0000000001303514
AUTHOR
Hyui Sul Lee
Sterically crowded triazenides as novel ancillary ligands in copper chemistry
Abstract We have synthesized copper salts MN3RR′ derived from the biphenyl- or m-terphenyl-substituted triazenes Tph2N3H (1a) and Dmp(Tph)N3H (1b) (Dmp = 2,6-Mes2C6H3 with Mes = 2,4,6-Me3C6H2; Tph = 2-TripC6H4 with Trip = 2,4,6-i-Pr3C6H2). The homoleptic copper triazenide [CuN3Tph2] (2a) was obtained in high yield from the metallation of 1a with mesityl copper in n-heptane, while the complex [CuN3(Dmp)Tph] (2b) was generated by the same method in situ only. Reaction of 2a with triphenylphosphane gave the 2:1 adduct [CuN3Tph2(PPh3)2] (3a), regardless of the used complex/donor ratio, while reaction of 2a or 2b with a stochiometric amount of t-butylisonitrile afforded the 1:1 adducts [Tph2N3Cu…
Homoleptic heavy alkaline Earth and europium triazenides.
The sigma-bond metathesis reaction between PhSiH(3) and the heteroleptic metal pentafluorophenyl compounds [Dmp(Tph)N(3)MC(6)F(5)(thf)(n)] (Dmp = 2,6-Mes(2)C(6)H(3) with Mes = 2,4,6-Me(3)C(6)H(2); Tph = 2-TripC(6)H(4) with Trip = 2,4,6-(i)Pr(3)C(6)H(2); n = 1, 2; M = Sr, Ba, Eu) supported by sterically crowded, biphenyl- and terphenyl-substituented triazenido ligands afforded the first homoleptic stontium, barium, and europium triazenides [M{N(3)Dmp(Tph)}(2)] {M = Sr (2), Ba (4), Eu (5)}. Crystallization of 2 from an n-heptane/1,2-dimethoxyethane mixture gave the complex [Sr{N(3)Dmp(Tph)}(2)(dme)] (3). All new compounds have been characterized by (1)H and (13)C NMR spectroscopy (not 5), ele…
Rare-earth metal bis(tetramethylaluminate) complexes supported by a sterically crowded triazenido ligand
Complexes [NNN]Ln(AlMe(4))(2) (Ln = Y, La, Nd, Lu) bearing the sterically demanding aryl-substituted triazenido ligand [(Tph)(2)N(3)] (Tph = [2-(2,4,6-iPr(3)C(6)H(2))C(6)H(4)]) can be obtained from homoleptic complexes Ln(AlMe(4))(3) in moderate yields, both via protonolysis with [(Tph)(2)N(3)]H and a salt metathesis reaction pathway utilizing [(Tph)(2)N(3)]K. In the solid state the Y and Lu derivatives are isostructural, with both tetramethylaluminate groups coordinated in an eta(2) fashion, while one of the [AlMe(4)] ligands of the Nd derivative features a distorted eta(2) coordination mode. Due to the high affinity of the triazenido ligand toward the more Lewis-acidic and harder aluminiu…
Isostructural potassium and thallium salts of sterically crowded triazenes: a structural and computational study.
