Stoichiometric and catalytic reactivity of Ni(6-Mes)(PPh3)2

Sara Sabater; Michael Page; Mary F Mahon; Michael K Whittlesey

doi:10.1021/acs.organomet.7b00129

Stoichiometric and catalytic reactivity of Ni(6-Mes)(PPh₃)₂

Sara Sabater, Michael Page, Mary F Mahon, Michael K Whittlesey

Department of Chemistry

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Abstract

The three-coordinate Ni(0) N-heterocyclic carbene complex Ni(6-Mes)(PPh3)2 (1; 6-Mes = 1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene) is formed in the reaction of Ni(cod)2 with a 1:2 mixture of 6-Mes and PPh3 or upon reduction of Ni(6-Mes)(PPh3)Br (2) with KOtBu. Facile substitution of PPh3 in 1 gave a range of Ni(6-Mes)(PPh3)(L) products (L = PhC≡CMe (3), PhCH═CH2 (4), Ph2CO (5), PhCHO (6)). Oxidative addition of C6F6 gave Ni(6-Mes)(PPh3)(C6F5)F (7), while 1 was also oxidized by 4-BrC6H4F to afford a mixture of 2 and Ni(6-Mes)(PPh3)(C6H4F)Br (8). Surprisingly, 1 was also oxidized upon reaction with the small 5-membered ring NHC IMe4 to give the terminal Ni(II) phosphido complex Ni(IMe4)2(PPh2)Ph (9). Compounds 1 and 5 proved to be active as a precursors for the catalytic transfer hydrogenation of ketones.

Original language	English
Pages (from-to)	1776-1783
Journal	Organometallics
Volume	36
Issue number	9
Early online date	19 Apr 2017
DOIs	https://doi.org/10.1021/acs.organomet.7b00129
Publication status	Published - 8 May 2017

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Whittlesey revised submission
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see: https://doi.org/10.1021/acs.organomet.7b00129
Accepted author manuscript, 1.64 MB

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title = "Stoichiometric and catalytic reactivity of Ni(6-Mes)(PPh3)2",

abstract = "The three-coordinate Ni(0) N-heterocyclic carbene complex Ni(6-Mes)(PPh3)2 (1; 6-Mes = 1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene) is formed in the reaction of Ni(cod)2 with a 1:2 mixture of 6-Mes and PPh3 or upon reduction of Ni(6-Mes)(PPh3)Br (2) with KOtBu. Facile substitution of PPh3 in 1 gave a range of Ni(6-Mes)(PPh3)(L) products (L = PhC≡CMe (3), PhCH═CH2 (4), Ph2CO (5), PhCHO (6)). Oxidative addition of C6F6 gave Ni(6-Mes)(PPh3)(C6F5)F (7), while 1 was also oxidized by 4-BrC6H4F to afford a mixture of 2 and Ni(6-Mes)(PPh3)(C6H4F)Br (8). Surprisingly, 1 was also oxidized upon reaction with the small 5-membered ring NHC IMe4 to give the terminal Ni(II) phosphido complex Ni(IMe4)2(PPh2)Ph (9). Compounds 1 and 5 proved to be active as a precursors for the catalytic transfer hydrogenation of ketones.",

author = "Sara Sabater and Michael Page and Mahon, {Mary F} and Whittlesey, {Michael K}",

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doi = "10.1021/acs.organomet.7b00129",

language = "English",

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T1 - Stoichiometric and catalytic reactivity of Ni(6-Mes)(PPh3)2

AU - Sabater, Sara

AU - Page, Michael

AU - Mahon, Mary F

AU - Whittlesey, Michael K

PY - 2017/5/8

Y1 - 2017/5/8

N2 - The three-coordinate Ni(0) N-heterocyclic carbene complex Ni(6-Mes)(PPh3)2 (1; 6-Mes = 1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene) is formed in the reaction of Ni(cod)2 with a 1:2 mixture of 6-Mes and PPh3 or upon reduction of Ni(6-Mes)(PPh3)Br (2) with KOtBu. Facile substitution of PPh3 in 1 gave a range of Ni(6-Mes)(PPh3)(L) products (L = PhC≡CMe (3), PhCH═CH2 (4), Ph2CO (5), PhCHO (6)). Oxidative addition of C6F6 gave Ni(6-Mes)(PPh3)(C6F5)F (7), while 1 was also oxidized by 4-BrC6H4F to afford a mixture of 2 and Ni(6-Mes)(PPh3)(C6H4F)Br (8). Surprisingly, 1 was also oxidized upon reaction with the small 5-membered ring NHC IMe4 to give the terminal Ni(II) phosphido complex Ni(IMe4)2(PPh2)Ph (9). Compounds 1 and 5 proved to be active as a precursors for the catalytic transfer hydrogenation of ketones.

AB - The three-coordinate Ni(0) N-heterocyclic carbene complex Ni(6-Mes)(PPh3)2 (1; 6-Mes = 1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene) is formed in the reaction of Ni(cod)2 with a 1:2 mixture of 6-Mes and PPh3 or upon reduction of Ni(6-Mes)(PPh3)Br (2) with KOtBu. Facile substitution of PPh3 in 1 gave a range of Ni(6-Mes)(PPh3)(L) products (L = PhC≡CMe (3), PhCH═CH2 (4), Ph2CO (5), PhCHO (6)). Oxidative addition of C6F6 gave Ni(6-Mes)(PPh3)(C6F5)F (7), while 1 was also oxidized by 4-BrC6H4F to afford a mixture of 2 and Ni(6-Mes)(PPh3)(C6H4F)Br (8). Surprisingly, 1 was also oxidized upon reaction with the small 5-membered ring NHC IMe4 to give the terminal Ni(II) phosphido complex Ni(IMe4)2(PPh2)Ph (9). Compounds 1 and 5 proved to be active as a precursors for the catalytic transfer hydrogenation of ketones.

UR - https://doi.org/10.1021/acs.organomet.7b00129

U2 - 10.1021/acs.organomet.7b00129

DO - 10.1021/acs.organomet.7b00129

M3 - Article

VL - 36

SP - 1776

EP - 1783

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 9

ER -

Stoichiometric and catalytic reactivity of Ni(6-Mes)(PPh₃)₂

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