Highly Chemo- and Stereoselective Transfer Semihydrogenation of Alkynes Catalyzed by a Stable, Well-defined Manganese(II) Complex

Aleksandra Brzozowska; Luis Azofra Mesa; Viktoriia Zubar; Iuliana Atodiresei; Luigi Cavallo; Magnus Rueping; Osama El-Sepelgy

doi:10.1021/acscatal.8b00983

Highly Chemo- and Stereoselective Transfer Semihydrogenation of Alkynes Catalyzed by a Stable, Well-defined Manganese(II) Complex

Aleksandra Brzozowska, Luis Azofra Mesa, Viktoriia Zubar, Iuliana Atodiresei, Luigi Cavallo, Magnus Rueping, Osama El-Sepelgy

Research output: Contribution to journal › Article › peer-review

95 Scopus citations

Abstract

The first example of manganese catalyzed semihydrogenation of internal alkynes to (Z)-alkenes using ammonia borane as a hydrogen donor is reported. The reaction is catalyzed by a pincer complex of the earth abundant manganese(II) salt in the absence of any additives, base or super hydride. The ammonia borane smoothly reduces the manganese pre-catalyst [Mn(II)-PNP][Cl]2 to the catalytically active species [Mn(I)-PNP]-hydride in the triplet spin state. This manganese hydride is highly stabilized by complexation with the alkyne substrate. Computational DFT analysis studies of the reaction mechanism rationalizes the origin of stereoselectivity towards formation of (Z)-alkenes.

Original language	English (US)
Pages (from-to)	4103-4109
Number of pages	7
Journal	ACS Catalysis
Volume	8
Issue number	5
DOIs	https://doi.org/10.1021/acscatal.8b00983
State	Published - Mar 30 2018

Access to Document

10.1021/acscatal.8b00983

https://repository.kaust.edu.sa/bitstream/10754/627512/1/acscatal.8b00983.pdf

Cite this

@article{d2a684d576c94e4c9279f55ef6bf8c3a,

title = "Highly Chemo- and Stereoselective Transfer Semihydrogenation of Alkynes Catalyzed by a Stable, Well-defined Manganese(II) Complex",

abstract = "The first example of manganese catalyzed semihydrogenation of internal alkynes to (Z)-alkenes using ammonia borane as a hydrogen donor is reported. The reaction is catalyzed by a pincer complex of the earth abundant manganese(II) salt in the absence of any additives, base or super hydride. The ammonia borane smoothly reduces the manganese pre-catalyst [Mn(II)-PNP][Cl]2 to the catalytically active species [Mn(I)-PNP]-hydride in the triplet spin state. This manganese hydride is highly stabilized by complexation with the alkyne substrate. Computational DFT analysis studies of the reaction mechanism rationalizes the origin of stereoselectivity towards formation of (Z)-alkenes.",

author = "Aleksandra Brzozowska and {Azofra Mesa}, Luis and Viktoriia Zubar and Iuliana Atodiresei and Luigi Cavallo and Magnus Rueping and Osama El-Sepelgy",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: L.M.A. and L.C., acknowledge King Abdullah University of Science and Technology (KAUST) for support. Gratitude is also due to the KAUST Supercomputing Laboratory using the supercomputer Shaheen II for providing the computational resources.",

year = "2018",

month = mar,

day = "30",

doi = "10.1021/acscatal.8b00983",

language = "English (US)",

volume = "8",

pages = "4103--4109",

journal = "ACS Catalysis",

issn = "2155-5435",

publisher = "American Chemical Society",

number = "5",

}

TY - JOUR

T1 - Highly Chemo- and Stereoselective Transfer Semihydrogenation of Alkynes Catalyzed by a Stable, Well-defined Manganese(II) Complex

AU - Brzozowska, Aleksandra

AU - Azofra Mesa, Luis

AU - Zubar, Viktoriia

AU - Atodiresei, Iuliana

AU - Cavallo, Luigi

AU - Rueping, Magnus

AU - El-Sepelgy, Osama

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: L.M.A. and L.C., acknowledge King Abdullah University of Science and Technology (KAUST) for support. Gratitude is also due to the KAUST Supercomputing Laboratory using the supercomputer Shaheen II for providing the computational resources.

PY - 2018/3/30

Y1 - 2018/3/30

N2 - The first example of manganese catalyzed semihydrogenation of internal alkynes to (Z)-alkenes using ammonia borane as a hydrogen donor is reported. The reaction is catalyzed by a pincer complex of the earth abundant manganese(II) salt in the absence of any additives, base or super hydride. The ammonia borane smoothly reduces the manganese pre-catalyst [Mn(II)-PNP][Cl]2 to the catalytically active species [Mn(I)-PNP]-hydride in the triplet spin state. This manganese hydride is highly stabilized by complexation with the alkyne substrate. Computational DFT analysis studies of the reaction mechanism rationalizes the origin of stereoselectivity towards formation of (Z)-alkenes.

AB - The first example of manganese catalyzed semihydrogenation of internal alkynes to (Z)-alkenes using ammonia borane as a hydrogen donor is reported. The reaction is catalyzed by a pincer complex of the earth abundant manganese(II) salt in the absence of any additives, base or super hydride. The ammonia borane smoothly reduces the manganese pre-catalyst [Mn(II)-PNP][Cl]2 to the catalytically active species [Mn(I)-PNP]-hydride in the triplet spin state. This manganese hydride is highly stabilized by complexation with the alkyne substrate. Computational DFT analysis studies of the reaction mechanism rationalizes the origin of stereoselectivity towards formation of (Z)-alkenes.

UR - http://hdl.handle.net/10754/627512

UR - https://pubs.acs.org/doi/10.1021/acscatal.8b00983

UR - http://www.scopus.com/inward/record.url?scp=85046679566&partnerID=8YFLogxK

U2 - 10.1021/acscatal.8b00983

DO - 10.1021/acscatal.8b00983

M3 - Article

SN - 2155-5435

VL - 8

SP - 4103

EP - 4109

JO - ACS Catalysis

JF - ACS Catalysis

IS - 5

ER -

Highly Chemo- and Stereoselective Transfer Semihydrogenation of Alkynes Catalyzed by a Stable, Well-defined Manganese(II) Complex

Abstract

Access to Document

Other files and links

Fingerprint

Cite this