In situ Mo(CO)₆-based catalysts for alkyne metathesis: Silanols vs phenols as co-catalysts under thermal and photochemical activation

Zaranek, Maciej; Robaszkiewicz, Jakub; Janica, Iwona; Gauvin, Régis M.; Pawluć, Piotr; Mortreux, André

doi:10.1016/j.catcom.2020.105944

Cited by 5 publications

(2 citation statements)

References 26 publications

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“…135 Combination of 70 with tridentate ligands like 75 and 76 generated catalytic systems that are highly tolerant of sensitive functional groups and protic sites. 136 Complexes without a M�CR moiety could also serve as alkyne metathesis catalyst precursors, e.g., WO 3 on silica, 137 Mo(CO) 6 /phenols (or silanols), 138 Mo{N(tBu)Ar} 3 /CH 2 Cl 2 , 50 MoCl{N(tBu)-Ar} 3 , 49 and Mo(VI) nitrido complexes L n Mo�N (see below).…”

Section: High Valent Hydrocarbyl Alkylidyne Complexes Of Mo and Wmentioning

confidence: 99%

Organometallic Chemistry of Transition Metal Alkylidyne Complexes Centered at Metathesis Reactions

Cui

Jia

2022

J. Am. Chem. Soc.

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Transition metals form a variety of alkylidyne complexes with either a d0 metal center (high-valent) or a non-d0 metal center (low-valent). One of the most interesting properties of alkylidyne complexes is that they can undergo or mediate metathesis reactions. The most well-studied metathesis reactions are alkyne metathesis involving high-valent alkylidynes. High-valent alkylidynes can also undergo metathesis reactions with heterotriple bonded species such as NCR, PCR, and NNR+. Metathesis reactions involving low-valent alkylidynes are less known. Highly efficient alkyne metathesis catalysts have been developed based on Mo(VI) and W(VI) alkylidynes. Catalytic cross-metathesis of nitriles with alkynes has also been achieved with M(VI) (M = W, Mo) alkylidyne or nitrido complexes. The metathesis activity of alkylidyne complexes is sensitively dependent on metals, supporting ligands and substituents of alkylidynes. Beyond metathesis, metal alkylidynes can also promote other reactions including alkyne polymerization. The remaining shortcomings and opportunities in the field are assessed.

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Section: High Valent Hydrocarbyl Alkylidyne Complexes Of Mo and Wmentioning

confidence: 99%

Organometallic Chemistry of Transition Metal Alkylidyne Complexes Centered at Metathesis Reactions

Cui

Jia

2022

J. Am. Chem. Soc.

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“…Dimethyl(naphthyl)silanol was synthesised as reported previously. [19] [Mo(CO)3(mes)], [20] [Mo(CO)4(nbd)], [21] [Mo(CO) 4 (cod)], [22] [Mo(CO) 3 (MeCN) 3 ], [23] [Mo(CO) 3 (PhCN) 3 ], [24] and [Mo(CO) 3 (py) 3 ] [25] were synthesised according do known literature procedures. GC analyses were performed on a Bruker 436-GC gas chromatograph with a TCD detector using decane as reference.…”

Section: General Remarksmentioning

confidence: 99%

Acceleration of alkyne metathesis in multicomponent catalytic systems by use of alternative Mo(0) sources under optimised conditions

Zaranek

Robaszkiewicz

2021

Preprint

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Abstract. Alkyne metathesis in multicomponent catalytic systems, although subject to changes, is still a domain of molybdenum hexacarbonyl as a source of Mo(0). Our findings show that this coordination compound is relatively inert under metathesis conditions, which results in noticeably long induction of catalytic activity, and the kinetics of this transformation can greatly benefit from switching to more labile Mo(0) complexes. Several easily obtainable ones had been tested and [Mo(CO)3(py)3] has been chosen as the one exhibiting the most desired features, i.e. nearly instant catalytic activity and relative stability in the air.

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Acceleration of alkyne metathesis in multicomponent catalytic systems by use of alternative Mo(0) sources under optimised conditions

Zaranek

Robaszkiewicz

2022

Catalysis Communications

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In situ Mo(CO)₆-based catalysts for alkyne metathesis: Silanols vs phenols as co-catalysts under thermal and photochemical activation

Cited by 5 publications

References 26 publications

Organometallic Chemistry of Transition Metal Alkylidyne Complexes Centered at Metathesis Reactions

Organometallic Chemistry of Transition Metal Alkylidyne Complexes Centered at Metathesis Reactions

Acceleration of alkyne metathesis in multicomponent catalytic systems by use of alternative Mo(0) sources under optimised conditions

Acceleration of alkyne metathesis in multicomponent catalytic systems by use of alternative Mo(0) sources under optimised conditions

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