Diamine Intercalates of Titanium and Vanadium Oxychloride. Evidence for the Subsequent Substitution Reactions of TiOCl with Amines

The intercalation reactions of several new guest molecules [ethylenediamine (EN), N, N ‘-dimethylethylenediamine (DMEN), N, N, N ‘-trimethylethylenediamine (TMEN), N, N, N ‘, N ‘-tetramethylethylenediamine (TMEDA) and diethylenetriamine (3N)] into the layered compounds VOCl and TiOCl are reported. At 75 °C, both TiOCl and VOCl reacted with EN to yield dark blue-gray solids. X-ray diffraction (XRD) of these materials indicated formation of new compounds with b axes of 11.45(4) and 11.39(5) Å, respectively. Microanalysis and thermogravimetry indicated formulas of TiOCl(EN) 0.4 and VOCl(EN) 0.4 . Reaction with N, N ‘-dimethylethylenediamine (DMEN) resulted in the formation of the new intercalation products TiOCl(C 4 H 12 N 2 ) 0.4 and VOCl(DMEN) 0.3 with b axes of 11.38(9) Å (M = Ti) and 11.33(7) Å (M = V). Both TMEN and TMEDA were intercalated into VOCl (48 h at 100 °C). The products in this case were VOCl(TMEDA) 0.25 and VOCl(TMEN) 0.3 with Δ b = 5.63 Å ( b = 13.54(5) Å) 4.33 Å, respectively. In contrast, even under forcing conditions (170 °C, 5 days), TiOCl does not intercalate TMEDA or TMEN. Reaction of MOCl with diethylenetriamine (3N) gave TiOCl(3N) 0.2 ( b = 12.06(4) Å) or VOCl(3N) 0.15 ( b = 12.07(4) Å). As expected for the product of an intercalation reaction, rapidly heating these intercalates under N 2 regenerated the XRD patterns of the starting materials. These guests appear to adopt preferentially a parallel orientation relative to the MO planes of the host. With extended reaction times, the intercalation products of TiOCl with EN and DMEN gave products of substitution reactions: TiOCl 0.5 (C 2 H 7 N 2 ) 0.5, b = 14.46(9) Å, and TiOCl x (C 4 H 11 N 2 ) 1 - x, b = 14.57(2) Å. Concurrent appearance diammonium salt of EN, (H 3 NC 2 H 4 NH 3 )Cl 2, or the diammonium salt of DMEN, [H 2 (Me)NC 2 H 4 N(Me)H 2 ]Cl 2, is confirming evidence that the amines are now directly bonded to the Ti−O double layers by substitution of Cl anions.