SYNTHESIS AND STRUCTURE OF TITANIUM TETRATHIOLATE AND TANTALUM PENTATHIOLATE COMPLEXES - METAL SULFUR BONDING IN EARLY TRANSITION-METAL COMPOUNDS | Health & Environmental Research Online (HERO)

HERO ID

1753013

Reference Type

Journal Article

Title

SYNTHESIS AND STRUCTURE OF TITANIUM TETRATHIOLATE AND TANTALUM PENTATHIOLATE COMPLEXES - METAL SULFUR BONDING IN EARLY TRANSITION-METAL COMPOUNDS

Author(s)

Corwin, DT; Corning, JF; Koch, SA; Millar, M

Year

1995

Is Peer Reviewed?

1

Journal

Inorganica Chimica Acta
ISSN: 0020-1693
EISSN: 1873-3255

Publisher

ELSEVIER SCIENCE SA LAUSANNE

Location

LAUSANNE 1

Volume

229

Issue

1-2

Page Numbers

335-342

Language

English

DOI

10.1016/0020-1693(94)04263-U

Web of Science Id

WOS:A1995QN47500045

Abstract

The reaction of TiCl4 with potassium 2,3,5,6 tetramethylbenzenethiolate (KS-2,3,5,6-Me(4)C(6)H) in THF gives [Ti(S-2,3,5,6-Me(4)C(6)H)(4)] (1)
in 50% yield. Compound 1 crystallizes in the triclinic space group with a =
11.666(4), b = 19.417(5), c = 8.916(7) Angstrom, alpha = 97.09(2), beta = 110.30(2), gamma =
87.95(3)degrees, V = 1880(3) Angstrom(3), Z = 2. The monomeric [Ti(S-2,3,5,6-Me(4)C(6)H)(4)] has
a distorted tetrahedral structure with Ti-S bonds of 2.292(6) Angstrom. One of the thiolate
groups has a very acute M-S-C angle of 86.5(5)degrees. The reaction of TaCl5 with excess (LiS-
2,3,5,6-Me(4)C(6)H) in hexane gives [Ta(S-2,3,5,6-Me(4)C(6)H)(5)] (2). Compound 2 crystallizes in
the triclinic space group, with a = 11.165(9), b = 11.890(5), c = 18.675(11)
Angstrom, alpha = 90.87(4), beta = 101.83(6), gamma = 96.77(5)degrees, V = 2407(5) Angstrom(3)
with Z = 2. [Ta(S-2,3,5,6-Me(4)C(6)H)(5)] is a monomeric compound with a distorted five-
coordinate geometry. The average Ta-S bond distance is 2.37(3) Angstrom and TaS-C-av angle is
116(7)degrees. structural comparisons of 1 and 2 with analogous phenolate complexes reveal large
values for Delta[(MS)-(M-O)]. The extent of the S to M pi-bonding in these electron deficient
early transition metal thiolates is considerably reduced compared to the O to M pi-bonding in
phenolate analogs. The observation of the acute Ti-S-C angles suggests that the limited thiolate
metal pi-bonding in 1 can not compensate for the strong electron deficiency of the Ti(IV)
center.

Keywords

CRYSTAL STRUCTURES; TITANIUM COMPLEXES; TANTALUM COMPLEXES; THIOLATE COMPLEXES