TY - JOUR
T1 - Synthesis of group 14 metal enamido, alkenyl, imido and alkenyl-amido complexes from a monoanionic pyridyl-1-azaallyl ligand
AU - Leung, Wing Por
AU - So, Cheuk Wai
AU - Wu, Yuen Sze
AU - Li, Hung Wing
AU - Mak, Thomas C.W.
PY - 2005/2/4
Y1 - 2005/2/4
N2 - The reactivity of the lithium pyridyl-1-azaallyl complex [Li{N(SiMe 3)C(Ph)C(R)(C5H4N-2)}]2 [R = SiMe3 (1) or H (10)] with group 14 metal halides has been studied under various conditions. It undergoes a salt-elimination reaction with MCl 2 (M = Ge, Sn or Pb) to form [Ge{C(C5H4N-2) C(Ph)N-(SiMe3)2}{N(SiMe3)C(Ph)C(SiMe 3)(C5H4N-2)}] (2), [M{N-(SiMe 3)C(Ph)C(SiMe3)(C5H4N-2)} 2] [M = Sn (3), Pb (4)], and [M{N(SiMe3)C(Ph)C(SiMe 3)(C5H4N-2)}Cl] [M = Ge (5), Sn (6), Pb (7)], where the azaaalyl moiety acts as a monodentate ligand. However, the reaction of 1 with GeCl4 or HSiCl3 forms [Ge{C(C5H 4N-2)C(Ph)N(SiMe3)}Cl2]2 (8) or [{(C5H4N-2)C(SiMe3)C(Ph)N}(μ-SiHCl)] 2 (9), respectively, by elimination of both the lithium salt and Me3SiCl; the reaction of 10 with GeCl4 gives [{(C 5H4N-2)C(H)C(Ph)N}(μ-GeCl2)]2 (11) in a similar manner. X-ray structural analysis of compounds 2-5, 7-9 and 11 showed that the pyridyl-1-azaallyl ligand bonds to the metal center in enamido, alkenyl, alkenyl-amido, and imido bonding modes. A mechanism for the formation of these compounds is proposed and discussed.
AB - The reactivity of the lithium pyridyl-1-azaallyl complex [Li{N(SiMe 3)C(Ph)C(R)(C5H4N-2)}]2 [R = SiMe3 (1) or H (10)] with group 14 metal halides has been studied under various conditions. It undergoes a salt-elimination reaction with MCl 2 (M = Ge, Sn or Pb) to form [Ge{C(C5H4N-2) C(Ph)N-(SiMe3)2}{N(SiMe3)C(Ph)C(SiMe 3)(C5H4N-2)}] (2), [M{N-(SiMe 3)C(Ph)C(SiMe3)(C5H4N-2)} 2] [M = Sn (3), Pb (4)], and [M{N(SiMe3)C(Ph)C(SiMe 3)(C5H4N-2)}Cl] [M = Ge (5), Sn (6), Pb (7)], where the azaaalyl moiety acts as a monodentate ligand. However, the reaction of 1 with GeCl4 or HSiCl3 forms [Ge{C(C5H 4N-2)C(Ph)N(SiMe3)}Cl2]2 (8) or [{(C5H4N-2)C(SiMe3)C(Ph)N}(μ-SiHCl)] 2 (9), respectively, by elimination of both the lithium salt and Me3SiCl; the reaction of 10 with GeCl4 gives [{(C 5H4N-2)C(H)C(Ph)N}(μ-GeCl2)]2 (11) in a similar manner. X-ray structural analysis of compounds 2-5, 7-9 and 11 showed that the pyridyl-1-azaallyl ligand bonds to the metal center in enamido, alkenyl, alkenyl-amido, and imido bonding modes. A mechanism for the formation of these compounds is proposed and discussed.
KW - Germanium
KW - Group 14 elements
KW - Lead
KW - N ligands
KW - Tin
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U2 - 10.1002/ejic.200400641
DO - 10.1002/ejic.200400641
M3 - Article
AN - SCOPUS:14544283562
SN - 1434-1948
SP - 513
EP - 521
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 3
ER -