Synthesis and characterisation of second-generation metallodithiolene complexes of the type [Tp*ME(dithiolene)] (M = Mo, W; E = O, S) and a novel ‘organoscorpionate’ complex of tungsten

Sproules, S. A. , Morgan, H. T., Doonan, C. J., White, J. M. and Young, C. G. (2005) Synthesis and characterisation of second-generation metallodithiolene complexes of the type [Tp*ME(dithiolene)] (M = Mo, W; E = O, S) and a novel ‘organoscorpionate’ complex of tungsten. Dalton Transactions, 2005(21), pp. 3552-3557. (doi: 10.1039/B506050H)

Abstract

Paramagnetic, chalcogenido–M(V) dithiolene complexes, [Tp*ME{S2C2(CO2Me)2}] [M = Mo, E = O (1), S (2); M = W, E = O (3), S (4); Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate] are generated in the reactions of dimethyl acetylenedicarboxylate (DMAC) and the sulfur-rich complexes NEt4[Tp*MoS(S4)] and NEt4[Tp*WS3]; the oxo complexes result from hydrolysis of the initialsulfido products. As well, a novel ‘organoscorpionate’ complex, [W{S2C2(CO2Me)2}{SC2(CO2Me)2–Tp*}] (5), has been isolated from the reactions of NEt4[Tp*WS3] with excess DMAC. Complexes 1, 4 and 5 have been isolated and characterised by microanalytical, mass spectrometric, spectroscopic and (for 4 and 5) X-ray crystallographic techniques. Complexes 2and 3 have been partially characterised by mass spectrometry and IR and EPR spectroscopy. Six-coordinate, distorted-octahedral 4 contains a terminal sulfido ligand (W S = 2.108(3) Å), a bidentate dithiolene ligand (S–Cav = 1.758 Å, C C = 1.332(10) Å) and a fac-tridentate Tp* ligand. Seven-coordinate 5 contains a planar, bidentate dithiolene ligand (S–Cav = 1.746 Å, C C = 1.359(5) Å) and a novel pentadentate ‘organoscorpionate’ ligand formed by the melding of DMAC, sulfido and trispyrazolylborate units. The latter is coordinated through two pyrazolyl N atoms (κ2-N,N′) and a tridentate κ3-S,C,C′ unit appended to N-β of the third (uncoordinated) pyrazolyl group. The second-generation [Tp*ME(dithiolene)] complexes represent a refinement on first-generation [Tp*ME(arene-1,2-dithiolate)] complexes and their synthesis affords an opportunity to compare and contrast the electronic structures of true vs. pseudo-dithioleneligands in otherwise analogous complexes.

• Item Type: Articles
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Sproules, Dr Stephen
• Authors: Sproules, S. A., Morgan, H. T., Doonan, C. J., White, J. M., and Young, C. G.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Dalton Transactions
• Publisher: Royal Society of Chemistry
• ISSN: 1477-9226
• ISSN (Online): 1477-9234