The title complex [Ti(salen)Cl2] (1) [salen = NN′-ethylenebis(salicylideneiminate)] reacts with a thf solution of LiBH4 to give [{Ti(salen)(BH4)2}2]·2thf (2) as an orange crystalline solid. Complex (2) is formed by the substitution of Cl- by BH4- followed by addition of BH4- to the imino-groups of the salen ligand. The i.r. spectrum shows the disappearance of bands due to -C=N- and the presence of strong bands due to Ti-H and B-H vibrations, which are shifted to lower values in the deuteriated derivative [{Ti(salen)(BD4)2}2]·thf (3). Crystals of (2) are formed in dimeric units having crystallographic Ci(1̄) symmetry. Each metal atom surrounded by the sexidentate ligand (salen) (BH4)2 having a H2N2O2 set of donor atoms achieves seven-co-ordination by sharing one of the salen oxygens with the other titanium of the dimeric unit. Other relevant structural features of complex (2) are the presence of BNH2 groups bonded to titanium through a bridging hydrogen, and the consequent existence of two electron-deficient four-membered rings, B-H-Ti-N. The Ti(salen)(BH4)2 unit is supposed to form from a titanium-promoted activation of the 2 bonds on the lefthand side signC=N- bond in [Ti(salen)Cl2]. [{Ti(salen)(BH4)2}2]·2thf (2) crystallises in the space group P21/c with a = 11.802(9), b = 20.039(15), c = 9.272(6) Å, β = 90.00(5)°, and Z = 2. The final R factor was 0.068 for 1 028 observed reflections.

Peripheral Electrophilic Properties of Dichloro[N,N'-ethylenebis (salicylideneiminato)]titanium(IV): A Route leading to a Stable Ti-H-B Unit.

DELL'AMICO, GIANCARLO;MARCHETTI, FABIO;
1982

Abstract

The title complex [Ti(salen)Cl2] (1) [salen = NN′-ethylenebis(salicylideneiminate)] reacts with a thf solution of LiBH4 to give [{Ti(salen)(BH4)2}2]·2thf (2) as an orange crystalline solid. Complex (2) is formed by the substitution of Cl- by BH4- followed by addition of BH4- to the imino-groups of the salen ligand. The i.r. spectrum shows the disappearance of bands due to -C=N- and the presence of strong bands due to Ti-H and B-H vibrations, which are shifted to lower values in the deuteriated derivative [{Ti(salen)(BD4)2}2]·thf (3). Crystals of (2) are formed in dimeric units having crystallographic Ci(1̄) symmetry. Each metal atom surrounded by the sexidentate ligand (salen) (BH4)2 having a H2N2O2 set of donor atoms achieves seven-co-ordination by sharing one of the salen oxygens with the other titanium of the dimeric unit. Other relevant structural features of complex (2) are the presence of BNH2 groups bonded to titanium through a bridging hydrogen, and the consequent existence of two electron-deficient four-membered rings, B-H-Ti-N. The Ti(salen)(BH4)2 unit is supposed to form from a titanium-promoted activation of the 2 bonds on the lefthand side signC=N- bond in [Ti(salen)Cl2]. [{Ti(salen)(BH4)2}2]·2thf (2) crystallises in the space group P21/c with a = 11.802(9), b = 20.039(15), c = 9.272(6) Å, β = 90.00(5)°, and Z = 2. The final R factor was 0.068 for 1 028 observed reflections.
Dell'Amico, Giancarlo; Marchetti, Fabio; Floriani, C.
File in questo prodotto:
Non ci sono file associati a questo prodotto.

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11568/4614
 Attenzione

Attenzione! I dati visualizzati non sono stati sottoposti a validazione da parte dell'ateneo

Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus ND
  • ???jsp.display-item.citation.isi??? 30
social impact