TY - JOUR
T1 - Isolation of Bis- and Mono-Cyclometallated Ru-IMes Complexes Upon Reaction of [Ru(PPh3)3HCl], IMes and ZnMe2
AU - Pecharman, Anne-Frédérique
AU - Roberts, Erika
AU - Miloserdov, Fedor
AU - Varela-Izquierdo, Victor
AU - Mahon, Mary
AU - Whittlesey, Michael
N1 - Engineering and Physical Sciences Research Council - EP/T019743/1
Horizon 2020 Framework Programme - 792674
MINECO/FEDER - CTQ2017-83421-P
Funding Information:
This work was supported by the EPSRC (grant EP/T019743/1 for AFP) and the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska‐Curie grant agreement No 792674 (FMM). VVI thanks MINECO/FEDER (CTQ2017‐83421‐P) and Gobierno de Aragón (GA/FEDER, Inorganic Molecular Architecture Group E08_17R) for financial support and MINECO/FEDER for a FPI fellowship. We thank Dr David Liptrot for assistance with ATR‐IR measurements and the anonymous reviewers for valuable experimental suggestions.
Publisher Copyright:
© 2023 The Authors. European Journal of Inorganic Chemistry published by Wiley-VCH GmbH.
PY - 2023/2/17
Y1 - 2023/2/17
N2 - Addition of an excess of ZnMe
2 to a mixture of [Ru(PPh
3)
3HCl] and IMes (IMes=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene) yields the bis-cyclometallated complex, [Ru(IMes)“(PPh
3)
2] 2, together with the mono-cyclometallated, Ru−Zn heterobimetallic complex [Ru(IMes)′(PPh
3)
2(ZnMe)] 3. Treatment of 2 with H
2, PhSiH
3 or pinacolborane yields the previously reported complex, [Ru(IMes)′(PPh
3)
2H] 1, the synthesis of which has been reinvestigated. Further studies of small molecule reactivity show that 1 adds H
2 to give [Ru(IMes)(PPh
3)
2H
4] 4, whilst 2 reacts with catecholborane to give [Ru(IMes-Bcat)′(PPh
3)
2H] 5, in which (IMes-Bcat)′ signifies a borylated NHC ligand that is singly-metallated onto Ru. Treatment of 2 with CO gives the 18-electron dicarbonyl product [Ru(IMes)”(PPh
3)(CO)
2] 6. Compounds 1–3, 5 and 6 have been structurally characterised.
AB - Addition of an excess of ZnMe
2 to a mixture of [Ru(PPh
3)
3HCl] and IMes (IMes=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene) yields the bis-cyclometallated complex, [Ru(IMes)“(PPh
3)
2] 2, together with the mono-cyclometallated, Ru−Zn heterobimetallic complex [Ru(IMes)′(PPh
3)
2(ZnMe)] 3. Treatment of 2 with H
2, PhSiH
3 or pinacolborane yields the previously reported complex, [Ru(IMes)′(PPh
3)
2H] 1, the synthesis of which has been reinvestigated. Further studies of small molecule reactivity show that 1 adds H
2 to give [Ru(IMes)(PPh
3)
2H
4] 4, whilst 2 reacts with catecholborane to give [Ru(IMes-Bcat)′(PPh
3)
2H] 5, in which (IMes-Bcat)′ signifies a borylated NHC ligand that is singly-metallated onto Ru. Treatment of 2 with CO gives the 18-electron dicarbonyl product [Ru(IMes)”(PPh
3)(CO)
2] 6. Compounds 1–3, 5 and 6 have been structurally characterised.
KW - C−H activation
KW - carbene ligands
KW - ruthenium
KW - zinc
UR - http://www.scopus.com/inward/record.url?scp=85149310097&partnerID=8YFLogxK
U2 - 10.1002/ejic.202300037
DO - 10.1002/ejic.202300037
M3 - Article
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
SN - 1434-1948
M1 - e202300037
ER -