Synthesis and Structures of Alkali Metal Amides Derived from the Ligands [N(SiMe 2 Ph)(SiMe 3 )] − , [N( t Bu)(SiMe 3 )] − , [N(Ph)(2‐C 5 H 4 N)] − , and [N(2‐C 5 H 4 N) 2 ] −

The following crystalline complexes are reported: [(M{μ‐N(SiMe 2 Ph)(SiMe 3 )}) 2 ] n [the cis complex for n = 1 and M = Li ( 1 ); and the trans complexes with n = ∞ and M = Na ( 2 ), K ( 4 ), Rb ( 5 ), Cs ( 6 )], [(Na{μ‐ trans ‐N(SiMe 2 Ph)(SiMe 3 )}) 2 (tmeda)] ( 3 ), [(K{μ‐ trans ‐N( t Bu)(SiMe 3 )}) 4 (η‐C 6 H 6 ) 2 ] ( 7 ), [(K{μ‐ trans ‐N(Ph)(2‐C 5 H 4 N)}) 2 (μ′‐thf) 3 ] ∞ ( 8 ), and [K{μ‐N(2‐C 5 H 4 N) 2 }] ∞ ( 9 ). Each, except 3 , was obtained by metallation of the appropriate secondary amine with Li n Bu (for 1 ), MBzl [M = Na (for 2 ), K (for 4 and 7 ), Rb (for 5 ), Cs (for 6 )], or KH (for 8 and 9 ); treatment of 2 with an excess of tmeda yielded 3 . Each of 1 − 9 has an unusual, and in some cases unprecedented, molecular structure. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)