0000000000079600
AUTHOR
Juuso Valjus
Computational investigations of 18-electron triatomic sulfur–nitrogen anions
MRCI-SD/def2-QZVP and PBE0/def2-QZVP calculations have been employed for the analysis of geometries, stabilities, and bonding of isomers of the 18-electron anions N2S2−, NS2−, and NSO−. Isomers of the isoelectronic neutral molecules SO2, S2O, S3, and O3 are included for comparison. The sulfur-centered acyclic NSN2−, NSS−, and NSO− anions are the most stable isomers of their respective molecular compositions. However, the nitrogen-centered isomers SNS− and SNO− lie close enough in energy to their more stable counterparts to allow their occurrence. The experimental structural information, where available, is in good agreement with the optimized bond parameters. The bonding in all investigate…
Phosphorus-Chalcogen Ring Expansion and Metal Coordination
The reactivity of 4-membered (RPCh)2 rings (Ch = S, Se) that contain phosphorus in the +3 oxidation state is reported. These compounds undergo ring expansion to (RPCh)3 with the addition of a Lewis base. The 6-membered rings were found to be more stable than the 4-membered precursors, and the mechanism of their formation was investigated experimentally and by density functional theory calculations. The computational work identified two plausible mechanisms involving a phosphinidene chalcogenide intermediate, either as a free species or stabilized by a suitable base. Both the 4- and 6-membered rings were found to react with coinage metals, giving the same products: (RPCh)3 rings bound to the…
Haptotropism in a Nickel Complex with a Neutral, π‐Bridging cyclo ‐P 4 Ligand Analogous to Cyclobutadiene
Haptotropism in a Nickel Complex with a Neutral, π‐Bridging cyclo‐P4 Ligand Analogous to Cyclobutadiene
The reaction of ( 1 )Ni(η 2 -cod), 2 , incorporating a chelating bis( N -heterocyclic carbene) 1 , with P 4 in pentane yielded the dinuclear complex [( 2 )Ni] 2 (μ 2 ,η 2 :η 2 -P 4 ), 3 , formally featuring a cyclobutadiene-like, neutral, rectangular, π-bridging P 4 -ring. In toluene, the butterfly-shaped complex [( 1 )Ni] 2 (μ 2 ,η 2 :η 2 -P 2 ), 4 , with a formally neutral P 2 -unit was obtained from 2 and either P 4 or 3 . Computational studies showed that a low energy barrier haptotropic rearrangement involving two isomers of the μ 2 ,η 2 :η 2 -P 4 coordination mode and a low energy μ 2 ,η 4 :η 4 -P 4 coordination mode, as previously predicted for related nickel cyclobutadiene complexes…
Preparation and Characterization of P2 BCh Ring Systems (Ch=S, Se) and Their Reactivity with N-Heterocyclic Carbenes
Four-membered rings with a P2BCh core (Ch = S, Se) have been synthesized via reaction of phosphinidene chalcogenide (Ar*P=Ch) and phosphaborene (Mes*P=BNR2). The mechanistic pathways towards these rings are explained by detailed computational work that confirmed the preference for the formation of P–P, not P–B, bonded systems, which seems counterintuitive given that both phosphorus atoms contain bulky ligands. The reactivity of the newly synthesized heterocycles, as well as that of the known (RPCh)n rings (n = 2, 3), was probed by the addition of Nheterocyclic carbenes, which revealed that all investigated compounds can act as sources of low-coordinate phosphorus species. peerReviewed
Ammonia Activation by a Nickel NCN-Pincer Complex featuring a Non-Innocent N-Heterocyclic Carbene: Ammine and Amido Complexes in Equilibrium
A Ni0-NCN pincer complex featuring a six-membered N-heterocyclic carbene (NHC) central platform and amidine pendant arms was synthesized by deprotonation of its NiII precursor. It retained chloride in the square-planar coordination sphere of nickel and was expected to be highly susceptible to oxidative addition reactions. The Ni0 complex rapidly activated ammonia at room temperature, in a ligand-assisted process where the carbene carbon atom played the unprecedented role of proton acceptor. For the first time, the coordinated (ammine) and activated (amido) species were observed together in solution, in a solvent-dependent equilibrium. A structural analysis of the Ni complexes provided insig…
