Syntheses and Structure of Heterometallic Complexes Containing Tripodal Group 13 Ligands [RE(2-py)₃]^- (E = Al, In)

Abstract

Reactions of the Al(III) complex [{MeAl(2-py)3}Li·THF] (1), containing the tripodal [MeAl(2-py)3]- ligand, with [(C7H8)Mo(CO)3], CaI2, and ZnCl2 give the trimetallic and bimetallic complexes [{MeAl(2-py)3}Mo(CO)3Li(THF)3] (2), [{MeAl(2-py)3}2Ca] (3), and [{MeAl(2-py)3}ZnCl] (4), respectively. [{ n BuIn(2-py)3}Li·THF] (5), an InIII analogue of 1 containing the [ n BuIn(2-py)3]- anion, is obtained by the one-pot reaction of n BuLi with InCl3 followed by reaction with 2-Li-py. Complex 5 reacts with [(C7H8)Mo(CO)3] to give [{ n BuIn(2-py)3}Mo(CO)3Li(THF)2]∞ (6) (analogous to the AlIII complex 2). The X-ray structures of the new complexes 2, 3, 4, 5, and 6 are reported.

Pyridylborates as a New Type of Robust Scorpionate Ligand: From Metal Complexes to Polymeric Materials

“…Pyridine donor‐containing tripod ligands have previously been reviewed, and a variety of bridgehead atoms such as carbon, nitrogen,[32a] phosphorus,[32a] arsenic, aluminum, indium,[34a] silicon, tin, and lead have been incorporated to tune the metal coordination properties both in terms of geometry and electronic structure (Figure ). As early as 1933, Wibaut and La Bastide first reported the synthesis of tris(2‐pyridyl)amine by sequential condensation of 2‐halopyridine with 2‐aminopyridine .…”

Alkali and alkaline-earth metals

“…four H atoms were desorbed per [Mg(NH 2 ) 2 CaH 2 ] after ball milling. 140 The first homoleptic alkaline earth (Tf 142 Complexes of the heavier alkaline earth metals containing bulky b-diketiminate and iodide ligand sets have been described. Treatment of the potassium b-diketiminate with equimolar amounts of MI 2 (M = Ca, Sr, Ba) afforded a variety of hapticities from Z 2 to Z 5 -, which were dependent upon the identity of the metal and the molecularity of the complex.…”

Cyclooctadiene Rh(I) Bis- and Tris(pyrazolyl)aluminate Complexes and Their Catalytic Activity on the Polymerization of Phenylacetylene

“…9 These results highlight the difficulties of this chemistry and underpin the need for a better understanding of the factors that might lead to well-defined poly(pyrazolyl)aluminate metalloligands and complexes as it has been shown for the related tris(pyridyl)aluminates. [10][11][12][13][14][15][16][17] We surmised that a better performance of the poly(pyrazolyl)aluminate ligand system towards its transfer to a transition metal center could be achieved using alkyl groups on the aluminum atom instead of hydrogen to prevent hydride transfer on the one hand and, on the other hand, by using a more electron rich low-valent organotransition metal center, potentially leading to more stable, less reactive complexes. Indeed, we report herein the preparation and full characterization of the The X-ray crystallographic studies of complexes 1 and 2 reveal mononuclear complexes.…”