Because of their similar cationic radii, potassium and thallium(I) compounds are usually regarded as closely related. Homologous molecular species containing either K(+) or Tl(+) are very rare, however. We have synthesized potassium and thallium salts MN3RR' derived from the biphenyl- or terphenyl-substituted triazenes Tph2N3H (1a), Dmp(Mph)N3H (1b), Dmp(Tph)N3H (1c), and (Me4Ter)2N3H (1d) (Dmp=2,6-Mes 2C6H3 with Mes=2,4,6-Me3C6H2; Me4Ter=2,6-(3,5-Me2C6H3)2C6H3; Mph=2-MesC6H4; Tph=2-TripC6H4 with Trip=2,4,6-(i)Pr3C6H2). The potassium complexes 2a- d were obtained in almost quantitative yield from the reaction of 1a- d with potassium metal in n-heptane. Metalation of 1a- d with TlOEt afforde…
CCDC 672474: Experimental Crystal Structure Determination
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CCDC 751109: Experimental Crystal Structure Determination
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CCDC 757140: Experimental Crystal Structure Determination
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CCDC 296486: Experimental Crystal Structure Determination
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CCDC 800787: Experimental Crystal Structure Determination
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CCDC 800785: Experimental Crystal Structure Determination
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CCDC 672477: Experimental Crystal Structure Determination
Related Article: Hyui Sul Lee, S.-O.Hauber, D.Vindus, M.Niemeyer|2008|Inorg.Chem.|47|4401|doi:10.1021/ic800029z
CCDC 757141: Experimental Crystal Structure Determination
Related Article: R.Litlabo, Hyui Sul Lee, M.Niemeyer, K.W.Tornroos, R.Anwander|2010|Dalton Trans.|39|6815|doi:10.1039/b925837j
CCDC 800788: Experimental Crystal Structure Determination
Related Article: Hyui Sul Lee, M.Niemeyer|2011|Inorg.Chim.Acta|374|163|doi:10.1016/j.ica.2011.01.079
CCDC 800783: Experimental Crystal Structure Determination
Related Article: Hyui Sul Lee, M.Niemeyer|2011|Inorg.Chim.Acta|374|163|doi:10.1016/j.ica.2011.01.079
CCDC 751112: Experimental Crystal Structure Determination
Related Article: Hyui Sul Lee, M.Niemeyer|2010|Inorg.Chem.|49|730|doi:10.1021/ic902055h
CCDC 757142: Experimental Crystal Structure Determination
Related Article: R.Litlabo, Hyui Sul Lee, M.Niemeyer, K.W.Tornroos, R.Anwander|2010|Dalton Trans.|39|6815|doi:10.1039/b925837j
CCDC 672479: Experimental Crystal Structure Determination
Related Article: Hyui Sul Lee, S.-O.Hauber, D.Vindus, M.Niemeyer|2008|Inorg.Chem.|47|4401|doi:10.1021/ic800029z
CCDC 800784: Experimental Crystal Structure Determination
Related Article: Hyui Sul Lee, M.Niemeyer|2011|Inorg.Chim.Acta|374|163|doi:10.1016/j.ica.2011.01.079
CCDC 672475: Experimental Crystal Structure Determination
Related Article: Hyui Sul Lee, S.-O.Hauber, D.Vindus, M.Niemeyer|2008|Inorg.Chem.|47|4401|doi:10.1021/ic800029z
CCDC 672476: Experimental Crystal Structure Determination
Related Article: Hyui Sul Lee, S.-O.Hauber, D.Vindus, M.Niemeyer|2008|Inorg.Chem.|47|4401|doi:10.1021/ic800029z
CCDC 296487: Experimental Crystal Structure Determination
Related Article: Hyui Sul Lee, M.Niemeyer|2006|Inorg.Chem.|45|6126|doi:10.1021/ic060873f
CCDC 800786: Experimental Crystal Structure Determination
Related Article: Hyui Sul Lee, M.Niemeyer|2011|Inorg.Chim.Acta|374|163|doi:10.1016/j.ica.2011.01.079
CCDC 672473: Experimental Crystal Structure Determination
Related Article: Hyui Sul Lee, S.-O.Hauber, D.Vindus, M.Niemeyer|2008|Inorg.Chem.|47|4401|doi:10.1021/ic800029z
CCDC 672478: Experimental Crystal Structure Determination
Related Article: Hyui Sul Lee, S.-O.Hauber, D.Vindus, M.Niemeyer|2008|Inorg.Chem.|47|4401|doi:10.1021/ic800029z
CCDC 751111: Experimental Crystal Structure Determination
Related Article: Hyui Sul Lee, M.Niemeyer|2010|Inorg.Chem.|49|730|doi:10.1021/ic902055h
CCDC 757139: Experimental Crystal Structure Determination
Related Article: R.Litlabo, Hyui Sul Lee, M.Niemeyer, K.W.Tornroos, R.Anwander|2010|Dalton Trans.|39|6815|doi:10.1039/b925837j
CCDC 751110: Experimental Crystal Structure Determination
Related Article: Hyui Sul Lee, M.Niemeyer|2010|Inorg.Chem.|49|730|doi:10.1021/ic902055h