Calcium Bis[bis(trimethylsilyl)amino‐triethylgallate] — A Molecule with Ca‐C‐Ga Three‐Center Bonds

Abstract

The reaction of calcium‐bis[bis(trimethylsilyl)amide] with two equivalents triethylgallium yields nearly quantitatively the addition product. In the solid state the calcium atoms are coordinated by two nitrogen atoms and two ethyl groups, whereas in solution all ethyl substituents are magnetically equivalent even at low temperatures. The Ca‐C‐Ga two‐electron three‐center bonds show mean Ca‐N and Ca‐C distances of 243 and 268 pm, respectively.

Polar Molecular Precursors for Alkali and Alkaline Earth Metal Clusters and Low‐Dimensional Polymer Structures: the Solid‐State Structures of [CaI(dme)3]I, and cis‐[SrI2(diglyme)2] (dme = CH3OC2H4OCH3; diglyme = CH3(OC2H4)2OCH3)

“…[17Ϫ19, 22] Unfortunately, the polarity of the molecules of 1 is not maintained in the overall solid state as the compound crystallizes in a centrosymmetric space group.…”

Heavy Grignard Reagents: Synthesis, Physical and Structural Properties, Chemical Behavior, and Reactivity

“…Thus, combination of CaR 2 and organometallics with less electronegative metals leads to the formation of calcium metalates, whereas more electropositive metals form metal calciates. Thus, heterobimetallic complexes are obtained from a Lewis acid–base reaction of Ca[N(SiMe 3 ) 2 ] 2 with GaEt 3 and Al(CH 2 SiMe 3 ) 3 yielding Ca[N(SiMe 3 ) 2 (GaEt 3 )] 2 [Eq. ] and [{(Me 3 Si) 2 NCa(Al{CH 2 SiMe 3 } 4 )} 2 ], respectively, with bridging alkyl groups.…”

Synthesis and Reactivity of Discrete Calcium Imides

“…TheCaatoms in 2a and 2b are coordinated in adistorted octahedral fashion by bridging imido and methyl groups as well as by four molecules of thf.A sexpected for m 2 -bridging imido ligands,t he CaÀNb onds in 2a (2.236(2) )a nd 2b (2.280(2) )are even shorter than those in the homometallic imide 1.T he Ca À C(m-CH 3 )b onds (2.651(2) (2a)a nd 2.668(2) (2b)) are longer than those in the six-coordinate bis(tetramethylaluminate) complex [(phen)Ca(AlMe 4 ) 2 ] [11] (av.2.584 (7) )and similar to the distances in the structurally related amide complex [Ca{N(SiMe 3 ) 2 (GaEt 3 )} 2 ] [24] (2.656(5) and 2.697(4) ). TheA l ÀNb ond lengths of 1.849(2) (2a) and 1.831(2) (2b)m atch those of comparable imidoalanes.…”