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…

Low‐Valent Germanylidene Anions: Efficient Single‐Site Nucleophiles for Activation of Small Molecules

Abstract Rare mononuclear and helical chain low‐valent germanylidene anions supported by cyclic (alkyl)(amino)carbene and hypermetallyl ligands were synthesised by stepwise reduction from corresponding germylene precursors via stable and isolable germanium radicals. The electronic structures of the anions can be described with ylidene and ylidone resonance forms with the Ge−C π‐electrons capable of binding even weak electrophiles. The germanylidene anions reacted with CO2 to give μ‐CO2‐κC:κO complexes, a rare coordination mode for low‐valent germanium and inaccessible for the related neutral germylones. These results implicate low‐valent germanylidene anions as efficient single‐site nucleop…

Tetracyclic silaheterocycle formed through a pericyclic reaction cascade including a two-fold intramolecular C–C bond activation

Reductive debromination of the tribromoamidosilane 2 gave the tetracyclic silaheterocycle 3 through a unique reaction cascade involving unprecedented two-fold intramolecular cycloaddition by transient silylenes. Experimental and computational analyses of the reaction mechanism allowed the identification of the key intermediates that lead to the silaheterocycle 3 or, alternatively, to the cyclotrisilene 19. peerReviewed

Divergent reactivity of nucleophilic 1-bora-7a-azaindenide anions

The reactions of 1-bora-7a-azaindenide anions, prepared in moderate to excellent yields by reduction of the appropriate 1-bora-7a-azaindenyl chlorides with KC8 in THF, with alkyl halides and carbon dioxide were studied. With alkyl halides (CH2Cl2, CH3I and BrCH(D)CH(D)tBu), the anions behave as boron anions, alkylating the boron centre via a classic SN2 mechanism. This was established with DFT methods and via experiments utilizing the neo-hexyl stereoprobe BrCH(D)CH(D)tBu. These reactions were in part driven by a re-aromatization of the six membered pyridyl ring upon formation of the product. Conversely, in the reaction of the 1-bora-7a-azaindenide anions with CO2, a novel carboxylation of …

Side‐on Coordination in Isostructural Nitrous Oxide and Carbon Dioxide Complexes of Nickel

Abstract A nickel complex incorporating an N2O ligand with a rare η2‐N,N′‐coordination mode was isolated and characterized by X‐ray crystallography, as well as by IR and solid‐state NMR spectroscopy augmented by 15N‐labeling experiments. The isoelectronic nickel CO2 complex reported for comparison features a very similar solid‐state structure. Computational studies revealed that η2‐N2O binds to nickel slightly stronger than η2‐CO2 in this case, and comparably to or slightly stronger than η2‐CO2 to transition metals in general. Comparable transition‐state energies for the formation of isomeric η2‐N,N′‐ and η2‐N,O‐complexes, and a negligible activation barrier for the decomposition of the lat…

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 2090125: Experimental Crystal Structure Determination

Related Article: Chris Gendy, J. Mikko Rautiainen, Aaron Mailman, Heikki M. Tuononen|2021|Chem.-Eur.J.|27|14405|doi:10.1002/chem.202102804

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 1584568: Experimental Crystal Structure Determination

Related Article: Matthew M. Morgan, J. Mikko Rautiainen, Warren E. Piers, Heikki M. Tuononen, Chris Gendy|2018|Dalton Trans.|47|734|doi:10.1039/C7DT04350C

CCDC 2090128: Experimental Crystal Structure Determination

Related Article: Chris Gendy, J. Mikko Rautiainen, Aaron Mailman, Heikki M. Tuononen|2021|Chem.-Eur.J.|27|14405|doi:10.1002/chem.202102804

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 2090122: Experimental Crystal Structure Determination

Related Article: Chris Gendy, J. Mikko Rautiainen, Aaron Mailman, Heikki M. Tuononen|2021|Chem.-Eur.J.|27|14405|doi:10.1002/chem.202102804

CCDC 2023412: Experimental Crystal Structure Determination

Related Article: Braulio Michele Puerta Lombardi, Chris Gendy, Benjamin S. Gelfand, Guy M. Bernard, Roderick E. Wasylishen, Heikki M. Tuononen, Roland Roesler|2021|Angew.Chem.,Int.Ed.|60|7077|doi:10.1002/anie.202011301

CCDC 2118011: Experimental Crystal Structure Determination

Related Article: Joschua Helmer, Olli J. Pakkanen, Chris Gendy, Alexander Hepp, Heikki M. Tuononen, Felicitas Lips|2022|Chem.Commun.|58|3549|doi:10.1039/D2CC00298A

CCDC 1584567: Experimental Crystal Structure Determination

Related Article: Matthew M. Morgan, J. Mikko Rautiainen, Warren E. Piers, Heikki M. Tuononen, Chris Gendy|2018|Dalton Trans.|47|734|doi:10.1039/C7DT04350C

