Heterobimetallic Ruthenium-Zinc Complexes with Bulky N-Heterocyclic Carbenes: Syntheses, Structures and Reactivity

Maialen Espinal-Viguri, Victor Varela-Izquerido, Fedor Miloserdov, Ian Riddlestone, Mary Mahon, Michael Whittlesey

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Abstract

The ruthenium-zinc heterobimetallic complexes, [Ru(IPr)2(CO)ZnMe][BArF4] (7), [Ru(IBiox6)2(CO)(THF)ZnMe][BArF4] (12) and [Ru(IMes)(PPh3)(CO)ZnMe] (15), have been prepared by reaction of ZnMe2 with the ruthenium N-heterocyclic carbene complexes [Ru(IPr)2(CO)H][BArF4] (1), [Ru(IBiox6)2(CO)(THF)H][BArF4] (11) and [Ru(IMes)(PPh3)(CO)HCl] respectively. 7 shows clean reactivity towards H2, yielding [Ru(IPr)2(CO)(eta2-H2)(H)2ZnMe][BArF4] (8), which undergoes loss of the co-ordinated dihydrogen ligand upon application of vacuum to form [Ru(IPr)2(CO)(H)2ZnMe][BArF4] (9). In contrast, addition of H2 to 12 gave only a mixture of products. The tetramethyl IBiox complex [Ru(IBioxMe4)2(CO)(THF)H][BArF4] (14) failed to give any isolable Ru-Zn containing species upon re-action with ZnMe2. The cyclometallated NHC complex [Ru(IMes)'(PPh3)(CO)ZnMe] (15) added H2 across the Ru-Zn bond both in solution and in the solid-state to afford [Ru(IMes)'(PPh3)(CO)(H)2ZnMe] (17), with retention of the cyclometallation.
Original languageEnglish
Pages (from-to)4176-4189
Number of pages14
JournalDalton Transactions
Volume48
Issue number13
Early online date19 Feb 2019
DOIs
Publication statusPublished - 26 Mar 2019

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Heterobimetallic Ruthenium-Zinc Complexes with Bulky N-Heterocyclic Carbenes: Syntheses, Structures and Reactivity. / Espinal-Viguri, Maialen; Varela-Izquerido, Victor; Miloserdov, Fedor; Riddlestone, Ian; Mahon, Mary; Whittlesey, Michael.

In: Dalton Transactions , Vol. 48, No. 13, 26.03.2019, p. 4176-4189.

Research output: Contribution to journalArticle

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abstract = "The ruthenium-zinc heterobimetallic complexes, [Ru(IPr)2(CO)ZnMe][BArF4] (7), [Ru(IBiox6)2(CO)(THF)ZnMe][BArF4] (12) and [Ru(IMes)(PPh3)(CO)ZnMe] (15), have been prepared by reaction of ZnMe2 with the ruthenium N-heterocyclic carbene complexes [Ru(IPr)2(CO)H][BArF4] (1), [Ru(IBiox6)2(CO)(THF)H][BArF4] (11) and [Ru(IMes)(PPh3)(CO)HCl] respectively. 7 shows clean reactivity towards H2, yielding [Ru(IPr)2(CO)(eta2-H2)(H)2ZnMe][BArF4] (8), which undergoes loss of the co-ordinated dihydrogen ligand upon application of vacuum to form [Ru(IPr)2(CO)(H)2ZnMe][BArF4] (9). In contrast, addition of H2 to 12 gave only a mixture of products. The tetramethyl IBiox complex [Ru(IBioxMe4)2(CO)(THF)H][BArF4] (14) failed to give any isolable Ru-Zn containing species upon re-action with ZnMe2. The cyclometallated NHC complex [Ru(IMes)'(PPh3)(CO)ZnMe] (15) added H2 across the Ru-Zn bond both in solution and in the solid-state to afford [Ru(IMes)'(PPh3)(CO)(H)2ZnMe] (17), with retention of the cyclometallation.",
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T1 - Heterobimetallic Ruthenium-Zinc Complexes with Bulky N-Heterocyclic Carbenes: Syntheses, Structures and Reactivity

AU - Espinal-Viguri, Maialen

AU - Varela-Izquerido, Victor

AU - Miloserdov, Fedor

AU - Riddlestone, Ian

AU - Mahon, Mary

AU - Whittlesey, Michael

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AB - The ruthenium-zinc heterobimetallic complexes, [Ru(IPr)2(CO)ZnMe][BArF4] (7), [Ru(IBiox6)2(CO)(THF)ZnMe][BArF4] (12) and [Ru(IMes)(PPh3)(CO)ZnMe] (15), have been prepared by reaction of ZnMe2 with the ruthenium N-heterocyclic carbene complexes [Ru(IPr)2(CO)H][BArF4] (1), [Ru(IBiox6)2(CO)(THF)H][BArF4] (11) and [Ru(IMes)(PPh3)(CO)HCl] respectively. 7 shows clean reactivity towards H2, yielding [Ru(IPr)2(CO)(eta2-H2)(H)2ZnMe][BArF4] (8), which undergoes loss of the co-ordinated dihydrogen ligand upon application of vacuum to form [Ru(IPr)2(CO)(H)2ZnMe][BArF4] (9). In contrast, addition of H2 to 12 gave only a mixture of products. The tetramethyl IBiox complex [Ru(IBioxMe4)2(CO)(THF)H][BArF4] (14) failed to give any isolable Ru-Zn containing species upon re-action with ZnMe2. The cyclometallated NHC complex [Ru(IMes)'(PPh3)(CO)ZnMe] (15) added H2 across the Ru-Zn bond both in solution and in the solid-state to afford [Ru(IMes)'(PPh3)(CO)(H)2ZnMe] (17), with retention of the cyclometallation.

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