New group 14 element(IV) β-diiminates and a Sn(II) analogue

Seven group 14 element(IV) compounds 2–7 have been prepared, derived either (2–5) from the potassium β-diketiminate K(L) [L = {N(Ar)C(Me)}2CH, Ar = C6H3Pri2-2,6] (1) or the known lithium β-dialdiminate Li(L′)] [L′ = {N(Ar)C(H)}2CPh, Ar = C6H3Pri2-2,6]. Treatment of 1 with ButC(O)Cl, Me3SiCl, Ph3SnCl, or Me3SnCl afforded {N(Ar)C(Me)}2C(H)C(O)But (2), [ArNC(Me)C(H)C(Me)N(Ar)SiMe3] (3), [HN(Ar)C(Me)C(H)C(CH2SnPh3)N(Ar)] (4), or (5), respectively. Compounds 4 and 5 are remarkable as they have arisen from a tautomer of 1; crystalline centrosymmetric 5 has a fused tricyclic structure, a central eight-membered ring flanked by two six-membered rings. The compounds [GeCl2(L′)(OGeCl3)] (6) or [SnCl(L′)Me2] (7), the first group 14 metal β-dialdiminates, were obtained from Li(L′) and (GeCl3)2O or Me2SnCl2, respectively. The Sn(II) compound SnCl(L′) (8) was prepared from SnCl2 and K(L′). The molecular structures of the crystalline compounds 3–8 are reported.

Graphical abstractThe compounds {N(Ar)C(Me)}2C(H)C(O)But (2), [ArNC(Me)C(H)C(Me)N(Ar)SiMe3] (3), [HN(Ar)C(Me)C(H)C(CH2SnPh3)N(Ar)] (4), (5), [GeCl2(L′)(OGeCl3)] (6), [SnCl(L′)Me2] (7) and [SnCl(L′)] (8) are reported; the X-ray structures of 3–8 are presented [Ar = C6H3Pri-2,6; L′ = {N(C6H3Pri-2,6)C(H)}2CPh].Figure optionsDownload full-size imageDownload as PowerPoint slideFigure optionsDownload full-size imageDownload as PowerPoint slide