In:
Zeitschrift für Naturforschung B, Walter de Gruyter GmbH, Vol. 43, No. 11 ( 1988-11-1), p. 1501-1509
Abstract:
The reaction of TiCl 4 with (Me 3 Si) 2 S in dichloromethane yields black, insoluble, impure TiSCl 2 . In the presence of oxygen, additionally Ti 3 O(S 2 )3Cl 4 and Ti 4 O(S 2 ) 4 Cl 6 are formed. By reactions of TiSCl 2 with NEt 4 Cl and PPh 4 Cl in dichloromethane (NEt 4 ) 2 [TiSCl 2 ] and (PPh 4 ) 2 [TiSCl 4 ] · 2 CH 2 Cl 2 are formed, respectively. They were characterized by their IR spectra and by X-ray crystal structure determinations. They contain the square-pyramidal [TiSCl 4 ] 2- ion. which has a rather short Ti = S bond of 211.1(2) pm. Crystal data: (NEt 4 ) 2 [TiSCl 4 ]: tetragonal. P4/n, a = 923.9(3). c = 1406.7(2) pm. Z = 2. 966 unique observed reflexions. R = 0.053; positionally disordered ethyl groups. (PPh 4 )2[TiSCl 4 ] · 2CH 2 Cl 2 : triclinic, P1, a = 1009.7(4), b = 1115.1(3). c = 1242.1(5) pm, α = 70.27(3), β = 79.06(3), γ = 81.37(3)°, Z = 1, 1504 reflexions, β-(AsPh 4 ) 2 UCl 6 ·2CH 2 Cl 2 structure type, high R = 0.107 due to positional disorder of the anion. Addition of NEt 4 Cl or PPh 4 Cl in CH 2 Cl 2 to the primary reaction product in presence of O 2 yields (NEt 4 ) 2 [Ti 3 O(S 2 ) 3 Cl 6 ] and (PPh 4 ) 2 [Ti,O(S 2 ) 3 Cl 6 ] · CH 2 Cl 2 , respectively. Upon recrystallization of the latter from acetonitrile, (PPh 4 ) 2 [Ti 3 O(S 2 ) 3 Cl 6 ] · CH 3 CN is obtained which forms triclinic crystals with a = 1138.8(3). b = 1268.8(4), c = 2166.4(6) pm, α = 101.26(3). β = 97.21(2). γ = 109.24(2)°, Z = 2, P1 (3053 reflexions, R = 0.070). The [Ti 3 O(S 2 ) 3 Cl 6 ] 2- ion has a cluster-like structure with Ti atoms at the vertices of a triangle, with a μ 3 -O bridging atom and with tree bridging disulfide groups. Crystal data for Ti 4 O(S 2 ) 4 Cl 6 : monoclinic, C2/c, a - 917.3(2), b - 1632.5(2), c = 1268.5(2) pm, β - 108.35(2)°, Z = 4. 1009 reflexions. R = 0.027. In the Ti 4 O(S 2 ) 4 Cl 6 molecule, four Ti atoms form a distorted tetrahedron around an μ 4 -O atom; two edges of the tetrahedron are spanned by chloro bridges, four edges by disulfide bridges.
Type of Medium:
Online Resource
ISSN:
1865-7117
,
0932-0776
DOI:
10.1515/znb-1988-1118
Language:
English
Publisher:
Walter de Gruyter GmbH
Publication Date:
1988
detail.hit.zdb_id:
2078109-X
detail.hit.zdb_id:
124635-5
