Ring-expanded N-heterocyclic carbene complexes of rhodium with bifluoride, fluoride, and fluoroaryl ligands

C. Segarra, E. Mas-Marzá, John P Lowe, M.F. Mahon, R.C. Poulten, M.K. Whittlesey

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

Thermolysis of Rh(PPh)H in the presence of the six-membered N-heterocyclic carbene 1,3-bis(2-propyl)-3,4,5,6- tetrahydropyrimidin-2-ylidine (6-Pr) gave the monocarbene complex Rh(6-Pr)(PPh)H as a 1:2 mixture of the cis- and trans-phosphine isomers 1a and 1b. This same isomeric mixture was formed as the ultimate product from treating Rh(PPh)(CO)H with 6-Pr at room temperature, although pathways involving both CO and PPh loss were observed at initial times. Treatment of 1a/1b with EtN·3HF generated the bifluoride complex cis-Rh(6- Pr)(PPh)(FHF) (2a), which upon stirring with anhydrous MeNF was converted to the rhodium fluoride complex cis-Rh(6-Pr)(PPh)F (3a). Thermolysis of 1a/1b with CF resulted in C-F bond activation to afford a mixture of 3a and the pentafluorophenyl complex trans-Rh(6- Pr)(PPh)(CF) (5b). Complexes 1b, 2a, 3a, and 5b were structurally characterized.
Original languageEnglish
Pages (from-to)8584-8590
Number of pages7
JournalOrganometallics
Volume31
Issue number24
DOIs
Publication statusPublished - 24 Dec 2012

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Rhodium
carbenes
rhodium
Fluorides
fluorides
Thermolysis
phosphine
Carbon Monoxide
Ligands
ligands
rings
stirring
phosphines
Isomers
isomers
Chemical activation
activation
room temperature
products
carbene

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Ring-expanded N-heterocyclic carbene complexes of rhodium with bifluoride, fluoride, and fluoroaryl ligands. / Segarra, C.; Mas-Marzá, E.; Lowe, John P; Mahon, M.F.; Poulten, R.C.; Whittlesey, M.K.

In: Organometallics, Vol. 31, No. 24, 24.12.2012, p. 8584-8590.

Research output: Contribution to journalArticle

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AU - Poulten, R.C.

AU - Whittlesey, M.K.

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AB - Thermolysis of Rh(PPh)H in the presence of the six-membered N-heterocyclic carbene 1,3-bis(2-propyl)-3,4,5,6- tetrahydropyrimidin-2-ylidine (6-Pr) gave the monocarbene complex Rh(6-Pr)(PPh)H as a 1:2 mixture of the cis- and trans-phosphine isomers 1a and 1b. This same isomeric mixture was formed as the ultimate product from treating Rh(PPh)(CO)H with 6-Pr at room temperature, although pathways involving both CO and PPh loss were observed at initial times. Treatment of 1a/1b with EtN·3HF generated the bifluoride complex cis-Rh(6- Pr)(PPh)(FHF) (2a), which upon stirring with anhydrous MeNF was converted to the rhodium fluoride complex cis-Rh(6-Pr)(PPh)F (3a). Thermolysis of 1a/1b with CF resulted in C-F bond activation to afford a mixture of 3a and the pentafluorophenyl complex trans-Rh(6- Pr)(PPh)(CF) (5b). Complexes 1b, 2a, 3a, and 5b were structurally characterized.

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