Surprisingly Different Reaction Behavior of Alkali and Alkaline Earth Metal Bis(trimethylsilyl)amides toward Bulky N-(2-Pyridylethyl)-N'-(2,6-diisopropylphenyl)pivalamidine.

N-(2,6-Diisopropylphenyl)-N'-(2-pyridylethyl)pivalamidine (Dipp-N=C(tBu)-N(H)-C2 H4 -Py) (1), reacts with metalation reagents of lithium, magnesium, calcium, and strontium to give the corresponding pivalamidinates [(tmeda)Li{Dipp-N=C(tBu)-N-C2 H4 -Py}] (6), [Mg{Dipp-N=C(tBu)-N-C2 H4 -Py}2 ] (3), and heteroleptic [{(Me3 Si)2 N}Ae{Dipp-N=C(tBu)-N-C2 H4 -Py}], with Ae being Ca (2 a) and Sr (2 b). In contrast to this straightforward deprotonation of the amidine units, the reaction of 1 with the bis(trimethylsilyl)amides of sodium or potassium unexpectedly leads to a ß-metalation and an immediate deamidation reaction yielding [(thf)2 Na{Dipp-N=C(tBu)-N(H)}] (4 a) or [(thf)2 K{Dipp-N=C(tBu)-N(H)}] (4 b), respectively, as well as 2-vinylpyridine in both cases. The lithium derivative shows a similar reaction behavior to the alkaline earth metal congeners, underlining the diagonal relationship in the periodic table. Protonation of 4 a or the metathesis reaction of 4 b with CaI2 in tetrahydrofuran yields N-(2,6-diisopropylphenyl)pivalamidine (Dipp-N=C(tBu)-NH2 ) (5), or [(thf)4 Ca{Dipp-N=C(tBu)-N(H)}2 ] (7), respectively. The reaction of AN(SiMe3 )2 (A=Na, K) with less bulky formamidine Dipp-N=C(H)-N(H)-C2 H4 -Py (8) leads to deprotonation of the amidine functionality, and [(thf)Na{Dipp-N=C(H)-N-C2 H4 -Py}]2 (9 a) or [(thf)K{Dipp-N=C(H)-N-C2 H4 -Py}]2 (9 b), respectively, are isolated as dinuclear complexes. From these experiments it is obvious, that ß-metalation/deamidation of N-(2-pyridylethyl)amidines requires bases with soft metal ions and also steric pressure. The isomeric forms of all compounds are verified by single-crystal X-ray structure analysis and are maintained in solution.

Strong intramolecular calcium-π interactions with aryl substituents--requirements and limitations.

The amidines Dipp-N=C(tBu)-N(H)-Qu (1a) (Dipp = 2,6-diisopropylphenyl, Qu = 8-quinolyl) and Dipp-N=C(tBu)-N(H)-Py (1b) (Py = 2-pyridyl) are deprotonated with KN(SiMe3)2, yielding potassium N-(2,6-diisopropylphenyl)-N'-(8-quinolyl)pivalamidinate (2a) and potassium N-(2,6-diisopropylphenyl)-N'-(2-pyridyl)pivalamidinate (2b). Metalation of 1a with [(thf)2Ca{N(SiMe3)2}2] in tetrahydrofuran (thf) leads to the formation of ether-free calcium bis[N-(2,6-diisopropylphenyl)-N'-(8-quinolyl)pivalamidinate] (3a) with a strong intramolecular calcium-π interaction with one Dipp group. Furthermore, agostic bonds to one tert-butyl substituent complete the coordination sphere of the metal center and stabilize this bonding situation. The metathesis reaction of 2b with [(thf)4CaI2] yields the thf adduct of calcium bis[N-(2,6-diisopropylphenyl)-N'-(2-pyridyl)pivalamidinate] (3b). In addition to the bonds between calcium and the hard Lewis bases (oxygen of thf, nitrogen atoms of the pyridylamido moieties), anagostic Ca-H bonds to the tert-butyl substituents complete the coordination sphere. The intramolecular calcium-π interaction with an aryl group as observed in 3a requires steric shielding of the alkaline earth metal center, safely excluding the formation of a complex with more than one thf ligand.