Trapping Rare and Elusive Phosphinidene Chalcogenides
Four-membered rings with a P2Ch2 core (Ch=S, Se) and phosphorus in the +3 oxidation state have been synthesized. The utility of these rings as a source of monomeric phosphinidene chalcogenides was probed by the addition of an N-heterocyclic carbene, resulting in a base-stabilized phosphinidene sulfide. Similarly, persistence of the phosphinidene selenide in solution was shown through cycloaddition chemistry with 2,3-dimethylbutadiene at elevated temperatures. The observed reactivity was explained by detailed computational work that established the conditions upon which the P2Ch2 rings can liberate phosphinidene chalcogenides. peerReviewed
Nickel as a Lewis Base in a T‐Shaped Nickel(0) Germylene Complex Incorporating a Flexible Bis(NHC) Ligand
Flexible, chelating bis(NHC) ligand 2, able to accommodate both cis- and trans-coordination modes, was used to synthesize (2)Ni(η 2 -cod), 3. In reaction with GeCl2, this produced (2)NiGeCl2, 4, featuring a T-shaped Ni(0) and a pyramidal Ge center. Complex 4 could also be prepared from [(2)GeCl]Cl, 5, and Ni(cod)2, in a reaction that formally involved Ni-Ge transmetalation, followed by coordination of the extruded GeCl2 moiety to Ni. A computational analysis showed that 4 possesses considerable multiconfigurational character and the Ni→Ge bond is formed through σ-donation from the Ni 4s, 4p, and 3d orbitals to Ge. (NHC)2Ni(cod) complexes 9 and 10, as well as (NHC)2GeCl2 derivative 11, incor…
CCDC 1569579: Experimental Crystal Structure Determination
Related Article: Cameron M. E. Graham, Juuso Valjus, Taylor E. Pritchard, Paul D. Boyle, Heikki M. Tuononen, Paul J. Ragogna|2017|Inorg.Chem.|56|13500|doi:10.1021/acs.inorgchem.7b02217
CCDC 1861477: Experimental Crystal Structure Determination
Related Article: Chris Gendy, Akseli Mansikkamäki, Juuso Valjus, Joshua Heidebrecht, Paul Chuk-Yan Hui, Guy M. Bernard, Heikki M. Tuononen, Roderick E. Wasylishen, Vladimir K. Michaelis, Roland Roesler|2019|Angew.Chem.,Int.Ed.|58|154|doi:10.1002/anie.201809889
CCDC 1861476: Experimental Crystal Structure Determination
Related Article: Chris Gendy, Akseli Mansikkamäki, Juuso Valjus, Joshua Heidebrecht, Paul Chuk-Yan Hui, Guy M. Bernard, Heikki M. Tuononen, Roderick E. Wasylishen, Vladimir K. Michaelis, Roland Roesler|2019|Angew.Chem.,Int.Ed.|58|154|doi:10.1002/anie.201809889
CCDC 1861475: Experimental Crystal Structure Determination
Related Article: Chris Gendy, Akseli Mansikkamäki, Juuso Valjus, Joshua Heidebrecht, Paul Chuk-Yan Hui, Guy M. Bernard, Heikki M. Tuononen, Roderick E. Wasylishen, Vladimir K. Michaelis, Roland Roesler|2019|Angew.Chem.,Int.Ed.|58|154|doi:10.1002/anie.201809889
CCDC 1861479: Experimental Crystal Structure Determination
Related Article: Chris Gendy, Akseli Mansikkamäki, Juuso Valjus, Joshua Heidebrecht, Paul Chuk-Yan Hui, Guy M. Bernard, Heikki M. Tuononen, Roderick E. Wasylishen, Vladimir K. Michaelis, Roland Roesler|2019|Angew.Chem.,Int.Ed.|58|154|doi:10.1002/anie.201809889
CCDC 2115737: Experimental Crystal Structure Determination
Related Article: Chris Gendy, Juuso Valjus, Roland Roesler, Heikki M. Tuononen|2022|Angew.Chem.,Int.Ed.|61|e202115692|doi:10.1002/anie.202115692
CCDC 1405505: Experimental Crystal Structure Determination
Related Article: Rudy M. Brown, Javier Borau Garcia, Juuso Valjus, Christopher J. Roberts, Heikki M. Tuononen, Masood Parvez, and Roland Roesler|2015|Angew.Chem.,Int.Ed.|54|6274|doi:10.1002/anie.201500453
CCDC 2115739: Experimental Crystal Structure Determination
Related Article: Chris Gendy, Juuso Valjus, Roland Roesler, Heikki M. Tuononen|2022|Angew.Chem.,Int.Ed.|61|e202115692|doi:10.1002/anie.202115692
CCDC 1485222: Experimental Crystal Structure Determination
Related Article: Cameron M. E. Graham, Taylor E. Pritchard, Paul D. Boyle, Juuso Valjus, Heikki M. Tuononen, Paul J. Ragogna|2017|Angew.Chem.,Int.Ed.|56|6236|doi:10.1002/anie.201611196