CCDC 2118012: Experimental Crystal Structure Determination

Related Article: Joschua Helmer, Olli J. Pakkanen, Chris Gendy, Alexander Hepp, Heikki M. Tuononen, Felicitas Lips|2022|Chem.Commun.|58|3549|doi:10.1039/D2CC00298A

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 2090119: Experimental Crystal Structure Determination

Related Article: Chris Gendy, J. Mikko Rautiainen, Aaron Mailman, Heikki M. Tuononen|2021|Chem.-Eur.J.|27|14405|doi:10.1002/chem.202102804

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 2023411: Experimental Crystal Structure Determination

Related Article: Braulio Michele Puerta Lombardi, Chris Gendy, Benjamin S. Gelfand, Guy M. Bernard, Roderick E. Wasylishen, Heikki M. Tuononen, Roland Roesler|2021|Angew.Chem.,Int.Ed.|60|7077|doi:10.1002/anie.202011301

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 2090127: Experimental Crystal Structure Determination

Related Article: Chris Gendy, J. Mikko Rautiainen, Aaron Mailman, Heikki M. Tuononen|2021|Chem.-Eur.J.|27|14405|doi:10.1002/chem.202102804

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 2118009: Experimental Crystal Structure Determination

Related Article: Joschua Helmer, Olli J. Pakkanen, Chris Gendy, Alexander Hepp, Heikki M. Tuononen, Felicitas Lips|2022|Chem.Commun.|58|3549|doi:10.1039/D2CC00298A

CCDC 2090130: Experimental Crystal Structure Determination

Related Article: Chris Gendy, J. Mikko Rautiainen, Aaron Mailman, Heikki M. Tuononen|2021|Chem.-Eur.J.|27|14405|doi:10.1002/chem.202102804

CCDC 2023413: Experimental Crystal Structure Determination

Related Article: Braulio Michele Puerta Lombardi, Chris Gendy, Benjamin S. Gelfand, Guy M. Bernard, Roderick E. Wasylishen, Heikki M. Tuononen, Roland Roesler|2021|Angew.Chem.,Int.Ed.|60|7077|doi:10.1002/anie.202011301

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 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 2090126: Experimental Crystal Structure Determination

Related Article: Chris Gendy, J. Mikko Rautiainen, Aaron Mailman, Heikki M. Tuononen|2021|Chem.-Eur.J.|27|14405|doi:10.1002/chem.202102804

CCDC 2090120: Experimental Crystal Structure Determination

Related Article: Chris Gendy, J. Mikko Rautiainen, Aaron Mailman, Heikki M. Tuononen|2021|Chem.-Eur.J.|27|14405|doi:10.1002/chem.202102804

CCDC 2023414: Experimental Crystal Structure Determination

Related Article: Braulio Michele Puerta Lombardi, Chris Gendy, Benjamin S. Gelfand, Guy M. Bernard, Roderick E. Wasylishen, Heikki M. Tuononen, Roland Roesler|2021|Angew.Chem.,Int.Ed.|60|7077|doi:10.1002/anie.202011301

CCDC 2090123: Experimental Crystal Structure Determination

Related Article: Chris Gendy, J. Mikko Rautiainen, Aaron Mailman, Heikki M. Tuononen|2021|Chem.-Eur.J.|27|14405|doi:10.1002/chem.202102804

CCDC 2090124: Experimental Crystal Structure Determination

Related Article: Chris Gendy, J. Mikko Rautiainen, Aaron Mailman, Heikki M. Tuononen|2021|Chem.-Eur.J.|27|14405|doi:10.1002/chem.202102804

CCDC 2090129: Experimental Crystal Structure Determination

Related Article: Chris Gendy, J. Mikko Rautiainen, Aaron Mailman, Heikki M. Tuononen|2021|Chem.-Eur.J.|27|14405|doi:10.1002/chem.202102804

CCDC 2118008: Experimental Crystal Structure Determination

Related Article: Joschua Helmer, Olli J. Pakkanen, Chris Gendy, Alexander Hepp, Heikki M. Tuononen, Felicitas Lips|2022|Chem.Commun.|58|3549|doi:10.1039/D2CC00298A

CCDC 2118010: Experimental Crystal Structure Determination

Related Article: Joschua Helmer, Olli J. Pakkanen, Chris Gendy, Alexander Hepp, Heikki M. Tuononen, Felicitas Lips|2022|Chem.Commun.|58|3549|doi:10.1039/D2CC00298A

CCDC 2090121: Experimental Crystal Structure Determination

Related Article: Chris Gendy, J. Mikko Rautiainen, Aaron Mailman, Heikki M. Tuononen|2021|Chem.-Eur.J.|27|14405|doi:10.1002/chem.202102804