%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDP%2F50006%2F2020/PT#
info:eu-repo/grantAgreement/FCT/Concurso para Atribuição do Estatuto e Financiamento de Laboratórios Associados (LA)/LA%2FP%2F0008%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDB%2F04378%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDP%2F04378%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/LA%2FP%2F0140%2F2020/PT#
info:eu-repo/grantAgreement/FCT/Concurso de avaliação no âmbito do Programa Plurianual de Financiamento de Unidades de I&D (2017%2F2018) - Financiamento Programático/UIDP%2F50011%2F2020/PT#
info:eu-repo/grantAgreement/FCT/Concurso de avaliação no âmbito do Programa Plurianual de Financiamento de Unidades de I&D (2017%2F2018) - Financiamento Base/UIDB%2F50011%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/LA%2FP%2F0006%2F2020/PT#
info:eu-repo/grantAgreement/FCT/OE/PD%2FBD%2F147841%2F2019/PT#
The NMR spectrometers are part of the National NMR Network (PTNMR) and are partially supported by Infrastructure Project No 022161 (cofinanced by FEDER through COMPETE 2020, POCI and PORL and FCT through PIDDAC). The authors also acknowledge Va\u0302nia Andre\u0301 for X-ray data acquisition, Gonc\u0327alo Justino for Mass Spectrometry data and Marina Kirillova for the use of the GC.
Publisher Copyright:
© 2024 American Chemical Society.
PY - 2024/12/9
Y1 - 2024/12/9
N2 - The reactivity of ruthenium hydride complexes supported by 2-((di-tert-butylphosphaneyl)methyl)pyridine, L1 and 2-(di-tert-butylphosphaneyl)pyridine, L2, was explored. The reaction of {Ru(COD)Cl2}x with L1 in the presence of base and 10 bar of H2 gave the expected complex [Ru(L1)2(H)Cl], 1, while the same reaction with L2 gave [Ru(L2)(P(H)tBu2)(H)Cl], 2, that results from the cleavage of a C-P bond. We were able to establish that under the reaction conditions the first species formed is [Ru(L2)2(H)Cl], 3, and that this species decomposes to give complex 2 and is in equilibrium with [Ru(L2)2Cl2], 4. The proposed mechanism obtained by DFT has the protonation of the carbon as the highest energy step (38.9 kcal/mol), consistent with a slow reaction. Preliminary studies reveal that complex 2 is a very active catalyst in the hydrogenation of benzaldehyde (TONs up to 44,000).
AB - The reactivity of ruthenium hydride complexes supported by 2-((di-tert-butylphosphaneyl)methyl)pyridine, L1 and 2-(di-tert-butylphosphaneyl)pyridine, L2, was explored. The reaction of {Ru(COD)Cl2}x with L1 in the presence of base and 10 bar of H2 gave the expected complex [Ru(L1)2(H)Cl], 1, while the same reaction with L2 gave [Ru(L2)(P(H)tBu2)(H)Cl], 2, that results from the cleavage of a C-P bond. We were able to establish that under the reaction conditions the first species formed is [Ru(L2)2(H)Cl], 3, and that this species decomposes to give complex 2 and is in equilibrium with [Ru(L2)2Cl2], 4. The proposed mechanism obtained by DFT has the protonation of the carbon as the highest energy step (38.9 kcal/mol), consistent with a slow reaction. Preliminary studies reveal that complex 2 is a very active catalyst in the hydrogenation of benzaldehyde (TONs up to 44,000).
UR - http://www.scopus.com/inward/record.url?scp=85211447667&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.4c04275
DO - 10.1021/acs.inorgchem.4c04275
M3 - Article
C2 - 39589315
AN - SCOPUS:85211447667
SN - 0020-1669
VL - 63
SP - 23421
EP - 23430
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 49
ER -