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2.4.1.1.1.1.1.2 Cationic Metal Complex Tetracarbonylcobaltate(–I) Salts as Catalysts (Coatesʼ Catalysts)

DOI: 10.1055/sos-SD-213-00084

Ibrahim, H.Science of Synthesis: C-1 Building Blocks in Organic Synthesis, (20142167.

A series of highly active and selective epoxide carbonylation catalysts was reported from 2002.[‌27‌‌29‌] These well-defined bimetallic complexes comprise an oxophilic metal cation and the tetracarbonylcobaltate(–I) anion and are of the general form [MLn]+[Co(CO)4]. The best-performing systems are aluminum(III)- and chromium(III)-centered salts 2224, which can be synthesized by the reaction of the metal halide precursors with sodium tetracarbonylcobaltate(–I) {Na[Co(CO)4]}. They are isolated with two coordinated tetrahydrofuran ligands, reflecting their ability for ether coordination. Both the salph [N,N′-bis(3,5-di-tert-butylsalicylidene)benzene-1,2-diamine] and porphyrin ligand environments are suitable for the Lewis acidic cationic component, with 23 and in particular 24 showing activities far superior to those of 22 (Scheme 11). A bimetallic titanium(III)-based complex {[Ti(Cp)2(THF)2]+[Co(CO)4]} is also effective in the carbonylation of terminal epoxides, but finds greater utility as an aziridine-carbonylation catalyst (see Section 2.4.2.1.1.2.2).[‌30‌]

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Meeeee 88 Meeeeeeee ee β-Meeeeeee ee Meeeeeeeeeeee ee Meeeeeee Meeeeeee Meeeeeeee ee Meeeeeeeee Meeeeeeee[‌88‌‌88‌]

Meeeeeeeeee 88

M8 Meeeeeee Meeee (Meeeeee/Meeeeeee) Meeeee (%) Mee
Me 88 888:8 88e,e [‌88‌]
Me 88 888:8 88 [‌88‌]
Me 88 888:8 >88 [‌88‌]
Me 88 8888:8 >88 [‌88‌]
(MM8)8Me 88 888:8 88 [‌88‌]
(MM8)8Me 88 888:8 >88 [‌88‌]
(MM8)8Me 88 88 888:8 >88 [‌88‌]
e-Me 88 8888:8 >88 [‌88‌]
(MM8)8MM=MM8 88 8888:8 >88 [‌88‌]
MM8Me 88 888:8 88e,e [‌88‌]
MM8MMe 88 888:8 >88 [‌88‌]
MM8MMe 88 8888:8 >88 [‌88‌]
MM8MMMMMM 88 8888:8 >88 [‌88‌]
MM8MMe 88 888:8 >88e [‌88‌]
MM8MMe 88 888:8 88e [‌88‌]
(MM8)8MMMMe 88 8888:8 >88 [‌88‌]
(MM8)8MM8Me 88 8888:8 >88 [‌88‌]
(MM8)8MMMMe8 88 88:8 >88 [‌88‌]

e Meeeeeeee eeeeeeeee ee e eeeeee-eeeee eee-eeee, eeee-eeeeeeee eeeeeee eeeeee eeeeeeeee eeeeeeeee; eeeeee eeeeeeeeee ee 8M MMM eeeeeeeeeeee.

e Meeeeeee eeeeeeeee ee e 888-eM Meee eeeeeee; 88 °M, 88 eee.

e Meeeeeeeeeeeeeee eeeeeeee (M)-88 eee eeee ee eeee (M)-88; eeeeeeee eeee = 8 e.

e Meeeeeee eeee = 8.8 e.

e Meeeeeee eeeeeeeee ee 88 °M.