CCDC 1861473: Experimental Crystal Structure Determination
Related Article: Chris Gendy, Akseli Mansikkamäki, Juuso Valjus, Joshua Heidebrecht, Paul Chuk-Yan Hui, Guy M. Bernard, Heikki M. Tuononen, Roderick E. Wasylishen, Vladimir K. Michaelis, Roland Roesler|2019|Angew.Chem.,Int.Ed.|58|154|doi:10.1002/anie.201809889
CCDC 1569581: Experimental Crystal Structure Determination
Related Article: Cameron M. E. Graham, Juuso Valjus, Taylor E. Pritchard, Paul D. Boyle, Heikki M. Tuononen, Paul J. Ragogna|2017|Inorg.Chem.|56|13500|doi:10.1021/acs.inorgchem.7b02217
CCDC 1861471: Experimental Crystal Structure Determination
Related Article: Chris Gendy, Akseli Mansikkamäki, Juuso Valjus, Joshua Heidebrecht, Paul Chuk-Yan Hui, Guy M. Bernard, Heikki M. Tuononen, Roderick E. Wasylishen, Vladimir K. Michaelis, Roland Roesler|2019|Angew.Chem.,Int.Ed.|58|154|doi:10.1002/anie.201809889
CCDC 2115738: Experimental Crystal Structure Determination
Related Article: Chris Gendy, Juuso Valjus, Roland Roesler, Heikki M. Tuononen|2022|Angew.Chem.,Int.Ed.|61|e202115692|doi:10.1002/anie.202115692
CCDC 1569577: Experimental Crystal Structure Determination
Related Article: Cameron M. E. Graham, Juuso Valjus, Taylor E. Pritchard, Paul D. Boyle, Heikki M. Tuononen, Paul J. Ragogna|2017|Inorg.Chem.|56|13500|doi:10.1021/acs.inorgchem.7b02217
CCDC 1861472: Experimental Crystal Structure Determination
Related Article: Chris Gendy, Akseli Mansikkamäki, Juuso Valjus, Joshua Heidebrecht, Paul Chuk-Yan Hui, Guy M. Bernard, Heikki M. Tuononen, Roderick E. Wasylishen, Vladimir K. Michaelis, Roland Roesler|2019|Angew.Chem.,Int.Ed.|58|154|doi:10.1002/anie.201809889
CCDC 1861474: Experimental Crystal Structure Determination
Related Article: Chris Gendy, Akseli Mansikkamäki, Juuso Valjus, Joshua Heidebrecht, Paul Chuk-Yan Hui, Guy M. Bernard, Heikki M. Tuononen, Roderick E. Wasylishen, Vladimir K. Michaelis, Roland Roesler|2019|Angew.Chem.,Int.Ed.|58|154|doi:10.1002/anie.201809889
CCDC 1485220: Experimental Crystal Structure Determination
Related Article: Cameron M. E. Graham, Taylor E. Pritchard, Paul D. Boyle, Juuso Valjus, Heikki M. Tuononen, Paul J. Ragogna|2017|Angew.Chem.,Int.Ed.|56|6236|doi:10.1002/anie.201611196
CCDC 1861478: Experimental Crystal Structure Determination
Related Article: Chris Gendy, Akseli Mansikkamäki, Juuso Valjus, Joshua Heidebrecht, Paul Chuk-Yan Hui, Guy M. Bernard, Heikki M. Tuononen, Roderick E. Wasylishen, Vladimir K. Michaelis, Roland Roesler|2019|Angew.Chem.,Int.Ed.|58|154|doi:10.1002/anie.201809889
CCDC 1569578: Experimental Crystal Structure Determination
Related Article: Cameron M. E. Graham, Juuso Valjus, Taylor E. Pritchard, Paul D. Boyle, Heikki M. Tuononen, Paul J. Ragogna|2017|Inorg.Chem.|56|13500|doi:10.1021/acs.inorgchem.7b02217
CCDC 1485223: Experimental Crystal Structure Determination
Related Article: Cameron M. E. Graham, Taylor E. Pritchard, Paul D. Boyle, Juuso Valjus, Heikki M. Tuononen, Paul J. Ragogna|2017|Angew.Chem.,Int.Ed.|56|6236|doi:10.1002/anie.201611196
CCDC 1405504: Experimental Crystal Structure Determination
Related Article: Rudy M. Brown, Javier Borau Garcia, Juuso Valjus, Christopher J. Roberts, Heikki M. Tuononen, Masood Parvez, and Roland Roesler|2015|Angew.Chem.,Int.Ed.|54|6274|doi:10.1002/anie.201500453
CCDC 1569582: Experimental Crystal Structure Determination
Related Article: Cameron M. E. Graham, Juuso Valjus, Taylor E. Pritchard, Paul D. Boyle, Heikki M. Tuononen, Paul J. Ragogna|2017|Inorg.Chem.|56|13500|doi:10.1021/acs.inorgchem.7b02217
CCDC 1569580: Experimental Crystal Structure Determination
Related Article: Cameron M. E. Graham, Juuso Valjus, Taylor E. Pritchard, Paul D. Boyle, Heikki M. Tuononen, Paul J. Ragogna|2017|Inorg.Chem.|56|13500|doi:10.1021/acs.inorgchem.7b02217
CCDC 1485221: Experimental Crystal Structure Determination
Related Article: Cameron M. E. Graham, Taylor E. Pritchard, Paul D. Boyle, Juuso Valjus, Heikki M. Tuononen, Paul J. Ragogna|2017|Angew.Chem.,Int.Ed.|56|6236|doi:10.1002/anie.201611196