TY - JOUR
T1 - Syntheses, X-ray structures and CVD of titanium(iv) arsine complexes
AU - Thomas, Tegan
AU - Pugh, David
AU - Parkin, Ivan P.
AU - Carmalt, Claire J.
PY - 2010
Y1 - 2010
N2 - Five titanium arsine compounds have been synthesised via the reaction of TiCl4 with AsPh3 (1:1 and 1:2 equivalents), or one equivalent of Ph2AsCH2AsPh2, tBuAsH2 and As(NMe2)3. In general, 1:1 and 1:2 adducts of the type [TiCl4(L)n] (n = 1, L = AsPh3, Ph2AsCH2AsPh2, and tBuAsH2; n = 2, L = AsPh3), were isolated and characterised. However, the reaction of TiCl4 with As(NMe 2)3 resulted in a novel exchange between a Cl and an NMe2 group, yielding the product [TiCl3(NMe 2)(μ-NMe2)2AsCl]. The crystal structure of [TiCl3(NMe2)(μ-NMe2)2AsCl] has been determined and showed that the titanium and arsenic atoms are linked via two bridging NMe2 groups. Additionally, crystal structures for the 1:1 and 1:2 adducts, [TiCl4(AsPh3)] and [TiCl 4(AsPh3)2] have been obtained, with Ti-As bond lengths of 2.7465(13) and 2.7238(7) Å observed respectively. The decomposition of the compounds has been investigated using thermogravimetric analysis, aerosol-assisted and low pressure chemical vapour deposition.
AB - Five titanium arsine compounds have been synthesised via the reaction of TiCl4 with AsPh3 (1:1 and 1:2 equivalents), or one equivalent of Ph2AsCH2AsPh2, tBuAsH2 and As(NMe2)3. In general, 1:1 and 1:2 adducts of the type [TiCl4(L)n] (n = 1, L = AsPh3, Ph2AsCH2AsPh2, and tBuAsH2; n = 2, L = AsPh3), were isolated and characterised. However, the reaction of TiCl4 with As(NMe 2)3 resulted in a novel exchange between a Cl and an NMe2 group, yielding the product [TiCl3(NMe 2)(μ-NMe2)2AsCl]. The crystal structure of [TiCl3(NMe2)(μ-NMe2)2AsCl] has been determined and showed that the titanium and arsenic atoms are linked via two bridging NMe2 groups. Additionally, crystal structures for the 1:1 and 1:2 adducts, [TiCl4(AsPh3)] and [TiCl 4(AsPh3)2] have been obtained, with Ti-As bond lengths of 2.7465(13) and 2.7238(7) Å observed respectively. The decomposition of the compounds has been investigated using thermogravimetric analysis, aerosol-assisted and low pressure chemical vapour deposition.
UR - http://www.scopus.com/inward/record.url?scp=77953482278&partnerID=8YFLogxK
U2 - 10.1039/c001359e
DO - 10.1039/c001359e
M3 - Article
AN - SCOPUS:77953482278
SN - 1477-9226
VL - 39
SP - 5325
EP - 5331
JO - Dalton Transactions
JF - Dalton Transactions
IS - 22
ER -