Structure and dynamics of neutral beta-H agostic nickel alkyls: a combined experimental and theoretical study

Journal of the American Chemical Society
Elzbieta KogutThomas Strassner

Abstract

Addition of BF(3).OEt(2) to ethereal solutions of the Ni(II) beta-diketiminates [Me(2)NN]Ni(R)(2,4-lutidine) (R = Et (1), Pr (2)) allows the isolation of the neutral beta-H agostic monoalkyls [Me(2)NN]Ni(R) (R = Et (3), Pr (4)). X-ray studies of primary alkyls 3 and 4a reveal acute Ni-C(alpha)-C(beta) angles with short Ni-C(beta) distances, indicating structures along the beta-H elimination pathway. Positional disorder of the alkyl group in the X-ray structure of 4 corresponds to partial (22%) occupancy by the secondary alkyl [Me(2)NN]Ni(CHMe(2)) (4b). Variable-temperature NMR spectra of 3 and 4 reveal fluxional behavior that result from beta-H elimination, in-plane rotation of the beta-CH(3) group, and a tetrahedral triplet structure for 3 that were investigated by density functional theory calculations at the Becke3LYP/6-31G level of theory without simplifications on the beta-diketiminate ancillary ligand. Calculations support low temperature NMR studies that identify the linear beta-H agostic propyl isomer 4a as the ground state with the branched beta-H agostic isomer 4b slightly higher in energy. NMR studies and calculations show that the beta-agostic 3 reluctantly coordinates ethene and that 3 is the ground state for this ...Continue Reading

References

Jan 1, 1995·Acta Crystallographica. Section A, Foundations of Crystallography·R H Blessing
Mar 26, 1999·Science·Z GuanS J McLain
Mar 18, 2000·Journal of Computer-aided Molecular Design·G Schaftenaar, J H Noordik
Apr 11, 2000·Accounts of Chemical Research·D SchröderH Schwarz
Dec 26, 2001·Chemical Reviews·S D IttelM Brookhart
Nov 28, 2002·Journal of the American Chemical Society·Patrick L HollandRene J Lachicotte
Oct 2, 2003·Chemical Communications : Chem Comm·Eric F ConnorRobert H Grubbs
Nov 16, 1998·Angewandte Chemie·Bernd DomhöverDietrich Mootz
Feb 15, 1999·Angewandte Chemie·George J P BritovsekDuncan F Wass

❮ Previous
Next ❯

Citations

Sep 11, 2010·Journal of the American Chemical Society·Stefan PfirrmannReinhard Stösser
May 24, 2012·Journal of the American Chemical Society·Stefan WieseTimothy H Warren
Jan 9, 2009·Journal of the American Chemical Society·Zengming ShenVy M Dong
Apr 29, 2009·Journal of the American Chemical Society·Taryn D ForsterRoland Roesler
Mar 16, 2006·Chemical Communications : Chem Comm·Zhiqiang WengT S Andy Hor
Jan 21, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Stefan PfirrmannBurkhard Ziemer
Jul 23, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Liqin XueZhenyang Lin
Jul 21, 2016·Chemical Reviews·Nathan A Eberhardt, Hairong Guan
Dec 15, 2016·Journal of the American Chemical Society·Eric D MetzgerMircea Dincă
Sep 6, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Francesca MiloccoBarbara Milani
Feb 14, 2006·Angewandte Chemie·Javier VelaPatrick L Holland
Mar 28, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Casper M MacaulayLaura Turculet
Jan 8, 2013·Chemistry : a European Journal·Henrike GehringChristian Limberg
Oct 31, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Boodsarin SawatlonPanida Surawatanawong
Aug 16, 2018·Royal Society Open Science·Qaiser Mahmood, Wen-Hua Sun
Oct 13, 2009·The Journal of Physical Chemistry. a·Vincent TognettiCarlo Adamo
Aug 25, 2005·Journal of the American Chemical Society·Travis M AndersonCraig L Hill
Apr 3, 2020·Accounts of Chemical Research·Justin DiccianniTianning Diao
Oct 18, 2014·Inorganic Chemistry·Brooke M OttenThomas R Cundari
Sep 11, 2014·Journal of the American Chemical Society·Shu A YaoJohn F Berry
Mar 3, 2005·Journal of the American Chemical Society·Bun Yeoul LeeYoung-Whan Park
Aug 23, 2007·Journal of the American Chemical Society·Rui CaoCraig L Hill
Aug 11, 2005·Journal of the American Chemical Society·Elzbieta KogutTimothy H Warren

❮ Previous
Next ❯

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.