Siloxymethylamines as Aminomethylation Reagents for Amines Leading to Labile Diaminomethanes That can be Trapped as Their [Mo(CO)4] Complexes

Compound Et3SiOCH2NMe2 transfers Me2NCH2 to R2NH (R2=Et2, PhMe, [Cr(η6‐C6H5)(CO)3]Me, PhH) to form previously unknown diaminomethanes, Me2NCH2NR2 and, in the case of R2=PhH, the triamine Me2NCH2N(Ph)CH2NMe2. The diaminomethanes exhibit an unreported disproportionation to a mixture of (R2N)2CH2, (Me2N)2CH2, and Me2NCH2NR2, which can be trapped as their [Mo(CO)4(diamine)] complexes. Whereas PhMeNCH2NMe2 is a labile material, the metal‐substituted ([(η6‐C6H5)Cr(CO)3]MeNCH2NMe2 is a stable material. The triamine Me2NCH2N(Ph)CH2NMe2 is unstable with respect to transformation to 1,3,5‐triphenyltriazine, but is readily trapped as the bidentate‐triamineMo(CO)4. All metal complexes were characterized by single‐crystal X‐ray diffraction. Previously unreported simple diaminomethanes were readily obtained from reactions of siloxymethylamines with secondary amines. They are labile materials that readily disproportionate, but can be trapped by metal coordination (see scheme).