Oxidative addition of thiols to (CO)3Mo(μ-dppm)2Ru(CO)3 with formation of hydrido, bridged-thiolate complexes (dppm=Ph2PCH2PPh2)

Khorasani-Motlagh, Mozhgan; Safari, Nasser; Pamplin, Craig B.; Patrick, Brian O.; James, Brian R.

doi:10.1016/j.ica.2009.12.002

Cited by 3 publications

(1 citation statement)

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“…Well-defined metal systems that can perform this type of reaction are actually scarce. Most of the known examples involve second or third row transition metals, heterobimetallic compounds, or clusters . As far as cobalt-based systems are concerned, trimethylphosphine-ligated complexes including (Me 3 P) 3 CoCl, (Me 3 P) 4 Co, (Me 3 P) 4 CoMe, , and even the high-valent (Me 3 P) 3 CoMe 3 have been used to activate thiols, although the mechanistic information about S–H oxidative addition is lost in the complexity of the reactions (e.g., consecutive S–H bond activation and/or an elimination step involving the SH hydrogen).…”

Section: Resultsmentioning

confidence: 99%

C(sp)–H, S–H, and Sn–H Bond Activation with a Cobalt(I) Pincer Complex

Saha,

Krause,

Guan

2024

Inorg. Chem.

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This study focuses on the stoichiometric reactions of {2,6-( i Pr2PO)2C6H3}Co(PMe3)2 with terminal alkynes, thiols, and tin hydrides as part of an effort to develop catalytic, two-electron processes with cobalt. This specific Co(I) pincer complex proves to be effective for cleaving the C(sp)–H, S–H, and Sn–H bonds to give oxidative addition products with the general formula {2,6-( i Pr2PO)2C6H3}CoHX(PMe3) (X = alkynyl, thiolate, and stannyl groups) along with the free PMe3. These reactions typically reach completion when the substituents on acetylene, sulfur, and tin are electron-withdrawing groups (e.g., phenyl, pyridyl, and alkenyl groups). In contrast, alkyl-substituted acetylenes, 1-pentanethiol, and tributyltin hydride are partially converted due to the equilibria with the corresponding oxidative addition products. The Co(I) pincer complex is not a hydrothiolation catalyst but capable of catalyzing the hydrostannation of terminal alkynes with Ph3SnH to produce β-(Z)-alkenylstannanes selectively.

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