Structure and Reactivity of [Ru-Al] and [Ru-Sn] Heterobimetallic PPh3-Based Complexes

Connie Isaac, Fedor Miloserdov, Anne-Frédérique Pecharman, John Lowe, Claire McMullin, Michael Whittlesey

Research output: Contribution to journalArticlepeer-review

3 Citations (SciVal)

Abstract

Treatment of [Ru(PPh3)(C6H4PPh2)2H][Li(THF)2] with AlMe2Cl and SnMe3Cl leads to elimination of LiCl and CH4 and formation of the heterobimetallic complexes [Ru(C6H4PPh2)2{PPh2C6H4AlMe(THF)}H] 5 and [Ru(PPh3)(C6H4PPh2)(PPh2C6H4SnMe2)] 6, respectively. The pathways to 5 and 6 have been probed by variable temperature NMR studies, together with input from DFT calculations. Complete reaction of H2 occurs with 5 at 60 °C and with 6 at room temperature to yield the spectroscopically characterized trihydride complexes [Ru(PPh2)2{PPh2C6H4AlMe}H3] 7 and [Ru(PPh2)2{PPh2C6H4SnMe2}H3] 8. In the presence of CO, 6 forms the acylated phosphine complex, [Ru(CO)2(C(O)C6H4PPh2)(PPh2C6H4SnMe2)] 9, through a series of intermediates that were identified by NMR spectroscopy in conjunction with 13CO labeling. Complex 6 undergoes addition and substitution reactions with the N-heterocyclic carbene 1,3,4,5-tetramethylimidazol-2-ylidene (IMe4) to give [Ru(IMe4)2(PPh2C6H4)(PPh2C6H4SnMe2)] 10, which converted via rare N-Me group C-H activation to [Ru(IMe4)(PPh3)(IMe4)′(PPh2C6H4SnMe2)] 11 upon heating at 60 °C and to a mixture of [Ru(IMe4)2(IMe4)′(PPh2C6H4SnMe2)] 12 and [Ru(PPh3)(PPh2C6H4)(IMe4-SnMe2)′] 13 at 120 °C.

Original languageEnglish
Pages (from-to)2716-2730
Number of pages15
JournalOrganometallics
Volume41
Issue number19
Early online date21 Sept 2022
DOIs
Publication statusPublished - 10 Oct 2022

Bibliographical note

This project has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No 792674 (FMM) and EPSRC (grant EP/T019743/1 to AFP, Doctoral Training Award to CJI). This research made use of the Balena and Anatra High Performance Computing (H.P.C.) Services at the University of Bath. We thank Dr Mary Mahon for X-ray assistance and Dr Dan Pantos for access to his UV-vis spectrometer

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