Formation of Calcium–Carbon Bonds From a Lewis Acid-Base Reaction of Calcium Bis[bis(trimethylsilyl)amide] and Tris(trimethylsilylmethyl)alane

Bis(trimethylsilyl)phosphide chemistry: a half-century of advances across the periodic table

“…164,165 We have found there to be relatively few p-block metal P′′ complexes, including no structurally authenticated group 15 and 16 metal(loid) P′′ complexes to date. 9 This is quite astonishing considering the potential of such molecular precursors in the synthesis of solid-state III–V semiconductors; 42–57 we noted that a Bi P′′ complex has been reported without a solid-state structure, 12 e and this is also the case for Sb. 166 We have identified multiple gaps in d-block metal P′′ chemistry that can be exploited, mainly for the second and third row d-transition metals.…”

“…In 21-AlR the mean Al–P bond lengths increase as the steric influence of the R group increases: 21-AlMe , 2.457(2) Å; 21-AlEt , 2.458(1) Å; 21-AlCH 2 i Pr , 2.476(2) Å; 21-AlCH 2 SiMe 3 , 2.483(1) Å. 43–46 This trend is also seen for the 21-GaR series: 21-GaMe , 2.450(1) Å; 21-GaEt , 2.4558(7) Å; 21-Ga n Bu , 2.4533(6) Å; 21-GaCH 2 t Bu , 2.517(3) Å; 21-GaCH 2 SiMe 3 , 2.4887(16) Å. 40,47–51 Finally, the In–P bond lengths in 21-InR vary similarly: 21-InMe , 2.630(1) Å; 21-InEt , 2.645(1) Å; 21-InPh , 2.612(1) Å; 21-InCH 2 Ph , 2.6123(6) Å; 21-CH 2 SiMe 3 , 2.655(3) Å.…”

Synthesis and Properties of Calcium Tetraorganylalanates with [Me4−nAlPhn]− Anions

“…14 Molecular [R 2 NCa(µ-CH 2 R) 2 Al(CH 2 R) 2 ] 2 (R ) SiMe 3 ) formed from the reaction of [Ca(NR 2 ) 2 ] 2 with Al(CH 2 R) 3 . 15 Incorporation of additional donor atoms supports the formation of molecular calcium bisalanates as shown for [Ca{(µ-2-Py) 3 -AlMe} 2 ] with a hexacoordinate calcium center. 16 Solventseparated ions were obtained from the reaction of (dme) 2 Ca(NPh 2 ) 2 and AlMe 3 in tetrahydrofuran, yielding [(thf) 6 Ca][Me 3 Al-NPh 2 ] 2 .…”

Alkaline-Earth Metal Alkylaluminate Chemistry Revisited

“…We have previously reported that heterobimetallic peralkylated rare-earth metal complexes [Ln(AlR 4 ) 2 ] n (Ln = Sm, Yb; R = Me, Et; herein referred as aluminates) are readily accessible by the silylamide elimination reaction protocol. , Similarly, the calcium derivatives [Ca(AlR 4 ) 2 ] n ( 1 , R = Me; 2 , R = Et) could be obtained from {Ca[N(SiMe 3 ) 2 ] 2 } 2 and an excess of AlR 3 in almost quantitative yield (Scheme ) …”