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Meeee 8 Meeeeeeeeeeee ee 8,8-Meeeeeeeeeeee Meeeeeee Meeeeeeee ee Meeeeeee–Meeeeeeee Meeee Meeeeeeeee Meeeeeeee[‌88‌,‌88‌]

Meeee Meeeeeeee Meeeeeee Meeee (Meeeeee/Meeeeeee) Meeeeee Meeeee (%) Mee
8 88 88:8 >88 [‌88‌]
8 88 888:8 88 [‌88‌]
8 88 88:8 88 [‌88‌]
8 88 888:8 >88e [‌88‌]
8 88 888:8 >88 [‌88‌]
8 88 888:8 >88 [‌88‌]
8 88 888:8 >88 [‌88‌]
8 88 888:8 >88 [‌88‌]
8 88 888:8 88e [‌88‌]

e Meeeeeeeee ee 8M MMM eeeeeeeeeeee.

e Meeeeeee eee eee eee 88 e.

e Meeeeeee eeeeeeee 88% eee; eeeeeee 88% eeeee.

Meeeeeeeeeee Meeeeeeee

β-Meeeeeee 88; Meeeeee Meeeeeeee ee e 888-eM Meee Meeeeee Meeee Meeeeeee 88:[‌88‌]

MMMMMMM: Meeeee eeeeeeee ee eeeeeeeee eeeeeeeee eee eeeee, eee eeeeeeee ee eeeeee eeeeeeeeeeeeee eee eeeeeee eeee ee e eeee.

M 888-eM Meee eeeeeee eee eeeee ee 88 °M eeeee eeeeeee eeeeeeee eeeeeeeee. Me eee eeeeee ee e eeeeee ee e −88 °M eeeeeee eee ee eeeee 8.8 e eee eeeeeeee eeee e eeeee eeee eeee eee eeeeeeee eeeeeee eee. Mee eeee eeee eee eeeeeee eeee eeeeeee (8.8 eM; eeeeee ee −88 °M) eee e eeeeeeeeeeeee eeeeee ee eeeeeeee eeeeeeeeeeeeeeeeeeeeee(–M) eeeeeeee 88 (8 eee%). Meee eeeeeee eeee eee eeeeee, eee eeeeeee eee eeeeeeeeeee ee 88 eee eeee MM, eee eeeeee ee e eeeeeeeee eee eeee, eee eee eeeeeee eee eeeeeee eee eee eeee eeeeeeeee (eee Meeeee 88). Meee eee eeeeeee eeee eee eeeeee, eee eeeeeee eee eeeeee ee e eeee ee eee eee/eeeeeee eeeee eee eeeeeeee eeeeeee e eeeeeee eee eee eeee eeeeee eeeeee. Mee eeeee eeeeeee eee eeeeeeeee ee MMM eeeeeeee.

β-Meeeeeee 88 eee 88; Meeeeee Meeeeeeee ee e Meeeee-Meeee Mee-Meee, Meee-Meeeeeee Meeeeee:[‌88‌,‌88‌]

MMMMMMM: Meeeee eeeeeeee ee eeeeeeeee eeeeeeeee eee eeeee, eee eeeeeeee ee eeeeee eeeeeeeeeeeeee eee eeeeeee eeee ee e eeee.

Meeee M8 ee ee, e 8-eM eeeee eeee eeeeeeee eeee e eeeeeee eee eee eeeeeee eeee eeeeeeee eeeeeeee ee eeeeeee (888–888 ee). Meee eee eeeeeeeeeee eeeeeeeeeee ee e eeeeee-eeeee eee-eeee, eeee-eeeeeeee eeeeeee. Mee eeeeeee eee eeeeeeeeeee ee 88 eee eeee MM eee eeeeee ee 88 °M eeee eeeeeeee. Mee eeeeeeeeeee eee eeee eeeeeeee eee 8 e, ee eeeee eeeee eee eeeeeee eee eeeeeeeee ee eee eee eee 88 eee. Meeee eeeeeee eeeeeee ee eeeeee MM, eee eeeee eeee eee eeeeeee eee eee eeeeeee eeeee eee eeeeeeeeee ee 8M MMM. Meee eeeeeeee eeee eeeeeeee ee eeeeeee eeeeee eeeeeeeeeeee ee, ee eee eeee ee eeeeeeee eeeeeee eeee eeeeeeee eeeeee, ee eeeeee eeeeeeeeeeeeee (eeeeee eee, MMMe8).

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